Sunny Cottage Holidays (SCH) Assignment Example | Topics and Well Written Essays - 1500 words

Radiant Cottage Holidays (SCH) - Assignment Example Cabin proprietors then again publicize with SCH dependent on the brand picture of the operator, trust and solace levels they appreciate with the organization. The office necessitates that advertising and correspondence systems be utilized keeping the accompanying standards in see. Transient correspondence destinations †¢The target portion of SCH is in different phases of various leveled reactions. Correspondence procedure must be utilized to initially make and increment mindfulness about cabin occasions as opposed to general occasions and brand mindfulness on the SCH bundle. This must be done through appealing publicizing methodology, great media arranging and limited time works out. Separation among SCH and its rivals must be plainly indicated. †¢Next the organization must concentrate on giving more data on SCH to the client. The ‘comprehension’ stage ought to permit improvement of site, direct mailers and so forth that gives data about the occasion bundles. †¢Endorsements by specialists or input photographs and remarks from fulfilled SCH clients are different instruments that the office can investigate to persuade clients. Conviction must be the third significant phase of the activity. †¢Desire to buy must be created through a solid limited time blend that incorporates great exposure and overwhelming proposals for the objective section. †¢Finally the crusade must inspire clients without hesitation which can be estimated by number of calls/messages questioning about the bundles. Criticism structures and fortunate coupons are different alternatives. The market and rivalry The market for free family occasions in bungalows is quickly developing, the same number of favor 'their space' as opposed to being a piece of a gathering. A developing 58% individuals incline toward the escape to the wide open for loosening up ends of the week and arranged get-aways. The opposition can be delegated, Neighborhood masters: Most bungalow operators are nearby pros who center around voyagers coming to explicit pieces of UK. For instance, the Wales bungalow occasions office in Wales has a far reaching posting of occasion houses in all pieces of Wales. Its site and pamphlet are its principle publicizing munititions stockpile. Other such region explicit cabin specialists incorporate Cumbria bungalows (the Lake locale), Classic Cottages (for Devon and Cornwall), Mann's Holidays (North West Wales), Nefyn Holidays (Lleyn Peninsula and Snowdonia National Park), Marsdens Cottage Holidays (North Devon) and Holiday Homes and Cottages (South West). Their primary medium is a hued leaflet which is regularly sent to clients. General experts: A little portion of general masters offer occasions across UK. For instance, Recommended bungalow occasions office offers a scope of houses across UK. It has a hued leaflet that rundowns the different cabins and a site that permits clients to check accessibility and reserve a spot. Its primary objective market is huge families and spotlights on family/corporate reunions. It advances itself as a prudent occasion supplier that offers a decent range. Other UK cabin occasion suppliers incorporate names of Hoseasons Holidays (entrenched and offers an incredible range) and Sykes houses. The objective market: clients Rather than settling on mass advertising, the organization must attempt target showcasing and must shape at least one market fragments applicable to purchasing conduct. The sub gatherings or specialty advertises inside its distinguished objective sections can be recognized as under. Geographic and Demographic division: Customers are normally couples matured 25 onwards

Barbara Kruger Contemporary Art Essay Example | Topics and Well Written Essays - 750 words

Barbara Kruger Contemporary Art - Essay Example The paper Barbara Kruger Contemporary Art discusses the Contemporary Art of Barbara Kruger. For example, in Your Body is a Battleground, Kruger picks a typical text style, which is emphatically stressed against a to some degree monochromatic photograph of an appealing lady. Be that as it may, in this specific work, the lady delineated in the photograph is divided into halves, with the left half of her face displaying a ruddy shaded, fairly positive appearance. The correct side of the subject's face is concealed, in a to some degree clouded light, with the craftsman utilizing an assortment of antiquing procedures to add further accentuation to the message Kruger is endeavoring to hand-off. Further, it is essential to recognize what explicit message is endeavoring to be sent in this banner picture titled Your Body is a Battleground. It is imperative to understand that during the last bit of the 1980's, respectful agitation and worldwide requests for freedom were being heard far and wid e. From the fall of the Berlin Wall to radical changes in women's liberation and ladies' privileges, it is no big surprise why Kruger decided to mix contemporary symbolism and the composed word (as a rule utilizing red as the textual style shade of decision) to show the torment, enduring, delight, and through and through unpredictability of being a lady in present day times. Having offered this, a few people seeing Kruger's fine art may think of her as endeavors at communicating woman's rights as being fairly freakish because of its effortlessness. Be that as it may, utilizing basic materials, for example, photography, words, and composition propelled plans.

Lord of the Flies William Golding Free Essays

string(31) essential concentration for that group. William Golding once said that, â€Å"the state of a general public must rely upon the moral idea of the individual and not on any political framework anyway obviously consistent or respectable† (186). He accepts that issues with society can be followed â€Å"back to the deformities of human nature† (186). In Lord of the Flies, Golding utilizes two young men from the generally socially inflexible nation of England to show the possibility that, whenever left unchecked, the carnal nature that dwells profound inside the hearts of individuals will defeat society’s rules and mores. We will compose a custom article test on Master of the Flies: William Golding or on the other hand any comparable theme just for you Request Now The characters in the novel are left to their own gadgets on a uninhabited island and must frame their own political framework. The genuine moral nature of the young men, delegate of people when all is said in done, turns out to be progressively perceptible over the long haul. Ralph is the case of development and majority rules system while Jack is the encapsulation of viciousness and creature conduct. The tale opens with a scene of two little youngsters on an island after a plane accident in the ocean. These young men, Ralph and Piggy, advance over the secluded island and locate a little pool of warm water close to an enormous, pink stone. After they discover a conch, Ralph blows into it; the clamor draws young men from everywhere throughout the island who are likewise casualties of the plane accident. The significant characters incorporate Jack, the pioneer of the ensemble, just as Sam, Eric, Simon and Roger. After an underlying gathering, the young men conclude that their gathering ought to have a pioneer, despite the fact that this is all the more a game than a methods for association: â€Å"This toy of casting a ballot was nearly as satisfying as the conch† (22). The conch and the arrangement of casting a ballot are the two remainders of the English society the young men occupied. Ralph routs Jack after a vote, yet Ralph places the ensemble, under the oversight of Jack, accountable for chasing. It is clear all through the novel, in any case, that this token position doesn't fulfill Jack and that he needs to get boss. At first, in any case, Jack says that â€Å"[he] agree[s] with Ralph. Very quickly, the initiative is assailed by a little kid who professes to have seen a nightmarish Beast. Ralph starts by guaranteeing him that such a Beast doesn't exist, however the little fellow demands that the Beast is genuine and requests o know when it will return. Jack intrudes on Ralph to tell the kid, â€Å"There isn’t a snake thing . . . be that as it may, if there was a snake we’d chase and slaughter it. We’re going to chase . . . what's more, we’ll search for the snake too †â€Å"(36). Ralph is â€Å"annoyed and . . . defeated† (37) by Jack’s usurpation of his power and is at a misfortune regarding how to manage it. F or the occasion, the gathering of young men trusts that the pendulum of power will swing somehow. It happens to swing in Ralph’s favor as he guarantees the young men that they will be protected. They accept his case, â€Å"unbacked by any confirmation yet the heaviness of Ralph’s new authority† (37), and he finds that the get together â€Å"liked and now regarded him† (37). Jack, in any case, only grins and applauds pitifully. One of the most piercing instances of the leftovers of human progress happens when a kid named Roger starts to toss rocks at a little youngster named Henry building sand palaces. He tosses stones, however deliberately misses, in light of the fact that, â€Å"there was a space round Henry, maybe 6 yards in distance across, in which he dare not toss. Here, imperceptible yet solid, was the no-no of the old life† (56). Significantly after his long time away from grown-ups, he is still socially adapted to abstain from hurting others. In any case, this human progress was declining quickly: â€Å"Roger’s arm was adapted by a development that†¦ was in ruins† (56). The decay of civilization’s hold is unnoticed by Ralph; he becomes focused on the fire that is worked to draw in the consideration of any close by boats or planes. Empowered by Piggy, Ralph feels that â€Å"the fire is the principle thing† (102) and demands that a sign fire be kept up consistently. Ralph centers around an arrival to human advancement and ordinariness. Jack, in any case, centers around living by impulse †chasing pigs turns into his fixation. He has a bloodlust: â€Å"He attempted to pass on the impulse to find and slaughter that was gulping him up† (51). He is more than substance to live on the island, without human advancement; he is glad to do as such. The two young men contrast on the issue of government, too. Ralph demands a majority rules system and permits the gathering to decide on specific issues. All young men are permitted to talk at gatherings in the event that they have a psyche to do as such; a conch found toward the start of the novel is held by a kid when he wishes to address the gathering. This is maybe probably the most grounded leftover of his time in acculturated England: the conviction that all individuals merit portrayal, paying little mind to their capacities. Jack, nonetheless, embraces all the more a tyrant like mentality, as represented when he says to Ralph, â€Å"It’s time a few people knew they’ve got the opportunity to stay silent and leave concluding things to the remainder of us† (102). He represents the possibility that the solid endure, so the most grounded must oversee. Ralph and Jack have a kind of common regard for one another, however they are altogether different and don't know precisely how to manage each other. They strolled along, two landmasses of experience and feeling, incapable to communicate†¦ They took a gander at one another, astounded, in affection and hate† (55). Jack is envious of Ralph’s position as boss, in any case, and after a long gathering during which Ralph put forward new guidelines for t he gathering, Jack leaves and starts his own clan. Since Jack and his first class friend network can chase and get meat, huge numbers of the young men join his clan. Just Sam, Eric, Simon, Piggy and Ralph stay in the edified gathering on the sea shore. After the greater part of the young men join Jack’s â€Å"tribe,† chasing turns into the essential concentration for that gathering. You read Ruler of the Flies: William Golding in class Papers They invest a lot of their energy chasing and this gives fervor and diversion to the young men: â€Å"[T]he sow stunned her way in front of the, draining and frantic, and the trackers followed, married to her in desire, energized by the long pursue and the dropped blood† (135). After this executing, Jack orders Roger to â€Å"[s]harpen a stick on both ends† (136), at that point continues to push one finish of the stick into the ground. On the opposite end, he pushes the leader of the pig and says, â€Å"This head is for the brute. It’s a gift† (137). This twisted demonstration gives the clarification to the Beast when a kid named Simon finds a pig’s head on a stick in the backwoods. Simon has a kind of insane scene where the pig’s head †who is alluded to as â€Å"the Lord of the Flies† (138) †addresses him. The Lord of the Flies says, I’m the Beast. Extravagant reasoning the Beast was something you could chase and execute! You knew, didn’t you? I’m part of you? Close, close, close! I’m the motivation behind why it’s no go? Why things are how they are? We will have a great time on this island! (143-144) The Beast isn't some creature that vanished toward the beginning of the day, turning â€Å"into them things like ropes in the trees† (36). Or maybe, the Beast is the creature nature inside all people, essentially hanging tight for an opportunity to get away. This bestial conduct isn't constrained to the unwarrantedly ridiculous and practically formal killings of the pigs. After Simon â€Å"listens† to the Lord of the Flies, he puts the leader of the butchered sow onto his head. The deranged youngster realizes that he is accomplishing something unusual: â€Å"He realized that one of his occasions was coming on† (143). Simon keeps on hearing the voice of the Lord of the Flies as he covers his head with that of the dead pig. The voice gives an anticipating to the occasions that will before long follow when he attempts to terrify the kid by saying, â€Å"We will have some good times on this island. Get it? We will have a ton of fun on this island! So don’t attempt [the head] on, my poor confused kid, or else†¦ Or else we will isn't that right? Do you. Could it be any more obvious? † (144) The kid crumples and awakens after he gets a nosebleed: â€Å"With the running of the blood Simon’s fit went into the exhaustion of sleep† (145). His fit, be that as it may, doesn't leave him without counsel, since now he realizes that the â€Å"beast was innocuous and unpleasant; and the news must arrive at the others at the earliest opportunity. † This last smidgen of trust in the humankind of the island, realized by the crazy scene of a little fellow, never arrives at the young men. At this point, Ralph and Piggy dare to Jack’s clan to appreciate some meat. A little contention among Ralph and Jack results and Jack chooses to have the clan do their â€Å"dance† as an approach to show his capacity and the pleasant that the young men in the clan have. Roger plays a pig and different young men claim to assault him. A serenade rises: â€Å"Kill the mammoth! Cut his throat! Violate his wellbeing! † (152) Suddenly a voice shouts out, â€Å"Him! Him! † (152) and Simon bumbles out of the woods, canvassed in pig’s blood just as his own. He frantically attempts to pass on the importance of the Beast to the young men gathered, â€Å"crying out something about a dead man on a hill,† however the young men drop upon him in lethal satisfaction. To those youngsters, Simon is the mammoth: â€Å"The brute was on its knees in the middle, its arms collapsed over its face. It was shouting out against the loathsome clamor something about a body on the slope. † Delighted by the possibility of devastating the Beast, â€Å"the swarm flooded after it, poured down the stone, jumped on to the monster, shouted,

Does God Exist And Where Can I free essay sample

Discover Him? Exposition, Research Paper God. The way that you are perusing this proposes you are at any rate mostly loosened to His being and detached to larning more. Provided that this is true, so this paper is for you. I need you to cognize that God is existent and that God adores you. Does God be and if so where is He # 8211 ; where would he be able to be found? As far as I can tell this is the request that numerous individuals are asking today. At a similar clasp numerous individuals have gotten to the heart of the matter in their lives where they have genuine vulnerabilities about God # 8211 ; or have just denied His being. Of class many have attempted to # 8220 ; turn out # 8221 ; God # 8217 ; s being with judicious explanations. Aquinas, Abelard, Anselm, Pascal, and Paley are a not many that have endeavored this. These assaults are of restricted support, for however we can approach God with our ground and watch Him in nature, He can non be to the full gotten a handle on as such. All the more fundamentally, these intelligent # 8220 ; proofs # 8221 ; for God # 8217 ; s being overlook the main issue. What is the point? I would say, a large portion of the individuals who question or deny God # 8217 ; s being, do non make so due to unfalteringly held philosophical solid convictions. They do so as a result of individual frustration with God. Besides, I # 8217 ; m suggesting that a considerable lot of the individuals who presently see themselves as questioning or denying God for philosophical grounds, got where they are on the grounds that they turned out to be by and by baffled with God at some point in the days of old. Individual Disappointment with God What kind of close to home setback? Dissatisfaction like unreciprocated petition. Numerous in close to home emergency have shouted out to God in request. They have shouted to Him for help. In any case, the guide they were searching for did non come. People groups like Frank from the Paralyzed Veterans Association, who called me for a commitment. As we talked he started offering a portion of his business to me via telephone. At the point when I disclosed to him I would petition God for him, he irately reacted, # 8220 ; Please wear # 8217 ; t. I # 8217 ; ve abandoned that person. # 8221 ; He had supplicated commonly however neer got the answer he anticipated. As an outcome he presently severely questions God # 8211 ; His being, His capacity, His affection. Others have been disillusioned or harmed by the individuals who speak to God. Sooner or later in the days of old they were disillusioned or harmed by an otherworldly pioneer or part. They were mishandled in some way, potentially, or given awful supporter, or censured. They were on the right track to foresee better conduct from the individuals who speak to God. Such awful mediation crushed and throb them ; and it drove them to question or deny God. They contemplated, # 8220 ; If God permits, for example, these to work Him, what kind of God right? Conceivably He doesn # 8217 ; t care by any stretch of the imagination. Perhaps He isn # 8217 ; t genuine. # 8221 ; Still others have been overpowered by the shamelessness and desolation of this universe. For some in this gathering this indecency and distress has contacted them by and by and as often as possible. Catastrophe has discovered them. Or then again they have been merciless treated by others. The rest of and hear it surrounding them. Savagery, abuse, need, sickness, and deficiency. Common calamities like fire, immersion, air current, and quake. Everything that debase and downgrade life. These individuals wonder, # 8220 ; How could an omnipotent and all-cherishing God permit such things? # 8221 ; They infer that it is questionable that such a God exists. Or then again # 8220 ; If He does, # 8221 ; they state, # 8220 ; I wear # 8217 ; t need to cognize Him. # 8221 ; In reconsidering these individual situations, I # 8217 ; m asking doubters and deniers for soul-looking through honestness. I # 8217 ; m asking that they be straightforward and lucid regarding why they presently question or deny God # 8217 ; s being. In all occasions, the individuals who question or deny God # 8217 ; s being a direct result of individual setback do so in light of the fact that God did non execute orchestrating to their viewpoints. Be that as it may, I would ask such individuals ( potentially you ) : Are you willing to in any event observe the likelihood that your viewpoints of God are or were in botch? You who shouted out in petition with no obvious answer. Might it be able to be that God did answer for your great, yet non in the way you anticipated? Or then again might it be able to be that the acceptable answer you were searching for didn # 8217 ; t come in light of the fact that there was something different in your life that was non right, that should have been tidied up and changed? Or on the other hand would it be able to be that you are non directly with God and you are searching for favors from Him before you are directly with Him? You who have been disillusioned or harmed by the individuals who speak to God, would you say you were really injured or was it in perceptual experience just? In the event that you were really harmed by those stand foring God, they were wrong to throb you and I am significantly remorseful that you were harmed. In any case, is it option to question or deny God in light of the fact that the individuals who speak to Him substantiate themselves wrongdoers? Might it be able to non be that God is saddening over this much more than you? You who have been moved by the unethical behavior and distress of this universe, you are non completely. We all at some clasp have been. However, requests should be replied. Did you pass on this unethical behavior and suffering upon yourself by confused judgments that you unreservedly made? Assuming this is the case, is it option to blame God for this, or to question or deny Him? Regardless of whether the shamelessness and distress happened upon you guiltlessly, is it option to question or prevent God in light of the fact that from claiming it? Could the underhandedness non hold another reason? Conceivably you state, # 8220 ; How could a caring God permit such indecency? # 8221 ; But is it God # 8217 ; s love that is broken or your anxiety of it? Most religions evenhandedly encourage that it was humankind that infused abhorrent into the request for things that despite everything are shooting it. God did non make or mean malice. We have welcomed it on ourselves. However, indeed, it is valid: Supreme being lets the corruption known to mankind to go on. Is it option to reason from this that subsequently God is non all-powerful or all-cherishing? Would it be able to be that He has decided to give His capacity and love in another and substantially more incredible way? Also, this God has done ; and He has made this affection and force accessible to all who realize where to look! Increasingly about this underneath. The individuals Who Doubt or Deny God for Philosophical Reasons Presently it other than evident that there are some who do question or deny God # 8217 ; s being a direct result of philosophical grounds. They question or deny God in light of the fact that their perspective does non go forward space for an individual God. Every one of those whose perspective is # 8220 ; shut # 8221 ; fall into this class. By # 8220 ; shut # 8221 ; I mean a perspective that sees the presence as a shut framework, that works blending to perpetual Torahs, permits no outside mediation, and can be seen simply by ground and the faculties. Such a perspective does non let for strict presences or anything brilliant. Into this class travel naturalists, mainstream humanists, cynics, skeptics, and numerous evolutionists. However I am persuaded there is something different in the perspective of numerous # 8220 ; shut universe # 8221 ; advocates that rules out an individual God. I am recommending that this # 8220 ; something different # 8221 ; is an unquestionably all the more noteworthy ground with regards to why their perspective doesn # 8217 ; Ts leave space for God. To recognize to the being of an individual God is to recognize that I should answer to Him, that my life is responsible to Him, and that I should obey Him. To recognize that this individual God exists implies that I so should turn over an amazing reins to Him. Numerous individuals by and by decline to concede the being ( or possibly the assurance ) of an individual God since they do non want such answerability, respect, or control! Outright close to home freedom and opportunity is their guiding principle. They will non let anybody or anything to possess this core esteem. It is this reality that attracts numerous individuals to the varying generic # 8220 ; Gods # 8221 ; that by and by exist. America Online late advanced another book by Deepak Chopra, # 8220 ; Seven Spiritual Laws for Parents. # 8221 ; This Random House book is an aftereffect to a prior book, â€Å"Seven Spiritual Laws, † that the essayist claims brought expansive congrats. Thousands reached him to express gratitude toward him. In the two books Chopra talks about â€Å"God† and â€Å"Nature† as all-infesting and extremely generic Torahs in the presence that request things. The key to life, he asserts, is to cognize these Torahs. Notice that in his framework, â€Å"God† is non an individual being, yet an indifferent arrangement of Torahs. The ground that 1000s are attracted to a book about an unoriginal # 8220 ; god # 8221 ; is a similar ground that such a large number of who question or deny an individual God are attracted to # 8220 ; spiritualty # 8221 ; and # 8220 ; heavenly attendants. # 8221 ; You wear # 8217 ; Ts need to answer to a generic God, or a holy messenger, or to spiritualty. One can benefit from outside intervention by them without considering to be responsible or devoted to them. Supreme individual freedom is less undermined by an indifferent God than an individual One. So the existent request is non, # 8220 ; Is the entire impression of God experimentally conceivable or certifiable? # 8221 ; I am recommending that the existent request for the vast majority is, # 8220 ; Am I ready to set aside past disappointments and show signs of improvement of my fear of losing individual freedom so I can cognize God? # 8221 ; God is Real # 8211 ; Here is How to Find Him Cherished peruser, God is existent and needs you to cognize Him by and by. Be that as it may, where do we happen Him? We discover God in Jesus Christ. We can cognize that there is a God, and what god's identity is, on the grounds that the imperishable God entered history and presented Himself by and by through Jesus Christ. Jesus Christ is God made seeable. Jesus Christ is the answer to the request, # 8220 ; What is God like? # 8221 ; Jesus Christ is God # 8217 ; s way of expressing, # 8220 ; I am existent. I love you. I am God for you. # 8221 ; Jesus is God # 8217 ; s extreme divulgence of Himself to humankind. Jesu

32 Proven Ways to Make Money Fast

32 Proven Ways to Make Money Fast Ever feel your job isn’t paying you enough to afford a vacation for yourself?While your job is the primary source of employment that pays the bills and meets the mortgages â€" what about the inner desires that arise frequently? How do you satisfy them?By coming up with a quick strategy to make money when you aren’t working your day shift.Extra money is always a good thing to have â€" you can open a savings account, you can plan a vacation, you can gift your lovely spouse a surprise gift, or you can buy yourself something you’ve always wanted.THE RIGHT ATTITUDE THAT IS REQUIRED FOR MAKING A QUICK BUCKMaking quick money isn’t as easy as it sounds or everyone in the world would be doing it.The success of making money fast requires 3 factors â€" patience, a plan, and consistency.Fast money is something the modern individual looks forward to but doesn’t come up with a plan to make it. The below methods usually require a keen sense of mind and a laptop with a working internet con nection to get you started in the money-making business.Ever hear of a get-rich-quick scheme from a friend?This is one of the best ways to fall prey to the many internet scams that usually charge a small upfront fee for you to be rolling in millions.Don’t fall for this trick!Making money legitimately isn’t necessarily hard but requires some amount of patience and the right mindset.As an individual, question yourself how much you need the money to stay afloat and how much an extra job on the side will help you reach your goals.Once you’ve determined this, you proceed by setting your ego down and come to terms that not all jobs are well-respected.Let’s take driving, for example, you may be a software professional with your ethics and driving a car may not really be ethical for you to perform.Once you’ve set down your ego, you can proceed to earn those extra bucks and live a much happier life knowing you can afford the things in life that you seek instead of complaining how b ad your software job pays.Hence, keeping these factors in mind the following 32 strategies are some of the best ways to make a quick buck on the side.32 EFFICIENT WAYS TO MAKE LUCRATIVE PROFITS1. Trade Old Books on AmazonAmazon is a convenient shopping destination known globally for listing various kinds of items.If you’ve got old books lying around in the house that you no longer read, a good idea is to sell them to people that might be interested in reading them.Old books also have a collector’s value, so ensure you establish the worth of the book before you list your product on Amazon.College books or educational books that you no longer have any use for are always required by students studying for their exams.By simply listing your books online, you make a good amount of profit in no time.2. Gardening ServicesIf you live in a suburban neighborhood or have plenty of homes with lawns around, you could work as a local gardener during the weekends to earn some extra bucks.Every home with a lawn requires management such as mowing the grass and pulling out weeds. These tasks aren’t complicated and it’s easy to pick up and learn.Go door-to-door to inquire and once you’ve got a few homes ready to hire you as a local gardener, you can quickly setup a part-time gardening business to add in more profits.3. BloggingBlogging is a popular means to earn extra income on the side.All you need is a domain name and website hosting from one of the top providers â€" Bluehost, In Motion, HostGator, etc. Several providers usually offer a discount on a 1-year or 2-year hosting plan, so the longer duration you purchase the better your savings.Once you’ve got a hosting provider and your preferred domain name, simply start blogging about your favorite topic and after you’ve gained enough readers, you can start to make income through the sale of your products or advertising through Google AdSense.Although this money-making method isn’t instant, it’s a great way to e arn passive income for life once you’ve got a well-written list of articles. 4. Gigs on FiverrFiverr is a popular website to sell your professional services such as graphic designing, web development, content writing, virtual assistant, etc.Fiverr provides you with an easy platform to reach your clients and host plenty of plans to set up your business. It’s a great way to have a job apart from your real job.Many freelancers have a full-time working career on Fiverr by doing gigs. There are absolutely no fees to join Fiverr and it’s completely free. Gaining clients isn’t hard on Fiverr with the right profile and portfolio set up.5. Babysitting with Care.comBabysitting is a popular part-time job especially for students looking to earn while studying. Parents are always on the lookout for a nanny that can ensure protection and provide the right care for their little tyke.You can sign up at Care.com as a babysitter and provide all your details so the company can check if you are indeed the right fit for a caretaker.Babysitting can also be conducted directly by approaching households and inquiring if they need a caretaker to look after their kid. You can start with your neighborhood. 6. Drive for Uber or LyftDriving doesn’t have to be a full-time profession, you can do it during the weekends or when you feel like taking your car out for a spin.Driving for companies such as Uber and Lyft can be a great opportunity to make some extra dough after your office hours. Driving can be a relaxing activity and all you have to do is ensure your passenger reaches their destination on time.Few things to keep in mind while drivingEnsure you maintain the speed limitIf the passenger turns up late don’t argue, instead raise a complaint to the company via an app7. Teach a Course on UdemyIf you’ve had a dream to teach individuals but never had the opportunity to join a university, why not start a course on Udemy?All you need is a laptop or desktop to get started along w ith a screen recording software and a working microphone. With this set up you can make as many educative courses as you want and upload them to Udemy.Every time a student is interested in learning a course from you, they buy your tutorials and you end up taking a share of the profits.You don’t have to be an expert at teaching a course but some knowledge in a specific subject is necessary.For example â€" You could teach basic grammar punctuation for foreign students looking to learn English.8. Rent out your spaceMany households usually have a spare room that is never used.  If you have one, this is your chance to earn quick money by opening up a lodging space on websites such as Airbnb or HomeAway.To make the lodging more hospitable, you can offer a free breakfast and free wi-fi during the guest’s stay to attract more visitors.Lodging is a great way to earn extra money without having to invest much. You could also provide maps and other useful tourist requirements for making a few extra bucks on the side.9. Sell PhotosMaking money while selling high-quality photographs is an exceptional income tactic and lets you start a passive income business.Websites such as Shutterstock and iStock Photo offer royalty schemes where if a buyer were to purchase your photos, you earn a percentage of the profits.In this way, you can click photos during the weekend and upload them to the following websites and end up making money while you work on the weekdays.You can also act as a part-time wedding photographer during the weekends.The first thing that you need to invest in is a professional camera that can click high-quality photographs to impress your clients.10. Housecleaning ServicesAmazon’s Home Services is a great platform to find house cleaning jobs that involve tasks such as cleaning bedrooms, painting, scrubbing window panes and many house-related jobs.Housecleaning services can be done on weekends or holidays as an extra source of quick income.You can also perfo rm housecleaning services in your neighborhood by inquiring door-to-door. You can earn up to $30 per hour by cleaning up homes.Another great way is by creating your own personal website and advertising your housecleaning services. 11. Personal Training sessionsFitness is an industry that is growing by the hour and lots of newbie fitness enthusiasts need a trainer to teach them the ropes.Being a personal trainer during your off-work hours is a great way to earn money and also to keep yourself in a healthy and fit shape.Services such as Fitness Trainer is a great method to advertise your personal training services along with your prices.You will need a certification course before you can pursue training but once you invest in gaining one, you can gain a healthy way of making your side income.12. Become a Dog Walker on RoverNot all pet lovers have the time to take their pooches for a walk every day.In these cases, a dog walker is assigned to take a bunch of dogs from a neighborhood and bring them back home safely. 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Supercritical Fluids - Free Essay Example

I. ABSTRACT (ENGLISH) The experimental determination of the yield of pyrethrins from the Chrysanthemum cinerariaefolium flower is usually carried out with Chromatographic Techniques. A lot of methods about this have been reported over the years [Z-M. ChertY.H. Wang (1996)]. These include HPLC [13 -22], GC [22-26] and SFC [B. Wenclawiak, A. Otterbach (2000) methods. Because of the need for only analyzing the pyrethrins (not reporting for the individual six pyrethrins but analyzing for total pyrethrins), GC was selected as a method of choice. The yield reported from literature usually ranges from 0.91 1.30% of the dry weight [Kolak et al., 1999], 0.60 0.79% [Bakari (2005)], 0.75 1.04% [Bhat (1995)], 1.80 2.50% [Morris et al. (2005), Bhat and Menary, (1984); Fulton, (1999)], 0.50 2.0% [Kiriamiti et al. (2003)], and 0.90 1.50% [Pandita and Sharma (1990)]. However, Casida and Quistad (1995) in their book: Pyrethrum Flowers: Production, Chemistry, Toxicology and Uses (pp123-193), states that it is possible to obtain pyrethrin yield of 3.0% or even more. We obtained, with hexane extraction in a water bath at controlled temperatures and vigorous stirring (with three magnetic stirrers at a speed of 30rpm); pyrethrin yields varying from 0.85 3.76% of the dry weight. To our knowledge, this is the first time to report of pyrethrins yield above 3% envisaged by Casida and Quistad. Key words: Supercritical Fluid Extraction, Supercritical Carbon Dioxide, Pyrethrins, Solvent extraction, Extraction Yield, Gas Chromatography, Pyrethrin concrete, Crude Hexane Extract. III. ABBREVIATIONS AND SYMBOLS GC Gas Chromatography HPLC High Performance Liquid Chromatography SFC Supercritical Fluid Chromatography SCF Supercritical Fluid SCFs Supercritical Fluids SFE Supercritical Fluid Extraction SC-CO2 Supercritical Carbon Dioxide SC Supercritical CO2 Carbon Dioxide et al et alii (and others) pp page % percentage CHE crude hexane extracts BC Before Christ PY pyrethrin PYI pyrethrin 1 PYII pyrethrin 2 C1 cinerin 1 C2 cinerin 2 J1 Jasmolin 1 J2 Jasmolin 2 P1 pyrethrin 1 P2 Pyrethrin 2 A1 area of pyrethrins 1 A2 area of pyrethrins 2 WHO world health organization Fig Pc critical pressure Tc critical Temperature Cp critical point Cm centimeters ~ Approximately oC degree centigrade MPa mega Pascal FID flame ionization detector n-hexane normal hexane mL milliliters /min per minute Soc. Society Eds editions Sci. Science m meters mm millimeters tR retention time k Retention factor R2 Pearson correlation coefficient LOQ limit of quantification LOL limit of linearity LOD limit of detection BOD beyond limit of detection IS internal standard k response factor f relative response factor m micro meters L micro liters rpm revolutions per minute 1.0. CHAPTER 1: Introduction and Literature Review 1.1.0 Supercritical Fluids (SCF) When a fluid is forced to a pressure and temperature above its critical point (Fig. 1), it becomes a supercritical fluid. Under these conditions, various properties of the fluid are placed between those of a gas and those of a liquid. The supercritical state of a fluid is thus defined as one whose liquid and gas are indistinguishable from each other, or one in which the fluid is compressible (i.e. behaves as a gas) while having a density similar to a liquid and, therefore, similar solvating power. Their low viscosity and relatively high diffusivity gives them better transport properties than liquids, can diffuses easily through solid materials and hence faster and better extraction yields. The most important properties of a SCF are its density, viscosity, diffusivity, heat capacity and thermal conductivity. Higher densities of SCFs contribute to greater solubilization of compounds, while low viscosities enable Easy penetration into solids and facilitate flow with fewer hindrances. Manipulating the temperature and pressure above the critical points affects the properties of SCFs and enhances their ability to penetrate and extract targeted molecules from the source materials [1]. Since density is directly related to solubility, by altering the extraction pressure, the solvent strength of the fluid can be modified to exhibit desirable transport properties that enhance its adaptability as a solvent for liquid extraction processes. The density of a SCF is closer to that of liquids and its viscosity is comparable with gases, hence high diffusivity and faster dissolution of solute particles (the diffusivity of SCFs is ~10-4 cm2 s-1 while that of liquid solvents is ~10-5 cm2 s-1). This has contributed to the increasing use of SCF as solvents for extraction purposes. 1.2.0 Supercritical Fluid Extraction (SFE) Supercritical Fluid Extraction (SFE) is a separation technology that uses supercritical fluid as the solvent. Every fluid is characterized by a critical point, which is defined in terms of the critical temperature and critical pressure. Fluids cannot be liquefied above the critical temperature regardless of the pressure applied, but may reach a density close to the liquid state as mentioned earlier. The consumer and public awareness of the health, environmental and safety issues emanating from organic solvents use in chemical processes and above all, the possibility of contaminating the final products with the solvent are forces to reckon with in recent times. This has driven the chemical industry looking for the best separation technologies to obtain natural compounds from high purity and healthy products that are of excellent quality [2]. The high cost of organic solvents, environmental regulations, and new requirements in the medical fields, for all time purer and highly valuable products have also revitalized the need for the development of new but clean technologies for products processing [3]. 1.3.0 Supercritical Carbon Dioxide (SC-CO2) SFE with Carbon dioxide (CO2), for this and many reasons is most unique and is able to save both time and money while retaining an overall extraction precision and accuracy. CO2, therefore, compressed to pressures above its critical pressure [4]; isothermally shows effective solubility powers in the region of its critical temperature [5-6]. Though a lot of SCFs can be adapted as solvents, CO2 is by far, the most extensively used due to its non-toxic, inert and non-flammable nature. It is also inexpensive and is generally environmentally accepted substance [7]. Biological products are often thermally labile, lipophilic, and non-volatile and as such required to be kept and processed at around room temperatures. CO2 has a critical temperature of 31oC which makes it particularly an attractive medium for this task. Other fluids show critical temperatures in the vicinity of critical state but are often difficult to handle and to obtain in pure state, may be toxic, explosive or ecologically unsafe. For such logical reasons, SFE using CO2 has emerged as an attractive unit operation for processing biomaterials. However, its limitations include the difficulty of extracting polar analytes, owing to the non-polar character of CO2, the different recoveries obtained from spiked and natural samples, and the frequent need for clean-up steps after extraction. Poor thermodynamic description of Supercritical (SC) solvent-solute mixtures, high capital cost for its extraction processes and an almost absence of engineering data to facilitate scale-up and design are also the prime factors that limits the use in industrial and commercial scales. For an excellent engineering design requires reliable data on the transport of a given biomaterial into the SC-CO2; such as the thermodynamic properties, fluid-liquid or fluid-solid equilibrium data of the biomaterial in the region of the temperatures and pressures where processing is technically and economically viable. Also, the measurements for the biomaterial plus SC-CO2 mixture in this condition, any mass transfer limitations for the bulk material into the SC solvent and the selectivity for the desired chemical species with the rest of the solubles in the biomaterial is paramount. Nonetheless, SFE with CO2 has great potential in the field of biomaterial processing as evidenced by the many papers published and the communications presented at the recent symposia on Supercritical fluid Technology [8]. CO2 is a good solvent for extracting lipid-soluble compounds and enables a high level of recovery [9]. CO2 is supercritical above 31.10C and 7.38 MPa, which makes it an ideal solvent for extracting thermally sensitive materials such as pyrethrins. 1.4.0 Set-Up and Principle A Pilot plant equipped with two fractionation cells. (1) CO2 pump; (2) modifier pump; (3) solid samples extraction cell; (4) fractionation cell 1; (5) fractionation cell 2; (6) valve. A fluid (CO2) is brought to a specific pressure-temperature combination, which allows it to attain supercritical solvent properties for the selective extraction of active ingredients from the sample matrix of a biomaterial (in this case Pyrethrum). The sample is exposed to the SC- CO2 under controlled conditions; time, temperature, and pressure that allow dissolution of the active ingredients (Pyrethrins) from the sample in the SCF. The dissolved active ingredients will then be separated from the supercritical solvent by a significant drop in solution pressure [10]. Several guiding principles can be utilized to effect the extraction of these ingredients, particularly the quantitative extraction. This ideal extraction method would afford total recovery and high purity of the isolated desired ingredients (Pyrethrins). Due to the inherent variability in density, chemical composition etc, many substances that can be extracted by SFE, modification of the extraction conditions; specificall y temperatures, pressures, and extraction time, may be necessary to obtain maximum extraction yield. In addition to being used for total active ingredient (Pyrethrins) quantification, the pressure-temperature-time variables in this case would be manipulated to allow selective extraction of minute quantities of polar or non-polar analyses from the Pyrethrum sample matrices. This will help attain the optimum extraction time for the process. 1.5.0 Pyrethrum Pyrethrum flowers come from the Chrysanthemum genus. Due to the size, shape, and colour of the petals; and the daisy-like appearance, they are often called painted daisies or painted ladies. Other names given to it are Buhach, Chrysanthemum Cinerariaefolium, Ofirmotox, Insect Powder, Dalmatian Insect Flowers, and Parexan. According to Visiani (1842-1852), it was first recorded in Dalmatia [11]. Other writers [Bakari P. (2005)] believe that the Pharmacist Antun Drobac (1810-1882) from Croatia was the first to prove its insecticidal activity [12]. Yet there are claims that it was first identified to possess insecticide properties in Asia around 1800 or about 300 B.C.[ Jeanne Roberts]; and that the Crushed and powdered plants were used as insecticides by the Chinese as early as 1000 BC. The Pyrethrum contains about 1-2% pyrethrins by dry weight, but approximately 94% of the total yield is in the seeds of the flower [Casida J.E., Quistad G.B. (1995)] [13]. From literature [14] [Coomber H.E. (1948)], the chemical structures of the active ingredients, pyrethrin I and pyrethrin II was identified in 1924 by a German chemist Herman Staudinger and a Croatian scientist Lavoslav Ruika. Kenya is the worlds main producer today, producing more than 70% of the global supply [Casida (1973)]. [15-17] 1.6.0 Pyrethrins Pyrethrins are the natural active ingredients of the chrysanthemum. Pyrethrin I, cinerin I and jasmolin I are esters of the chrysanthemic acid, and cinerin II, pyrethrin II, and jasmolin II are esters of the pyrethric acid. The three chrysanthemic acid esters are referred to as pyrethrins I (PYI), and the pyrethric acid esters as pyrethrins II (PYII) [Essig K., Zhao Z. J. (2001)]. Pyrethrins I, though insoluble in water, are soluble in some hydrocarbons and organic solvents [WHO (1975)]. According to Todd et al. (2003), they are non-volatile at ambient temperatures, non-toxic to mammals and other worm-blooded animals; and highly unstable in light (photodegradable) [Chen and Casida, (1969)], biodegradable [WHO (1975)], but toxic to aquatic animals. They are mainly used for biological crop protection and as domestic insecticides; and are the major formulations of synthetic pyrethroids. Pyrethrins when used in sufficient amounts are very effective in killing many insects. Although pyrethrins are soluble in a number of organic solvents such as hexane, acetone, benzene, petroleum ether, methanol, chlorinated hydrocarbons, etc; other considerations as practical, economic and environmental concerns limit the use of many of these solvents. This reduces the options to just a few. One of the qualities of Hexane in the extraction of pyrethrins is that it can dissolve the active ingredients effectively without dissolving all the other natural contaminants (pigments, waxes, fatty acids, etc), which are present and must be removed. Removing it from the concrete is also possible at lower temperatures, which limits degradation due to prolonged heating. Its low boiling point is also an added quality. Again, it can be recovered for recycling and reduces the weight of the concrete. Above all, it is inexpensive, accessible and environmentally friendly. It is non-toxic, non-corrosive, non-reactive, and non-flammable. 1.7.0 Pyrethrin Extracts Although pyrethrins are soluble in a number of organic solvents such as hexane, acetone, benzene, petroleum ether, methanol, chlorinated hydrocarbons, etc; other considerations as practical, economic and environmental concerns limit the use of many of these solvents. This reduces the options to just a few. Normal Hexane (n-hexane) is the solvent for the extractions. One of the qualities of Hexane in the extraction of pyrethrins is that it can dissolve the active ingredients effectively without dissolving all the other natural contaminants (pigments, waxes, fatty acids, etc), which are present and must be removed. Removing it from the concrete is also possible at lower temperatures, which limits degradation due to prolonged heating. Its low boiling point is also an added quality. Again, it can be recovered for recycling and reduces the weight of the concrete. Above all, it is inexpensive, accessible and environmentally friendly. It is non-toxic, non-corrosive, non-reactive, and non-flammable. The Hexane is heated above ambient temperature, considering its boiling point (pyrethrum is 170 oC 200 oC) [23] as the upper limit; for efficient extraction but raising the temperature has an effect. It promotes and aids degradation of the active ingredients. The concentration of pyrethrins in the concrete is expected to be 30 10% by weight with contaminants. Organic compounds that have lower molecular weights (ester, ether, etc) are soluble in liquid carbon dioxide. Some constituents of pyrethrum are partially soluble in liquid CO2, while others are not. Fatty acids, alkanes, triterpenols, Water, are those slightly soluble yet inorganic salts, amino acids, sugars, carotenoids, and fruit acids are insoluble [Marc Sims, (1981)]. Pyrethrins are very soluble in liquid CO2 due to the lone ketone and at least one or ester in its molecules. The rest of the molecule is hydrocarbon. Normally, GC analysis of the Pyrethrin components is difficult because Pyrethrin I and II undergo thermal isomerization to form isopyrethrin I and II at temperatures above 200oC [24-27]. These temperatures can neither be avoided in split or splitless injection systems nor in the elution from capillary columns. This brings about a transition of the isopyrethrins continuously and lead to improper integration of Pyrethrin I and II the peaks. The use of very short thin film columns combined with an on-column injection system17 will reduce this thermal conversion. Yet even with such columns the capacity and the separation performance will be insufficient. It also means that the natural Pyrethrins will appear together but the overall detection of the total amount of the pyrethrins is therefore feasible. 1.8.0 Properties Pyrethrum is very important due to these key properties: 1.8.1 Action: It attacks rapidly, the nervous system of the insects providing knockdown and killing effects eventually. 1.8.2 Immunity: In fact, there are beliefs that insects developing resistance to Pyrethrum is not practicable due to the complex nature of its structure 1.8.3. Toxicity: For a long time, it has proven to be safe for humans and other warm blooded animals but some claim it is toxic for cats [PetEducation.com], but toxic to aquatic animals even at as 2 parts per trillion [Bhanoo, Sindya (2010)] Green Inc. Energy, Environment, and the Bottom Line. New York Times, https://greeninc.blogs.nytimes.com 1.8.4 Activity: It has a vast spectrum of activity and can be used against any insect species. This is because of its closely related group of compounds (PYI and PYII). 1.8.5 Repellency and inhibition/jamming: Pyrethrum is also used to repel insects in food and grain during storage and personal protection. Beside this, it is also used to inhibit insects biting efficiency [ ] or jam their biting ability 1.8.6 Flushing: It is considered to have the greatest flushing action than any insecticide. It disturbs and flashes out the insects in their hiding outs. 1.8.7 Environment: Pyrethrum is photodegradable and as such is environmentally friendly (half-life of 12 days in soil) [www.ehow.com]. It also decomposes in air and relatively high temperatures and therefore presents no hazards due to persistence [NPTN Fact Sheet]. National pesticide telecommunications network 1.9.0 Pyrethroids Pyrethroids are man-made (synthetic) but chemically stabilized form of natural pyrethrins. Their structures are adapted and resemble that of pyrethrins and as such have similar activities. They are altered to improve their stability and potency.There are two kinds. Type I include tetramethrin, Allethrin, bioresmethrin, resmethrin and permethrin. Some type II pyrethroids are cyfluthrin, cypermethrin, deltamethrin, fenvalerate, cyphenothrin, and fluvalinate. They are persistent compounds (cypermethrin, permethrin and deltamethrin) and are resistant to degradation by air and light and therefore, are appropriate for use in wide applications, but they have higher significant mammalian toxicities (Morgan, 1989). 1.10.0 Synergist Despite the potency and safety of pyrethrum, it has few limitations. Some insects are able to recover from the knockdown effect. Again, because it breaks down in air and sunlight, it looses its effectiveness quickly in outdoor use. These are combated by treating pyrethrum extract with a liquid called Synergist. This has the ability to protect the pyrethrum from breaking down in the insects system. Small quantities of pyrethrum are mixed with these chemicals to effectively and efficiently control insect populations. The most popular of there are MGK-264 and Piperonyl butoxide. 1.8.0 Experiments 1.8.1. Objective The purpose of this experiment is to determine, compare the efficiency and provide a method by which pyrethrins are obtained in an appreciably pure and at the same time stable form (yet economical) from pyrethrum flowers by extracting 1) with an organic solvent (n-hexane) in a Soxhlet extraction and finally obtaining the pyrethrins from the concrete using sc.CO2 (proposed method); and 2) Directly with SC.CO2 and finally dissolving the concrete in organic solvents (methanol, petroleum ether and n-hexane) to obtain the pyrethrins (Factory method). 1.8.2. Chemicals Grounded chrysanthemum cinerariaefolium, Hexane, CO2 SFE grade 1.8.3. Instruments Soxhlet apparatus, burner, and flask, filter paper 1.8.9. SFE apparatus A self built apparatus with the following parts will be used: the pump, cylinder, oven, flow valves, pressure gauges, and thermometers. 1.9.0. Normal (Organic) Solvent Extractions 1.9.1. Water bath Extraction of the pyrethrins from 100g of the grounded pyrethrum flowers with hexane would be conducted in a water bath (YUHUA, DF-101S) in batches at temperatures of 35oC, 40 oC, 45 oC, 50 oC, 60 oC and 70 oC in 3hrs, 4hrs, 5hrs, 6hrs and 7hrs; in a 1000mL round bottomed flask. Agitation would be achieved by stirring vigorously with three big size magnetic stirrers at a speed of 20rpm. The hexane would then be removed with a rotary evapourator (YUHUA, RE-2000B) at a temperature of 25 oC and at a speed of 180rpm; to obtain the pyrethrin concrete (20mL) also called Crude Hexane Extract (CHE). 1.9.2. Chromatographic Conditions A Gas Chromatogram with flame ionization detection (FID); Agilent., HP-5 capillary Column, 30mm 0.25mm id., 0.25um lm thickness would be used. Each run required about 50mins. The instrument would be calibrated with multiple-point standard additions calibration method using the six individual standard samples to be prepared. The peak area of each component in the sample solutions would be fitted within the linear range of the standard. The split/split less injector, in the ratio 20:1, would be kept at 250 C. Nitrogen would be the carrier gas at a ow rate of 1.6L/min with an injection volume of 0.1L. The temperature program would start at 180 oC, kept for 11 minutes, heated at 10C/ min to 200 C, kept for 8 minutes; heated to 210 C at 10 C/min, kept for 18 minutes, then heated to 245C at 30C/min, staying at this temperature for 4 minutes. 1.9.3. SFE Conditions The carrier gas will be Hexane with a constant flow rate of 2mL/min, pressure would be between 13-25Mpa. The temperature program would be from 35-45oC. Contact time would be within 3hrs to 6hrs. References 1) Dunford, N.T., Teel, J.A., King, J.W., 2003, A continuous counter current supercritical fluid deacidification process for phytosterol ester fortification in rice bran oil. Food Research International 36, 175-181. 2) Ravents, M., Duarte, S., Alarcn, R., 2002, Application and possibilities of supercritical CO2 extraction in food processing industry: an overview. Food Science Technology International 8 (5), 269-284. 3) Mohamed, R.S., Mansoori, G.A., 2002. The use of supercritical fluid extraction technology in food processing, featured article food technology magazine, June, The World Markets Research Centre, London, UK. 4) The pressure of a fluid in its critical state; i.e. when it is at its critical temperature and critical volume, source: Answers.com 5) The temperature above which a gas cannot be liquefied, regardless of the pressure applied, source: Answers.com 6) The solubility of naphthalene in supercritical ethylene., J. Am. Chem. Soc 7) Extraction with supercritical Gases, Verlag Chemie, Deerfield Beach, FL 8) Present state of extraction of natural materials with supercritical fluids and development trends in supercritical fluid science and technology, eds, K. P. Johnston and J. M. Penninger, ACS symposium series No. 406, pp. 478-498; Performance of a packed column for continuous SC-CO2 processing of anhydrous milk fat. Biotech, Progress, 9) Awasthi, A., Trivedi, R.K., 1997: A review on supercritical carbon dioxide extraction of natural products, Chemical Engineering World Feature/Article; Fattori, M., Bulley, N.R., Meisen, A., 1988. Carbon dioxide extraction of canola seed: oil solubility and effect of seed treatment. Journal of the American Oil Chemists Society 65, 968-974. 10) Food analysis second edition: crude fat analysis. Purdue University, West Lafayette, Indiana, pp. 203-214 11) Visiani R. (1842-1852). Flora Dalmatica 12) Bakari P. (2005), Buha prirodni insekticid. Gospodarski list 17: 41-45 13) Casida J.E., Quistad G.B. (1995). Pyrethrum flowers: Production, Chemistry, Toxicology, and Uses. Oxford University Press, New York. 14) Coomber H.E. (1948). The chemical evaluation of Pyrethrum flowers, Pyrethrum Post 1 (1): 16-19 15) Chandler S.E. (1948), The Origin and Early History of the Production of Pyrethrum in Kenya. Pyrethrum Post 1 (1): 10-13 16) Mocatta G. (2003). Pyrethrum- from ancient discovery to advanced agriculture; Agriculturalist, Botanical Resources Australia. 17) Jones, G. D. G. Pyrethrum production, In Pyrethrum; The Natural Insecticide. J. E. Cadisa (eds.). Academic Press. New York, NY. 1973. pp 17-21. 18) Essig K., Zhao Z. J. (2001b). Preparation and characterization of a Pyrethrum extract standard. LC/GC 19(7): 722-730 19) Head S.W. (1966). A study of the insecticidal constituents in Chrysanthemum cinerariaefolium. (1) Their development in the flower head. (2) Their distribution in the plant. Pyrethrum Post 8(4): 32-37 20) WHO (World Health Organization). 1975. Data Sheet on Pesticides No. 11; Pyrethrins. www.inchem.org/documents/pds/pds/pest11_e.htm 20) Todd, G. D., Wohlers, D., and Citra, M. Toxicology Profile for Pyrethrins and pyrethroids. Department of Health and Human Services. Agency for Toxic Substances and Disease Registry. Atlanta, GA. 2003. 21) Chen, Y-L., and Casida, J. E. 1969. Photodecomposition of pyrethrin I, allethrin, phthalthrin, and dimethrin. J. Agr. Food Chem. 17: 208-215. 22) W.H.T. Pan, C.K. Liu, L. Y. Chou and M.H. Lee, J. Chin. Med., 5 (1994) 71 23)M. MATSUMOTO, Jpn Patent 119,682, 1974 24) L.W.Levy, Br. Patent 870, 456, 1961 25) G. Foget , J. Toxicol.Environ. Health, 32 (1991) 11 26) V.M.Valentine, Veterinary Clinics of North America-Small Animal Practice, 20 (1990) 375 27) D.A. Otieno, I.J. Jondiko, P.G. McDowell, and F.J. Kezdy, J. Chromatogr. Sci. 20, 566 (1982). 28) Technical Data sheet, Wefco marketing international cc; www. Wefco.co.za 29) Zong-Mao Chen, Yun-Hao Wang, chroma. Methods for the determination of pyrethrin and pyrethroids pesticides in crops, foods and environmental samples; journal of chrom. A. 754 (1996) 367-395 30) Ernesto Reverchon, Iolanda De Marco, Supercritical fluid and fractionation of natural matter; J. of suppercrit. Fluids, 38 (2006) 146-166 31) Carlo Bicchi, Claudio Brunelli, Mario Galli, Abino Sironi, Conventional inner diameter capillary columns: an approach to speeding up GC; J. of chrom. A, 931 (2001) 129-140 32) Thomas J. Class and Joachim Kintrup, pyrethroids as household insecticides: analysis, indoor exposure and persistence; Fresenius J. Anal Chem (1991) 340: 446-453 33) B.W. Wenclawiak, M. Krappe, A. Otterbach, In situ transesterification of the nat. pyreth; J. of chrom. A, 785 (1997) 263-267 34) Wynn H.T. Pan, Cheng-Chin Chang, Tien-Tsu Su, Fong Lee, Ming-Ren Steve Fuh: prep. supercrit. Fluid extract. Of pyreth I and II from Pyrethrum flower; Talanta 42 (1995) 1745-1749 35) Amrith S. Gunasekara, environ. Fate of pyrethrins; depart. Of pesticide regulation 1001 I street, Sacremento, CA 95812: novenmber 2004, revised 2005 36) Martina Gardisa, Klaudija Carovic-Stanko, Ivan Kolak, Zlatko Satovic; Morphological and biological diversity of Dalmatian pyre. Review article. Croatia 37) Ken Essig and Zhouming J. Zhao; Aventis environ. Sci, 95 chestnut ridge road, Montvale, new jersey 07645 38) .[ Jeanne Roberts, www.celsias.com: Insecticide Treated Mosquito Nets and Malaria Prevention: Weighing the Benefits, Naming the Benefactors] 2.0. CHAPTER 2: Report on GC analysis and Organic (Normal) Extractions 2.1.0 Objective The objective of this section of the experiment was to establish standard curves, by gas chromatographic techniques; for pyrethrins 1 (PYI) and pyrethrins 2 (PYII); the two groups of the six essential ingredients (Cinerin 1, Jasmolin 1, Pyrethrin 1; and Cinerin 2, Jasmolin 2, Pyrethrin 2) of the chrysanthemum (with the standard sample provided by the company), and to determine the percentage yields (and global yield) after Hexane (normal) extractions. 2.2.0 Background In analytical chemistry, the accuracy of quantitative measurements of the constituents of samples, using standard samples of known composition usually requires calibration. It is usually, but not automatically, done with samples and standards dissolved in appropriate solvents. This is due to the ease of preparing and diluting accurately, mixture of standard samples. Several standard solutions are prepared and analysed or measured, a line or curve is drawn (fit) to the data points and the obtained equation is used to translate values from the unknowns into corresponding concentrations. It has the advantage that random errors in the preparation and readings of standard solutions are averaged over many standards. Again, non-linearity can be seen and eliminated by fitting into the linear sensitivity range by dilution. Yet still, this can be compensated for by using non-linear curve fitting methods. It is usually, but not limited to a first-order of measured fit signal (area) on the y-axis against concentration on the x-axis. The model equation is: y (signal) = m (slope) * x (concentration) + c (intercept) (1) It is the most common and straightforward method, but its main drawback is that it cannot compensate for non-linearity. A minimum of two data points are needed to construct the curve. The concentration, x of the unknown sample is given by x = (y-c)/m.. (2) Where y is the measuredsignal, m is the slope and c is the intercept from the curve (straight line fit). The value of c is zero if the curve is forced through the origin: then x = y/m.. (3) 2.3.0 Gas Chromatography Gas Chromatography (GC) is a means by which separations, quantifications and identifications of analytes of a given solution or mixture is done. The essentials required for this method are an injection port where samples are placed. There is also a column on where separations of the components are done; a carrier gas whose flow is regulated to carry the samples all along the instrument, and a detector for the identification of analytes as well as a data processor. By this tool, a sample is brought to the vapour form and a carrier gas sends the sample into a column. The carrier gas should be inert; chemically. The choice is often governed by the type of detector which is used. With a gas-liquid chromatography, the column is normally packed with a solid stationary phase. Once the sample moves along the column, the analytes that interact strongly with the phase spend more time in the stationary and the moving gas phases, hence will require more time to travel along the column. There are generally two types of columns: packed and capillary (sometimes called open tubular). Packed columns are 1.5 10m in length and have about 2 4mm internal diameter. Capillary columns are coated with liquid stationary phases or lined with thin layer which adsorb the stationary phase. They are more efficient than packed columns. After exiting the column the analytes once separated are detected by a detector and their response recorded for analysis. The time from injection of a sample to the time an analyte is detected is defined as Retention time tR. The boiling point of the sample is vital in determining retention time. Those with higher volatility (lower boiling points) tend to have shorter retention times as they spend more time in moving from the gas phase. Each analyte (component) will have a different retention time. Retention factor, k, (or capacity factor) is a term used to describe the travel rate of an analyte on a column. If the retention factor is less than one, elution will be quick such that to determine accurately the retention time is difficult; otherwise elution takes a very long time. The retention factor for an analyte is usually between one and five. For optimum efficiency, the volume must not be very large, and must be put in the column as a vapour plug. The most common injection method is the use of a micro syringe to inject the sample. For effective separations, peaks must symmetrical, sharp and hence no band broadening and trailing must be present. The greatest constraint of gas phase chromatography is the vaporization of the solid and liquid samples on the column in the gaseous state. This limits its use usually to the study of thermo stable and sufficiently volatile compounds (1) www.chromatographyonline.com 2.4.0 Determination of the Standard/Calibration Curve A calibration curve provides the relationship between a signal produced by an instrument and the concentration of the analytes being measured. Different analytes produces different and unique signals. The measurements (signals) of an analyte of unknown sample are commuted, from the standard curve into concentrations. Quantitative analysis with GC is based on comparative methods. The Concept is that the sample with the analyte and a standard Sample that has the same concentration of this analyte will produce similar results, using an instrument with the same conditions. Several standards of known are prepared and their concentrations calculated. Then a standard curve is established from the values of the analytical result (in this case; area) as a function of analyte concentration. This standard curve is then used to find the concentration of an unknown sample. Usually, the abscissa (x-axis) corresponds to the concentration and ordinate (y-axis) of the signal result (area). 2.4.1. Regression analysis The import of this analysis is to provide an equation that relates the instrument results to the concentrations used, such that with a given result the corresponding unknown concentration can be determined. The model of the function is y = f (x), defining y. The errors in calculating the concentrations would be acceptable (less) if the signal of the unknown are in the range (middle) of the signals of the standards. 2.4.2. Simple linear regression Once the results of the detectors are linear as a function of the measured variable, then the goal now is to obtain the parameters of a straight line of best fits. The least squares regression line, which reduces the sum of the square or the error of the data points; is represented by the linear equation, y = mx + c.. (4) x is the independent variable, and y is the dependent variable. The term c is the y-intercept or regression constant (c is the value when x = 0), and the term, m; is the slope (sensitivity) or regression coefficient. The Pearson correlation coefficient R2 gives a measure of the reliability of the linear relationship between the x and y values. If R2 = 1, the linear relationship between x and y exists and is exact. Values of R2 close to 1 indicate excellent linear reliability. If the correlation coefficient is far away from 1, the relationship is less reliable. A straight line suggests that the errors in y follow the law of normal distribution and usually, the experimental error is considered to affect the y value only but not the x value (concentration recorded). If the response of any unknown falls outside the range of the standard, then additional work is required. Likewise if it falls below the Limit of Detection, then the sample needs to be concentrated and must be diluted if it lies above the Limit of Linearity. 2.4.3 Calibration Methods There are about three methods for the determination of the standard/calibration curve. These are explained below. 2.4.3.1 External standard method This method involves the comparison of two chromatograms obtained successively but with the same control conditions. The first chromatogram is acquired from a standard solution (reference solution) of known concentration in a solvent, for which a known volume is injected and the corresponding area in the chromatogram is measured. The second chromatogram results from the injection of the same volume of the sample in a solution containing an unknown concentration of the compound to be measured. Since the same volumes of both samples are injected, the ratio of the areas is proportional to the ratio of the concentrations which depend upon the masses injected. For precision, several solutions of varying concentrations are used in order to create a calibration curve. 2.4.3.2 Internal standard method With internal standardization, a second compound, often related to the analyte but never found in the sample, is added at a known concentration to every sample and calibrator. It is the ratio of the analyte to internal standard that is the critical measurement in an internally standardized method. The calibration curve data are generated by injecting calibration samples of different concentrations, that all contain the same concentration of internal standard. The ratio of the analyte area to the internal standard area is calculated and plotted as the y-value against the concentration of the calibrator in x-axis. This compensates for any imprecision resulting from the injected volumes, which is the main drawback of the External standard method. This method relies on the relative response factor of each compound to be measured against the standard. It requires two chromatograms, one to calculate the relative response factors of the compounds of interest, and the other for analysis. The idea of relative response factors arises because the detector does not respond to each analyte in a mixture the same way. The areas of peaks could directly be used, if this was so; to obtain the total composition. This is done by dividing the peak area of each by the total area of the peaks. Hence, every peak area should be multiplied by an appropriate factor known as the response factor, (k) to compensate that. The compensated areas are then what are used to calculate the total mixture composition. Each response factor is then ratioed to that of a chosen component and this is termed relative response factor (f). The relative response factors then enable the determination of the total composition of any unknown mixture of similar components. The regression equation is rearranged as in equation (3), which allows calculation of the unknown concentration. 2.4.3.3. Method of Standard Additions Usually, in both the external and internal standard methods, matrix-based standards are prepared. This implies that the standard to be used for the calibration must not have any traces of the analyte. By this, reduces the likely signal stifling or interference of the matrix. To be exact, a blank matrix sample is analysed to ensure that no interfering peaks exist. Unfortunately sometimes, it is not possible to have an analyte without interfering peaks (free matrix). In such cases, this method is employed. A series of standards are obtained in several different concentrations. The standards are so added to portions of the sample. Several concentrations of the reference sample may be prepared (if available), without an internal standard. Thereafter, the samples are assayed and the corresponding results appropriately plotted. 2.5.0 How to determine an unknown concentration Determination of the unknown concentration of any sample can be done in two ways: 2.5.1. Graphically: Once the signal of the unknown is obtained, a horizontal line is drawn from the signal on the y axis (0.068) to meet the calibration curve and then a vertical line drawn straight down to the concentration on the x-axis (shown with blue arrows). The value at this point (estimated as 0.32M) is the concentration of the unknown sample as shown below. 2.5.2. Mathematically: The equation of the calibration curve is fitted to the data, and solved for concentration as a function of the signal (y). Then, the signal for each unknown is substituted into this equation and the corresponding unknown concentration calculated for. This gives more accurate concentration values compared with the graphical method. The fit equation is as in equation (1) and it is expressed mathematically as in equation (4) above. Solving equation (4) for Concentration (x) yields either equation (2) or (3) depending on whether the fit is forced through zero or intercept at c. i.e. x = (y c)/m (2) Or x = y/m (3) x is the unknown concentration to be calculated. 2.6.0 GC Analysis My first problem was to determine a set of experimental analysis conditions that give a better separation of the six analytes in a pure solution prepared from the standard sample provided by the company, in a reasonable time frame. Several conditions were tested until this particular one below chosen. Identification of the individual peaks was based on the similarities between the peaks produced and those from literature (B.W. Wenclawiak et al, 1997) with different conditions though. Analyses with these conditions were repeated three times for accuracy and reproducibility. Six standard solutions prepared were injected and chromatograms obtained. Replicate injections of each solution were made for precision and accuracy. The peaks from these chromatograms were compared with those found in literature for the identification of the individual analytes and their corresponding retention times noted. After this, the peak areas for PYI and PYII of all the six solutions were calculated by the software and recorded. A plot of these peak areas and the concentrations calculated earlier gave the standard curve for the analysis. 2.7.0 Experimental Procedure 2.7.1 Chemicals and Reagents Hexane: 110-54-3C6H14 97.0%86.18M Ethanol64-17-5 C2H5OH99.7% (46.07M) Ethyl dodecanoate: Filter papers (7cm and 15cm): Finel: filters (0.45m): Syringes (1mL): All the solvents were analytical-reagent grade. Hexane and Ethanol were purchased from Sinopharm Chemical Reagent Co., Ltd and used without any pre-treatment. 2.7.2 Equipment and Apparatus 2.8.0 Samples The grounded chrysanthemum (light green with a characteristic smell) was provided by the company in as well as two samples of the pyrethrum concrete (yellowish in colour). The first sample contained 50% of pyrethrins (i .e. 29.5% of pyrethrins 1 referred to as PYI and 20.5% of pyrethrins 2, called PYII); and the second one had 85.15%, comprising of 46.33% PYI and 38.82% PYII. 2.9.0 Conditions The conditions finally chosen as the best, after a series of conditions tried was: The split/split less injector, in the split ratio 20:1, was kept at 250 C. Nitrogen was used as carrier gas at a ow rate of 1.6L/min. The injection volume was of 0.1 L. The temperature program was started at 180 C kept for 11 minutes, heated at 10C/ min to 200 C, kept for 8 minutes; heated to 210 C at 10 C/min, kept for 18 minutes, then heated to 245C at 30C/min, staying at this temperature for 4minutes. The chromatographic analysis was performed in a gas chromatograph with an FID detector, Agilent GC, HP-5 Column, 30mm 0.25mm id., 0.25 m lm thicknesses. This column was chosen because it gives the best resolution, identication and quantication for products containing OH and C=O. (Rosana, Vanessa, 2003; Analytica Chimica Acta 505 (2004) 223-226). 2.10.0 Standard Curve Once the conditions were established, 2g of the PY concrete was transferred into a 100mL volumetric flask and Ethanol was filled to the mark and shook to mix. Knowing the mass, the concentration of the PY solution (20mg/mL) was then calculated using the relation: Concentration (mg/mL) = mass (mg)/Volume (mL) . (5) The concentration of PYI (9.266mg/mL) and PYII (7.764mg/mL) was calculated keeping in mind the % of each group in the sample provided (i.e. 46.33% and 38.82% respectively). Six standard aliquots; 1mL, 2mL, 4mL, 8mL, 16mL and 32mL of this PY solution was then transferred into a 50mL flask each and diluted with Ethanol again to the mark and mixed. The concentration of each standard portion and the PYI and PYII concentrations were then calculated appropriately. Pure PY sol PY conc.(mg/ml) PYI conc.(mg/ml) PYII conc.(mg/ml) pure sol 20 9.266 7.764 1ml 0.4 0.1853 0.1553 2ml 0.8 0.3706 0.3106 4ml 1.6 0.7413 0.6211 8ml 3.2 1.4826 1.2411 16ml 6.4 2.9651 2.4845 32ml 12.8 5.9302 4.969 Table 1: Concentrations of each standard portion calculated With a micro syringe, 0.1L of each of these solutions were injected into the GC for analysis. The elution times and the corresponding peak areas were noted and recorded. See the table below. Comp. 1ml 2ml 4ml 8ml 16ml 32ml Elution (min) Peak area Elution (min) Peak area Elution (min) Peak area Elution (min) Peak area Elution (min) Peak area Elution (min) Peak area Cinerin1 19.86 20.01 19.87 42.79 19.87 81.28 19.87 174.29 19.88 260.04 19.91 618.90 Jasmolin1 23.11 11.94 23.11 12.86 23.11 24.18 23.11 58.79 23.12 87.79 23.13 209.17 Pyrethrin1 24.27 56.51 24.29 121.83 24.29 227.91 24.31 487.30 24.34 722.69 24.43 1711.29 Cinerin2 38.44 24.09 38.46 37.92 38.47 75.19 38.48 161.23 38.51 238.44 38.57 581.32 Jasmolin2 42.06 19.06 42.07 29.42 42.06 48.35 42.07 114.08 42.07 161.40 42.09 390.64 Pyrethrin2 42.91 4.22 42.91 3.60 42.91 8.09 42.91 18.14 42.92 26.26 42.96 57.89 Table 2: Elution times and peak areas of analytes in standard sample The concentrations and the peak areas are then tabulated to construct the overall standard curves for PYI and PYII respectively. Soln. PY(mg/ml) PYI(mg/ml) A1 PYII (mg/ml) A2 pure sol 20 9.266 4436.5566 7.764 1790.7451 1ml 0.4 0.1853 88.4592 0.1553 47.3710 2ml 0.8 0.3706 177.4739 0.3106 70.9374 4ml 1.6 0.7413 333.3663 0.6211 131.6275 8ml 3.2 1.4826 720.3725 1.2411 293.4468 16ml 6.4 2.9651 1070.5243 2.4845 426.1003 32ml 12.8 5.9302 2539.3593 4.969 1029.8515 Table 3: concentration and corresponding peak areas The Pearson correlation coefficient R2 in each of the curves is about 0.99. From literaturechromatography online, this indicates the measure of the reliability of the linear relationship between the x (concentrations) and y (peak areas) values. Therefore, the standard curves could be used for the determination of corresponding unknown concentrations given their peak areas. 3.0 CHAPTER 3: Organic (Normal) solvent Extraction 3.1.0 Objective and Procedure The main objective of this extraction process is to obtain a light coloured Product with a high recovery rate of the six pyrethrin active ingredients [Kiriamiti et al. 2003]. Extraction essential components with an organic solvent is the simplest, commonest and most importantly, economic technique in modern Chemical industry Wikipedia. The desired samples are submerged completely and agitated in an organic solvent. This agitation (with or without heat) helps to dissolve the desired compounds needed. Hexane, dimethyl ether, methanol, ethanol are some of the most common organic solvents used for these kinds of extractions. However, not only the desired components are extracted during this process. Other soluble substances (waxes and pigments) that are hydrophobic are also extracted. The solvent is removed from the extract by vacuum processing at lower temperature, for re-use. The process can last for hours or weeks, or even more. After the solvent removal, the waxy thick mass left is the concrete. This is composed of essential oils and other oil soluble (lipophilic) materials (Wikipedia). The concrete is too thick (viscous), coupled with the presents of undesired components; to be used directly. A further treatment, usually with another solvent that only dissolve the desired compounds from the concrete is necessary. This solvent is again removed leaving behind the absolute (substance). 3.2.0 Sample Preparation For all chemical analyses, the analyte to be measured must be in a sufficient quantity and in a suitable form for the GC analysis. Usually, samples require pretreatment. This has an influence on the end result. Sample preparation is therefore an essential step in analysis just as measurements. Then appropriate extraction methods are employed. A 100g of the grounded chrysanthemum material containing the desired analytes was weighed out and placed inside a 500mL round bottom flask and a bottle of normal Hexane (as extraction solvent) was poured in to submerge the sample completely. This was then transferred into a water bath. The set up was then equipped with a condenser, to condensate the liquid vapour and connected to water source. The temperature program was set and the system was heated at various temperatures (40 oC, 50 oC, 60oC and 70 oC) each at times 5hrs and 7hrs. Magnetic stirrers were used to maintain equal distribution of heat and solvent and the rotation was set at 20rpm in each case. Each solution was filteredfilter paper-7cmwith the aid of a rotary evapourator after the set time and the extracted solid discarded. The filtered solution was condensed to 10ml each with a rotary evapourator to remove the solvent. This system has the advantage that the solvent is repeatedly recycled and also the temperature can be controlled (since the sample is thermo labile). Each concentrated sample was thereafter, filtered (0.45m) and 0.1L of each analysed in the GC. The results are below. Cp Art 40C (5Hrs) 50C (5Hrs) 60C (5Hrs) 70C (5Hrs) t A t A t A t A C1 19.91 20.88 23270.3 20.24 5483.71 20.25 5039.21 20.30 5921.06 J1 23.13 23.80 10711.0 23.33 3043.60 23.33 2753.30 23.39 3258.92 P1 24.43 25.44 19810.3 24.86 8830.62 24.87 7989.68 24.95 8956.26 C2 38.57 39.55 4121.32 39.16 3328.70 39.19 3132.16 39.35 3767.63 J2 42.09 42.289 1125.67 42.23 2075.81 42.25 1956.50 42.29 2505.47 P2 42.96 43.237 215.407 43.18 329.54 43.20 304.55 43.25 1030.98 Ttl 191.09 190.27 389.82 193.01 23091.95 193.09 21175.4 193.53 25440.32 Table 4: results for 5hrs analysis Cp Art 40C (7Hrs) 50C (7Hrs) 60C (7Hrs) 70C (7Hrs) t A t A t A t A C1 19.91 20.19 4175.84 20.13 3015.38 20.16 3069.10 20.96 21666.50 J1 23.13 23.31 2341.50 23.27 1642.98 23.32 1651.68 23.87 10253.00 P1 24.43 24.80 6795.98 24.72 5034.69 24.76 4946.84 25.51 18905.40 C2 38.57 39.08 2675.11 38.98 1841.87 39.06 1896.36 39.73 3905.71 J2 42.09 42.21 1638.08 42.18 1097.48 42.22 1206.58 42.34 1616.78 P2 42.96 43.16 284.72 43.11 182.52 43.15 187.01 43.28 167.43 Ttl 191.09 192.75 17911.23 192.39 12814.92 192.7 12957.57 195.69 56514.82 Table 5: results for 7hrs analysis The average elution time for each analyte was calculated within each time frame. Component Standard sample At 5hrs At 7hrs Cinerin 1 19.91 20.43 20.36 Jasmolin 1 23.13 23.46 23.44 Pyrethrin 1 24.43 25.03 24.95 Cinerin 2 38.57 39.31 39.21 Jasmolin 2 42.09 42.26 42.24 Pyrethrin 2 42.96 43.22 43.18 Total 191.09 193.71 193.38 Table 6: average retention times With the peak areas from Table 4, the concentrations and yields for PYI and PYII within these times was calculated as well. Concentrations (mg/ml) Num Comp Pyret Stand 5hrs 7hrs 40 50 60 70 40 50 60 70 1 C1 PYI 9.27 1175.54 379.33 344.90 396.34 290.94 211.83 211.27 1110.71 2 J1 3 P1 4 C2 PYII 7.76 247.65 259.97 244.51 331.15 208.46 141.52 149.16 257.96 5 J2 6 P2 Total PY 17.03 1423.19 639.30 589.41 727.49 499.40 353.35 360.43 1368.67 Table 7: concentrations of PYI and PYII Yields Num Comp Pyreth Stand 5hrs 7hrs 40 50 60 70 40 50 60 70 1 C1 PYI 0.46 1.18 0.38 0.34 0.40 0.29 0.21 0.21 1.11 2 J1 3 P1 4 C2 PYII 0.38 0.25 0.26 0.24 0.33 0.21 0.14 0.15 0.26 5 J2 6 P2 Total PY 0.85 1.42 0.64 0.59 0.73 0.50 0.35 0.36 1.37 Ratio (PYI : PYII) 1.21 4.75 1.46 1.41 1.20 1.38 1.50 1.40 4.27 Table 8: yields and ratio for PYI and PYII The areas of PYI and PYII for the various temperatures from the analysis (Tables 4 and 5), gave higher concentrations (Table 7). These exceeded the range set for the standard. The range for PYI is 9.27mg/ml and that of PYII is 7.79mg/ml. Yet the lowest concentrations for PYI and PYII (Table 7) are 211.27mg/ml and 141.52mg/ml respectively. The total PY concentration in the standard (range) is 17.03mg/ml and the highest PY concentration from the analysis (extractions) is 142.32mg/ml (since PYI and PYII have the same volume, their concentrations could be added). Therefore, and for accurate results, these concentrations should be diluted (mix with more solvent) to fit into the range before proceeding with the analysis. This can be done by ways: 1) Finding the Dilution Factor. This in a way will tell how many times the initial volume (before the analysis) should be diluted to fit into the range. For such cases, the concentrations gotten from the reading on standard curve should be multiplied by the dilution factor. Therefore, the dilution factor, Df = final concentration/initial concentration (6) The final concentration is 1423.19mg/ml and the initial concentration is 17.03mg/ml Therefore, Df = 1423.19(mg/ml)/17.03(mg/ml) Df = 83.56958 This show a that the initial concentrated volume of 10ml should be multiplied almost 84 (i.e. about 850ml) times. This is too much solvent to use, hence not economical. 1) By taking a portion (aliquot) of the concentrated concrete and diluting it with an amount of solvent. The concentration of the concentrated concrete, Cc = 142.32mg/ml and that of the diluted concrete is Cd. The volume of the concentrated concrete taken is Vc and that of the dilution targeted is Vd Using the dilution equation Cc * Vc = Cd * Vd.. (7), the diluted concentration, Cd can be calculated. Cc = 1432.19mg/mL, if Vc = 1mL and Vd = 50mL. Cd = ? Cd = 1432.19 x 1 / 50 (mg/mL) = 14.3219mg/mL This new diluted concentration falls within the range of 17.03mg/mL Therefore, after concentrating the extract to 10mL, 1mL aliquot is moved into a 50mL flask and solvent topped to the mark before the GC analysis. 2) Eliminating the use of the rotary evapourator. Since a bottle of Hexane (500mL) is used for the extraction each time, it is not necessary to concentrate the solution after filtration but top up with some hexane to 500mL (some hexane will escape during the extraction process) mark before the GC analysis. 3.3.0 Optimum Extraction Temperature Table 8 shows the extraction temperatures and the corresponding yields between 5hrs and 7hrs. The result in this case suggests that the optimum temperature is at 40oC. This is because pyrethrins are thermo labile and therefore degrade after 40oC [E. Stahl, 1998; C. Gourdon, 2002; W.H.T.Pan, 1994]. At 40oC, targeted PY components are extracted more but after this temperature (with the increase) more undesirable components are extracted at the expense of the pyrethrins components which decompose. Again, at 40oC 5hrs gave a better yield than 7hrs. This suggests that with prolong heating, even at a safer extraction temperature (40oC), the PY yield is affected negatively. Therefore, an investigation into the optimum time and yield at this temperature (40oC) was done and the results, by fitting into the concentration range this time, before GC analysis are below: Num Comp Pyret Stand 40oC 3hrs 4hrs 5hrs 6hrs 1 C1 PYI 9.27 4.23 5.72 3.77 3.59 2 J1 3 P1 4 C2 PYII 7.76 1.03 1.81 0.83 0.70 5 J2 6 P2 Total PY 17.03 5.26 7.53 4.60 4.29 Table 9: Concentrations at various times at 40oC The results show that the concentrations are fitted into the range such that all the concentrations less than the maximum range set (17.03). Even more, they are within half of the range. This is important because the errors in the concentrations will be minimal if the signal (area) from the unknown lies in the middle of the signals (areas) of all the standards (chromatography online). Num Comp Pyreth Stand 40oC 3hrs 4hrs 5hrs 6hrs 1 C1 PYI 0.46 2.12 2.86 1.88 1.80 2 J1 3 P1 4 C2 PYII 0.38 0.52 0.90 0.41 0.35 5 J2 6 P2 Total PY 0.85 2.64 3.76 2.29 2.15 Ratio (PYI: PYII) 1.21 4.10 3.16 4.56 5.15 Table 10: Yields and ratio of PYI and PYII 3.4.0 Results and Discussions The percentage yields I obtained are not out of place comparing with literature. In some cases, the yield of PY varies from 0.91 to 1.30% of the dry weight [Kolak et al., 1999; Casida and Quistad, 1995]. According to Bakari (2005), the yield is between 0.60 0.79%. Bhat (1995) reported content ranging from 0.75 to 1.04%. However, Morris et al. (2005), reported yields of approximately 1.80 to 2.50%. Still according to Kiriamiti et al. (2003) the yield ranges between 0.50 and 2.0% while Pandita and Sharma (1990) gave yields varying from 0.90 to 1.50%. Above all Casida and Quistad (1995) states that it is possible to obtain pyrethrin yield of 3.0% or more. Therefore, the yield from my analysis of 0.85 to 3.76% conforms to literature. From this analysis, the optimum extraction conditions with Hexane are at 40oC in 4 hours (yield 3.76) but is this the real optimum extraction conditions (especially the temperature)? Since PY does not decompose between 20oC and 40oC, is it possible to have the optimum temperature at 25oC, 30oC or even 35oC? With this in mind, a further investigation was carried out in the same time frame (4hrs) beginning with 30oC such that if the result gave more yield than the one at 40oC, then the next would be 25oC and possibly 20oC. On the other hand, if the result gave fewer yields then the next would be 35oC and possibly 45oC. This would confirm the optimum conditions for the extraction process. 3.5.0 Conclusion References 1) Wikipedia 2) chemical analysis book 3) www.chromatographyonline.com 5) B.W. Wenclawiak et al, 1997 6) Rosana, Vanessa, 2003; Analytica Chimica Acta 505 (2004) 223-226 7) Kolak et al., 1999; Casida and Quistad, 1995 8) Bakari (2005) 9) Bhat (1995) 10) Morris et al. (2005) 11) Kiriamiti et al. (2003) 12) Pandita and Sharma (1990) 13) Casida and Quistad (1995) 14) Journal of chemical education vol. 75, no. 9, September 1998 Pyrethrins are well separated on polar columns but their analysis with a conventional (normal) column takes about 1 h. This is unacceptable but with a short OV-1 column, analysis time is reduced and thermal decomposition is also drastically limited; since the residence time is shorter and the elution temperature of pyrethrins I and II is lower. [Recommendation] A cold-on-column injection system and a high constant flow rate can further reduce pyrethrin degradation and elution temperatures and as a consequence their isomerization. [Recommend]