[译文]Development of a novel amide-silica stationary phase

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early modern english

early modern english

1.6 Great Vowel Shift 元音大推移
1) gradual process began in Chaucer's time (early 15th C) and was continuing through the time of Shakespeare (early 17th C).
sameflowersmilestodaytomorrowdying34wordcoinagesclippingvanvanguard先锋reararrearfortnightfourteennightbackformationdifficultdifficultyunitunityblendingdumbfoundconfoundapatheticpatheticspluttersputter使人哑然失声使惊惶漠然可怜的无动于衷的噼啪声溅泼声劈啪声
② The sudden social mobility after the Black Death--- with people from lower levels in society moving to higher levels. ③ Hundred Years’ War: medieval aristocracy who had spoken French began using English: change--- either by making pronunciation more French in style, or by changing it to something thought to be "more English"
1.4 Enclosure movement = conversion of small farms to larger enclosed sheep pastures Effects *Urbanization (loss of regional dialects) * rise of urban middle class

新视野大学英语(第二版)第四册读写教程课文翻译

新视野大学英语(第二版)第四册读写教程课文翻译

新视野大学英语(第二版)第四册读写教程课文翻译.An artist who seeks fame is like a dog chasing his own tail who, when he captures it, does not know what else to do but to continue chasing it.艺术家追求成名,如同狗自逐其尾,一旦追到手,除了继续追逐不知还能做些什么。

The cruelty of success is that it often leads those who seek such success to participate in their own destruction.成功之残酷正在于它常常让那些追逐成功者自寻毁灭。

"Don't quit your day job!" is advice frequently given by understandably pessimistic family members and friends to a budding artist who is trying hard to succeed.对一名正努力追求成功并刚刚崭露头角的艺术家,其亲朋常常会建议“正经的饭碗不能丢!”他们的担心不无道理。

The conquest of fame is difficult at best, and many end up emotionally if not financially bankrupt.追求出人头地,最乐观地说也困难重重,许多人到最后即使不是穷困潦倒,也是几近精神崩溃。

Still, impure motives such as the desire for worshipping fans and praise from peers may spur the artist on.尽管如此,希望赢得追星族追捧和同行赞扬之类的不太纯洁的动机却在激励着他们向前。

新视野大学英语读写教程(第三版)第二册Unit1 An impressive English lesson翻译

新视野大学英语读写教程(第三版)第二册Unit1 An impressive English lesson翻译
It was, like, marvelous!简直奇妙极了 (it was like) whoa!How can you got a hundred percent correct on such a hard test?哇!这么难的考试你怎么全都答对了?
Paragraph 03
She nodded three or four times, searched the heavens for the right words, and then exclaimed, "It was, like, whoa!".
Unit 1
Language In Mission
An impressive
English lesson
Paragraph 01
If I am the only parent who still corrects his child's English, then perhaps my son is right. To him, I am a tedious oddity: a father he is obliged to listen to and a man absorbed in the rules of grammar, which my son seems allergic to.
full of 充满 get/be serious about 对…是认真的,并非开玩笑 run into sb 偶然遇见某人 fresh from 刚从….来的;刚有…的经历 how was it 怎么样raph 02
I think I got serious about this only recently when I ran into one of my former students, fresh from an excursion to Europe. "How was it?" I asked, full of earnest anticipation.

新视野大学英语第三版读写教程1-8单元课后汉译英

新视野大学英语第三版读写教程1-8单元课后汉译英

新视野大学英语第三版读写教程3 汉译英答案Unit1汉译英原文:如今,很多年轻人不再选择" 稳定" 的工作,他们更愿意自主创业,依靠自己的智慧和奋斗去实现自我价值。

青年创业(young entrepreneurship)是未来国家经济活力的来源,创业者的成功不但会创造财富、增加就业机会、改善大家的生活,从长远来看,对于国家更是一件好事,创业者正是让中国经济升级换代的力量。

尤其是在当前,国家鼓励大众创业、万众创新,在政策上给予中小企业支持,这更加激发了年轻人的创业热情。

Keys:Nowadays, many young people no longer choose "stable" jobs. Instead, they prefer to start their own businesses and realize their self-value through their own wisdom and efforts. Young entrepreneurship is the source of national economic vitality in the future. The success of entrepreneurs not only creates fortune, increases job opportunities, improves people's life, but it is also good for the country in the long term. Entrepreneurs are a driving force in upgrading China's economy. Especially for the time being, our country is encouraging people to start their own businesses and make innovations and giving policy support for medium and small businesses. This further arouses young people's enthusiasm to start their own businesses.Unit 2汉译英原文:实现中华民族伟大复兴(rejuvenation )是近代以来中国人民最伟大的梦想,我们称之为“中国梦”,其基本内涵是实现国家富强、民族振兴、人民幸福。

新视野大学英语第三版读写教程第三册课后翻译

新视野大学英语第三版读写教程第三册课后翻译

课后翻译参考答案Unit 1汉译英原文:如今,很多年轻人不再选择" 稳定" 的工作,他们更愿意自主创业,依靠自己的智慧和奋斗去实现自我价值。

青年创业(young entrepreneurship)是未来国家经济活力的来源,创业者的成功不但会创造财富、增加就业机会、改善大家的生活,从长远来看,对于国家更是一件好事,创业者正是让中国经济升级换代的力量。

尤其是在当前,国家鼓励大众创业、万众创新,在政策上给予中小企业支持,这更加激发了年轻人的创业热情。

Nowadays, many young people no longer choose "stable" jobs. Instead, they prefer to start their own businesses and realize their self-value through their own wisdom and efforts. Young entrepreneurship is the source of national economic vitality in the future. The success of entrepreneurs not only creates fortune, increases job opportunities, improves people's life, but it is also good for the country in the long term. Entrepreneurs are a driving force in upgrading China's economy. Especially for the time being, our country is encouraging people to start their own businesses and make innovations and giving policy support for medium and small businesses. This further arouses young people's enthusiasm to start their own businesses.Unit 2汉译英原文:实现中华民族伟大复兴(rejuvenation )是近代以来中国人民最伟大的梦想,我们称之为“中国梦”,其基本内涵是实现国家富强、民族振兴、人民幸福。

a little book of language

a little book of language

A Little Book of LanguageIntroductionLanguage is the foundation of human communication and one of the most fascinating aspects of our existence. It is the tool we use to express our thoughts, emotions, and ideas. From the moment we are born, language surrounds us, shaping our understanding of the world and enabling us to connect with others.This book, “A Little Book of Language,” aims to explore the intricacies, wonders, and importance of language. Through its pages, we will delve into various aspects of language, including its origins, structure, evolution, cultural influences, and impact on society. So, let’s embark on this linguistic journey together!Chapter 1: The Origins of LanguageThe origins of language have long been a subject of fascination and debate. While we may never know exactly how language emerged, several theories attempt to explain its inception. From the instinctual cries of our earliest ancestors to the development of complex grammar systems, language has evolved over millions of years.Chapter 2: The Structure of LanguageLanguage is more than just a random collection of sounds or symbols. It has a structure that allows us to convey meaning effectively. This chapter will explore the various components of language, including phonetics, phonology, morphology, syntax, and semantics. We will uncover how these elements work together to form words, sentences, and discourse.Chapter 3: The Evolution of LanguageLanguage is constantly changing and adapting to the needs of its users. In this chapter, we will explore the evolutionary aspects of language. From the rise and fall of dialects to the emergence of new languages, wewill examine how language evolves over time and across different cultures.Chapter 4: Language and CultureLanguage and culture are tightly intertwined. This chapter will delve into the relationship between language and culture, exploring how language reflects and shapes our identities, beliefs, traditions, and social structures. We will also examine the concept of linguistic relativity and its impact on our perception of the world.Chapter 5: Language in SocietyLanguage is not just a means of communication; it is also a powerful social tool. This chapter will provide an overview of how language functions in society, including its role in power dynamics, social hierarchies, and identity formation. We will also explore the challenges of language preservation and the impact of globalization on linguistic diversity.Chapter 6: Sign LanguagesSign languages are unique and fascinating forms of communication used by deaf communities around the world. In this chapter, we will explore the structure and cultural significance of sign languages. We will also discuss the challenges faced by sign language users and the importance of promoting inclusivity and accessibility.Chapter 7: Language AcquisitionHow do we learn language? This chapter will examine the process of language acquisition, from a baby’s first words to the complexities of second language learning. We will explore the role of nature and nurture in language development and discuss the critical period hypothesis.Chapter 8: Language and TechnologyTechnology has revolutionized the way we communicate, and language is no exception. This chapter will explore the relationship between language and technology, including the impact of the internet, social media, and artificial intelligence on language use and evolution. We will also discuss the challenges and opportunities presented by machine translation.ConclusionLanguage is a remarkable human invention that connects us, shapes our thoughts, and defines our cultural identity. In “A Little Book of Language,” we have explored its origins, structure, evolution, cultural influences, and impact on society. By understanding language, we gain insight into the complex workings of the human mind and the rich tapestry of human experience.Thank you for joining me on this linguistic journey. May your love for language continue to flourish as you explore its intricacies and delights.。

戴炜栋《简明语言学教程》配套笔记3

戴炜栋《简明语言学教程》配套笔记3

戴炜栋《简明语⾔学教程》配套笔记3Chapter 12 PsycholinguisticsThe study of language in relation to the mindP.S. some of the following discussed sometimes fall into the scope of neurolinguistics and sociolinguistics, esp. concerning the structure of the brain.[A] The biological foundations of languageHuman linguistic ability largely depends on the structure and dynamics of the human brain, rather than, the structure of the vocal cords.Neuronsàcerebral cortexàhemisphereBrain lateralization (specific to human beings): the left hemisphere has primary responsibility for language, while the right hemisphere controls visual and spatial skills as well as the perception of nonlinguistic sounds and musical melodies.The localization of cognitive and perceptual functions in a particular hemisphere of the brain is called lateralization.[B] Linguistic lateralizationLeft hemispheric dominance for language, this hypothesis has been proved by Dichotic listening research(两⽿分听试验)The sound presented in the right ear goes directly to the left brain. The sound heard in the left ear, on the other hand, must first go to the right hemisphere, from where it is transferred to the left side of the brain for processing.Right ear advantage:(右⽿优势)it appears to exist primarily for linguistic stimuli, both meaningful and nonsensical.[C] The language centers①Broca’s area (French surgeon and anatomist): The frontal lobe in the left cerebral hemisphere damaged extreme difficulty in producing speech;[Speech production deficit] word-finding difficulties and problems with syntax②Wernicke’s area (German physician, 1874): Strengthened Broca’s claim, and generated intense interest in the hypothesis that different areas within the left hemisphere fulfill different linguistic functions[Speech comprehension deficit] difficult in understanding speech (posterior speech cortex)③The angular gyrus(⾓形脑回): It is responsible for converting a visual stimulus into an auditory form and vice versaThe word is heard and comprehended via Wernicke’s area. This signal is then transferred via the arcuate fasciculus to Broca’s area (the angular gyrus), where preparations are made to produce it. A signal is then sent to the motor cortex to physically articulate the word.④language perception, comprehension and production[D] The critical period for language acquisitionßneurobiologist Eric LennebergIt refers to a period in one’s life extending from about two to puberty, during which the human brain is most ready to acquire a particular language and language learning can proceed easily, swiftly, and without explicit instruction.Language faculty of an average human degenerates after the critical period.{Language can be acquired after the critical period.}[E] Early views on language and thoughtMentalistà thought and language were identical, proposed by PlatoEmpiricistà languages were signs of psychological experiences (Aristotle)Bloomfield, American psychologist, founder of Behaviorism, supported the mentalist: thinking was a system of movements that had been reduced from actual speech to the point where they were no longer visible.Violates the following two phenomena:Non-speaking humansà display complex thought processI didn’t mean to say thatThe Sapir-Whorf hypothesis: (the American anthropologist-linguist Edward Sapir and his student Benjamin Lee Whorf)“We cut nature up, organize it into concepts, and ascribe significance as we do, largely because we are parties to an agreement to organize it in this way—an agreement that holds throughout our speech community and is codified in the patterns of our language.”Linguistic determination—the strong notion: Language determines thoughtLinguistic relativism—speakers of different language perceive and experience the world differently, i.e. relative to their linguistic backgroundThis hypothesis appears plausible, but its strong version has very few adherents today.Whorf did not only depend too heavily on the literal use of words but also on grammatical structure.The weaker version is accepted. Language may be used to provide ideas, bring about a change in beliefs and values, solve problems, and keep track of things in memory. Language does influence the perceptions, memory tasks, and other verbal and nonverbal behavior of human beings by its convenience, availability, and habitual use.[F] Argues for and against the Sapir-Whorf hypothesis①Words and meaning: Relation is arbitrary; without the particular words of snow doesn’t mean he can not perceive differences in varieties of snow…②Grammatical structureMany grammatical features of a language are purely superficial aspects of linguistic structure. They don’t have the kind of interdependent relationship with the perceptual system of the speakers of that language. (Grammatical gender)③TranslationSuccessful translation between languages can be made.That he (Sapir) can explain/describe Hopi concepts in English for an average English speaker to understand easily fully proves that translation can be obtained.④Second language acquisitionBilingualism: have a consistent conceptual-perceptual system of the physical world. Don’t have to have double minds.⑤language and world viewsPeople who use the same language may have different world views.People who use different languages may have the similar world views.One language can describe many different world views.[G] Understanding the relationship between language and thought①functions of language:Interpersonal communication: convey information, thoughts, feelings from one to anotherIntrapersonal communication: language facilitates thinking, speech behavior, and action for the individualHalliday: ideational, interpersonal and textual functionsa) Informativeb) Interpersonal function(1) Performative function(2) Emotive function(3) Expressive function(4) Phatic functionc) Recreational functiond) Metalingual function②Language and thought may be viewed as two independent circles overlapping in some parts.When language and thought are identical or closely paralleled to each other, we may regard thought as “subvocal speech”, and speech as “overt thought”Nonverbal signals: facial expression_r_rs, grimaces, gestures, postures, or proxemic space can be used to express thoughts.The relationship between the coding system of language on the one hand and the conceptualizing system of thought on the other is conventional rather than genetic. Bilingual speakers switch between the two languages concerned, not converting one mode of thinking into the other, but rather, making transition between the two linguistic coding systems.Chapter 13 First Language Acquisition (FLA)Language acquisition refers to children’s development of their first language, that is, the native language of the community in which a child has been brought up (naturally and successfully).[A] The biological basis of language acquisitionWhat is meant by the biological, or nativist, view of language acquisition is that human are equipped with the neural perquisites for language and language use, just as birds are biologically “prewired” to learn the songs of their species.No language is inferior, or superior, to any other language.No single human is a better or worse language acquire than any other human.Different languages have a similar level of complexity and detail, and reflect general abstract properties of the common linguistic system called the Universal Grammar (UG).[B] Language acquisition as the acquisition of grammatical rulesBefore 5, knowing most of the intricate grammatical system of their native languageWhat is acquired is not a bunch of utterances but a set of rules, conditions, and elements (fundamental grammatical rules) that allow one to speak and understand speech.[C] The role of input and interaction, instruction, correction and reinforcement, imitation①the role of input and interactionGenetic predisposition + an appropriate linguistic environmentAccess to language data and opportunities to interact with the inputModified speechßrelationshipà language acquisitionCaretaker speech (babytalk, motheress, or parentese): without it doesn’t mean acquiring language slowlyAdvantages: 1) help heighten its comprehensibility2) make it easier for children to match linguistic forms with their meanings②the role of instruction“Children learn to speak because adults teach them to speak.”1) this view overestimates what adults can do, and at the same time2) this view underestimates what children can do, and what they actually doChildren require little conscious instruction. Parents often fail their attempt to teach children grammatical rules, and only playing a minor role at best③the role of correction and reinforcementAssumption 1: children received constant correction for using a “bad” grammar and rewards when using a “good” grammar Assumption 2: children learnt to produce sentence because they were positively reinforced when they said something right and negatively reinforced when they said something wrong.Behaviorist learning theoryàa child’s verbal behavior was conditioned through association between a stimulus and a relevant response.Correction plays a minor role; even when syntactic correction does occur, children often do not know what the problem is and are unable to make corrections.④the role of imitationThe hypothesis that children learnt language by simply imitating the speech of those around them is not true.A more reasonable explanation is that: children are attempting to construct and generalize their own grammatical rules. Besides, children who cannot speak can learn the language spoken to them and understand what is said.Children don’t blindly mimic adult speech in a parrot fashion, but rather exploit it in very restricted ways to improve their linguistic skills[D] Stages of first language acquisitionIn general, children begin uttering their first words sometimes during the second year of life. During the following 4 to 5 years, linguistic development occurs quite rapidly.①the prelinguistic stage (babbling age)3 months: /k/, /u/3-4 months: babbling speech like sounds6 months: able to sit up; produce a number of different vowels and consonants (meaningless), deaf baby, baby born of non-speaking deaf parents also babble②the one-word stageàholophrastic sentences2 year-old: use one word to serve a naming function, to refer to familiar people, toys, pets, drinks and objects in the child’s environment, indicate certain actions and demands, or convey emotions.Simple nouns and verbsVery few functional words such as prep., art., and aux. verbsChoose the most informative word that applies to the situation being commented uponOverextension (underextension of reference): use the same word for things that have a similar appearance③the multiword stage2-3 year-old: the salient feature of the utterances at this stage ceases to be the number of words, but the variation in strings of lexical morphemes (telegraphic speech)Lacking grammatical morphemes, but following the principles of sentence formation [make no word order errors at this stage]5 year-old: has an operating vocabulary of more than 2000 words[E] The development of grammatical system①the development of phonologyThe emergence of articulatory skills begins around the age when children start to produce babbling sounds.Children first acquire the sounds found in all languages of the world, and in later stages acquire the “more difficult” sounds. Certain sounds that occur in babbling are lost when children began to speak the language, and then reappear at a later stage: /l/ and /r/②the development of syntaxChildren’s early language is not only semantically based, but also makes reference to syntactic categories, and grammatical relations.Two-word stage: noun-like element + predicate-like elementThen, add functional words as well as inflectional and derivational morphemes of the language-ing, in, on, the regular plural ending “-s”Negative sentences: no/all gone /// negative words occur at the beginning of expression_r_rs /// insert the negative “no”,“can’t” or “don’t” inside the sentence, usually between subject and the predicateEnglish questions have developed in the similar way, in an interrelated way with the development of the auxiliary verb system③the development of morphologyBeyond the telegraphic stage: incorporate some of the inflectional morphemes1st one: -ing; 2nd one: marking of regular plurals with the “-s” form (overgeneralization); 3rd one: -ed rule to all verbs; begin to learn both regular and irregular forms as individual words④the development of vocabulary of semanticsThe first two years: 50-100 wordsSemantic referent to a word expands: overgeneralizationThe age of two and a half years: vocabulary is expanding rapidlyThe age of three: hundreds of wordsConnection between a word and its denotative meaning is more like that of adult languageBy five: 4.6 words per sentenceIncrease of about 25 words per dayThe age of six: 7800 wordsà English-speaking school childrenBy the age of eight: 17600 words or 28300 including derived formsIn general, children have virtually acquired the basic fabric of their native language at the age of five or six.Per-school years are crucial period for first language acquisition.Chapter 14 Second language Acquisition/Learning[A] Acquisition v. learningAcquisition: refers to the gradual development of ability in a language by using it naturally in communicative situations; or the gradual and subconscious development of ability in the first language by using it naturally in daily communicative situations (by American SLA scholar Stephen Krashen)Learning: refers to a conscious process of accumulating knowledge of the vocabulary and grammar of a language, usually obtained in school setting.[B] Transfer and interferenceTransfer: while learning the target language consciously or unconsciously, learners will subconsciously use their L1knowledge in learning a second language.Positive or negativeInterference (negative transfer) was once believed to be the major source of difficulties experienced and errors made by L2 learners.Contrastive analysis: establish the linguistic differences between the native and target language systems, to predict problems and errors[Old view]: L2 errors were predominantly the result of negative transfer, or mother tongue interference. Thus, learning a L2 is always to overcome the differences.Empirical investigation:3%àinterference errors, 85%àdevelopmental errors[New view]: L2 learning is a process of contracting and modifying rules of communication[C] Error analysis and the natural route of SLA developmentThere was supposed to be a universal route in L2 learning because negative transfer is not the major factor in SLA as it was once assumed to be.L2=L1 hypothesis: the process of SLA and FLA are very similar.This was investigated through the analysis of learner errors. There are striking similarities in the ways in which different L2 learners acquire a new language.L2 learners follow broadly similar routes, although minor differences exist due to variable learner factors and learning situations.[D] Interlanguage and fossilizationInterlanguage: the language that a learner constructs at a given stage of SLA. It consists of a series of interlocking and approximate linguistic systems in between and yet distinct from the learner’s native and target languages. Fossilization: it was once assumed that learners’ Interlanguage would develop gradually in the direction of the target language competence if provided with sufficient and the right kind of language exposure and interaction. But most L2 learners failed to reach the end-point of the interlanguage continuum and acquire the native-like competence in the target language.Explanation: learns’ interlanguage fossilized some way short of target language competence while the internalized rule system contained rules that are different from those of the target language system.Chinese sound /d/àEnglish /W/, /T/; he for he or sheThe use of the present tense form for a past tense verb3rd person singular form without “s”[E] The role of input and formal instruction①SLA takes place only when the learner has access to L2 input and the opportunity to interact with the input. Input may take the form of exposure in natural settings or formal instruction, either spoken or written; optimum input is needed.Comprehensible input: the use of learned structures and vocabulary, the linguistic and extralinguistic contexts of the input data, and the learner’s general knowledge to interpret new language items.Two very important kinds of input methods:Interaction: taking parting in communication activitiesIntake: the input that is assimilated and fed into the interlanguage system②in general, studies of the effects of formal instruction support the hypothesis that instruction aids SLAL2 learners are much more likely to obtain comprehensible input in the intake-type environment of a classroom setting, other than in the exposure-type environment of a natural setting.Casual and spontaneous conversation helps a little, while planned speech, writing or career-oriented examination help a lot.[F] Individual leaner factors like age, motivation, acculturation and personalityThe rate and ultimate success in SLA are affected not only by learner’s experience with optimal input and instruction, but also by individual learner factors.①the optimum age for second language acquisitionAdolescents: quicker and more effective L2 learners than young childrenWhy: the learner’s flexibility of the language acquisition faculty has not been completely lost while one’s cognitive skills have developed considerably to facilitate the processing of linguistic features of a new language.②motivationMotivation: the learner’s overall goal and orientationInstrumental motivation: learner’s goal is functional (功能性学习动机)Integrative motivation: learner’s goal is social (介⼊性学习动机)③acculturation(⽂化移⼊,⽂化适应)It has some relation with integrative motivation, the extent to which learners differ in the process of adapting to the new culture of the L2 community. This adaptation process is called acculturationThe learning of a second language involves, and is dependent on, the acquisition of the culture of the target language community.The acculturation hypothesis states simply that the more a person aspires to acculturate to the community of the target language, the further he or she will progress along the developmental continuum, but focuses not so much on the actual processing of the second language as on the social and psychological conditions under which L2 processing is most likely to take place successfully.④personalityOutgoing personality may contribute to language acquisitionExtrovertedßàintrovertedResearch results lead only partial support to this hypothesis.Oral fluency, not overall proficiency in a second languageIn general, a good second language learner is, among other things, an adolescent who has a strong and well-defined motivation to learn, who is able to respond and adaptable to different learning situations, who seeks out all opportunities and makes maximum use of them to interact with the input, who employs appropriate learning strategies, and who is willing to identify himself or herself with the culture of the target language community.。

文学著作的英语

文学著作的英语

文学著作的英语1. Literature is a form of art that uses written wordsto express ideas, emotions, and stories. It includes various genres such as poetry, fiction, drama, and non-fiction.2. 文学是一种艺术形式,使用书面文字来表达思想、情感和故事。

它包括诗歌、小说、戏剧和非小说等各种流派。

3. Literature has been a fundamental part of human culture for centuries, serving as a means of communication, entertainment, and reflection. It allows people to explore different perspectives, experiences, and emotions through the words of others.4. 文学已经成为人类文化的基本组成部分几个世纪了,作为交流、娱乐和思考的手段。

它使人们能够通过他人的文字来探索不同的观点、经历和情感。

5. Through literature, authors can convey complex ideas and themes, evoke strong emotions, and create vivid imagery that resonates with readers. It has the power to inspire, challenge, and provoke thought.6. 通过文学,作者可以传达复杂的思想和主题,唤起强烈的情感,并创造生动的形象,引起读者共鸣。

它有激发、挑战和引发思考的力量。

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一种新型酰胺基固定相的研发——反相HPLC色谱对不同组分植物激素的分离摘要:一种新型酰胺基硅胶固定相的制备始于N-Boc-苯丙氨酸、酚酞单磷酸二环己胺盐以及球型硅胶(4 mm, 60Å)。

酰胺基配体的合成具有高收率。

通过SEM、IR以及元素分析对所得的酰胺基固定相进行表征。

得到能够承载极性酰胺基组分的选择体会被用于从13种不同组分植物激素的反相色谱分离。

酰胺基固定相分离所得的分析物的色谱分析状况会与相同条件下的RP-C18色谱柱的色谱分析状况进行比较。

流动相、pH值、流速、温度等因素对该分离系统的影响将会被研究。

通过调节梯度洗脱的水体流动相pH=6.85,磷酸钾缓冲液(20mM)以及20℃柱温度的乙腈的反相HPLC能够实现最佳分离。

在这些实验条件下,12种植物激素能够被分离出来并能够在230nm或270nm的波长下检测出来。

1.简介高效液相色谱分析对于化学物组分广泛的分析具有非常重要的作用。

所用固定相的性能对该技术分离效果的影响很大。

所以,高效固定相的设计对HPLC的色谱分析而言尤为重要。

对色谱分析来讲,新型酰胺基固定相的研发仍然是一个巨大的挑战。

C8和C18烷基链的改性硅胶仍然是反相HPLC应用最广泛的固定相。

除了用以分离酸性、碱性极性化合物的非极性RP配体以外,RPLC的最新发展趋势还涉及到含有极性基团的固定相的应用。

化学键合氰基,二醇,环糊精,内嵌酰胺聚乙二醇和烷基氨基甲酸酯或其他功能的中等极性固定相,最初主要打算在反相富水流动相中应用。

随后,极性固定相对极性分析物展现了新的性能。

最新的研究调查表明含有极性基团的固定相在分离碱性分析物方面要比传统的C8和C18色谱柱具有更为优越的性能。

极性基团,特别是酰胺基,最初之所以被选用就是因为其具有与碱性分析物发生反应的能力。

此外,酰胺基基团还对低分子量的酸性分析物有较高的选择性。

含有嵌入式极性基团的固定相具有不同的选择性,较小的保留性,流动相中有机溶剂的浓度更低。

低浓度的激素植物在植物发育的不同阶段,如细胞分裂,扩大和分化;器官形成;种子休眠与萌发;叶器官的衰老和脱落等,参与发挥了许多重要的作用。

自从第一个植物激素,生长素,发现于1926年,科学家发现植物激素的几种类型,主要包括生长素,细胞分裂素,赤霉素,脱落酸,乙烯。

与生长素类似性能的氯化苯氧基酸也被称为除草剂(方案1:2,4-D,2,4-DP,2,4-DB,2,4,5-T和4-PA)。

除草剂能够在农业生态系统迁移,由于其在水中的溶解度,会造成地表水和地下水的污染。

方案1. 通过新型酰胺基硅胶色谱柱分离的植物激素的化学结构HPLC在分离这些极性植物激素的分析物方面是一种应用极为广泛的技术手柱测定生长素和脱落酸。

段。

液相色谱与质谱联用技术(LC-MS)也被提出用于C18然而,生长素,细胞分裂素,脱落酸有着非常不同的植物生理功能和化学性质。

所以研发用以分离不同组分植物激素的反相HPLC的固定相和分离方法非常具有挑战性。

基于我们的文献综述,关于处理不同类型的植物激素分离的文章很有限。

在过去的几年中,据报道Zhen Maa和其同事采用液相色谱与质谱联用技术通过色谱柱成功分离了四组激素。

作者指出该论文是第一个实现四种类型植物激C18素分离的文章。

在这个研究种,8种植物激素在50分钟内被分离出来。

在许多其他类似的研究,反相高效液相色谱法多用于激素测定和分离。

在我们广泛的文献回顾种,我们未能发现任何一篇描述用高效液相色谱法测定不同类别的十二个激素的分离。

因此,我们在这里描述的是一种新的酰胺固定相的发展,用作13种植物激素分离的一种色谱柱,包括吲哚-3-乙酸(IAA),吲哚丙酸(IPA),吲哚丁酸(IBA),脱落酸(ABA),玉米素(Z),6-苄氨基嘌呤(BAP),激动素(K),萘乙酸(NAA),2,4,5 -三氯苯氧乙酸(2,4,5-T),2,4-二氯苯氧基丙酸(2,4-DP),2,4-滴丁酸(2,4-DB),对氯苯氧乙酸(抑制)和二氯苯氧乙酸(2,4-D)(方案1)。

新型固定相的制备涉及酰胺配体和通过将该配体附于球形硅胶粒子表面(4mm,60Å)的改性硅胶的合成。

流动相,流速和温度,pH值等不同分离条件在这个13种植物激素系统中的保留行为的影响的被研究,12种植物激素会被分在两种不同的pH条件下对13种植物离出来。

现有市场上效果最好的ODS柱C18激素进行反相色谱反相,两类色谱柱所得的结果会相互比较。

两类色谱柱的最佳分离条件在图1和图2.中已经给出。

图1. 在最佳条件下,pH=6.85时,L-Pr-Si和ACE-C18两类色谱柱对植物激素的分离。

梯度洗脱:磷酸缓冲液中的ACN(pH:6.85,20mM), 0–20 min;10–25%, 20–30 min;25–90%.流速:0–13min;0.9mL/min,13–30dk;1.2mL/min。

温度:22℃。

注入量:5mL。

检测波长:230nm。

分析物:1:IAA,2: 4-PA,3.IPA,4:ABA,5:IBA,6:2,4-D,7:2,4-DP, 8:NAA,9:2,4,5-T, 10:Z,11:2,4-DB,12:K,13:BAP.实验2.1. 试剂和材料球型硅胶 (SuperSpher Si 60 ,4 mm, 60Å),购买于Merck公司。

硅胶 60 (Merck,0.040–0.063mm)和硅胶/TLC卡 (F254),分别用于柱的色谱分析和TCL。

ACE 5C柱 (250–4.6 mm,5 mm, 100Å,碳负载15.5%,表面积300m2/g) 用于作18对比。

HPLC中所用到的溶剂是HPLC级别的,购买于Merck公司。

所有被选用的分析物和其它反应物、试剂购买于Sigma-Aldrich公司和Merck公司。

除了特别说明,所有用于合成的试剂均为试剂级别。

通过带有空心毛细管的电热9300仪测定熔点。

红外光谱记录在Mattson 1000 FT-IR光谱仪上。

通过 Thermo Scientific FLASH 2000仪进行元素分析。

去离子水是用微孔Milli-Q水系统纯化而成的。

用JEOL/JSM-6510 LV仪器获得扫描电子显微镜(SEM)的图像。

1H(400 MHz)和13C核磁共振谱(100 MHz)记录于Bruker DPX-400高性能数字FT-NMR 仪器上。

化学位移(D)和耦合常数(J)分别用每百万分之( ppm)和赫兹表示。

图2. 在低pH(3.25)条件下,L-Pr-Si和ACE-C18两类色谱柱对植物激素的分离。

梯度洗脱:磷酸缓冲液中的ACN(10mM), 0–30 min,20–80%.流速:1mL/min。

温度:22℃。

注入量:5 mL。

检测波长:230nm。

分析物:1:IAA,2:4-PA,3.IPA,4:ABA,5:IBA,6:2,4-D,7:2,4-DP,8:NAA, 9:2,4,5-T, 10:Z,11:2,4-DB,12:K,13:BAP.2.2.HPLC的条件色谱设备由Agilent 1260高效液相色谱系统,包括一个四元泵,脱气器,自动进样器,DAD检测器和恒温柱室(Agilent,Waldbronn,德国)组成。

填充柱(250-4.6mm,不锈钢)在高压下采用注浆技术将改性硅胶填充到柱内。

每个分析物的标准溶液(1mg/ml)要在乙腈中制备,而激动素(K)、6-苄氨基嘌呤(BAP)要在30:70的乙腈-0.1 NaOH的混合物中制备。

所有的溶液都要存储在−25℃。

用水进一步稀释溶液以获得每100 ppm最终浓度的分析物(1300 ppm的总浓度)。

检测波长分别为230nm和275nm。

色谱条件不同于本章节中给出的条件中所描述的数据。

2.3. 合成2.3.1. N-Boc-酰胺(1)将二环己基碳二亚胺(DCC, 1.71g, 8.3mmol)溶解在DCM(15mmol)中,再添加到N-Boc-苯丙氨酸(2g、7.55mmol)和环己胺(820mg,8.3mmol)的搅拌混合溶液中,之后再加入到放置在0℃下1小时的二氯甲烷(15ml)中。

在室温下搅拌一晚后,再将混合物过滤、蒸发。

残留物被通过硅胶柱层析法(H:EtOAc=4:1) 纯化,得到的N-boc-酰胺(1)是一种白色固体。

产量:3.11g,90%.Mp:134–135. 1H NMR (CDCI3) :δ(ppm);0.90–1.95(m, 19H),2.91–2.99(m,1H),3.053.15(m,1H), 3.65–3.76(m,1H),4.18-4.27(m,1H),5.18(bs,1H),5.57(bs,1H),7.21–7.33 (m,5H).13C NMR (CDCI3):δ(ppm);26.64,25.41,32.71,38.96,48.08,56.73, 79.11, 126.90,128.64,129.38,136.95,155.35,169.90.IR ν (cm-1);3341, 3060,3020,29.60,2930,2853,1690,1649,15.38,1521,1449,1386,1291,1264,11 66,743,699.2.3.2. N-Boc基团的脱保护(2)将TFA/AcOH (1:1) (1.2mL)添加到N-boc-酰胺(1)(1g, 2.89mmol)与0℃下5ml的二氯甲烷的搅拌混合溶液中。

溶剂被蒸发以后,再向残留物中加入1 N NaOH(5mL)。

用DCM(3*15mL)对混合物进行萃取,再用Na2SO4进行干燥,之后进行再过滤、真空条件下蒸发。

最终得到纯净的酰胺(2)是一种白色固体。

Mp:217(分解)。

产量:710mg,99%. 1H NMR (CDCI3):δ(ppm); 1.1–2.2(m,12H),2.90–2.95 (m,1H),3.18–3.23 (m,1H),3.75–3.81 (m,1H),4.164.19(m,1H), 6.07(s,1H),7.19–7.33 (m, 5H).13C NMR(CDCI3):δ(ppm); 24.94,25.77,28.99, 37.78,51.29,57.44,127.28,128.66,129.44,134.97,173.17.IR ν(cm−1);32 59,3235,3100,3028,2936,2854,1701,1625,1569,1442,1338, 1348,1241,1192, 1111,764,696.2.3.3. 3-氯丙基硅烷(3)高品质的HPLC球形硅胶(4 mm, 60Å)悬浮于甲苯(60mL)中,再把3-氯丙基三甲氧基硅烷(2g,CPTMS 10mmol)添加到混合物中。

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