說明aps復(fù)習(xí)應(yīng)化

1、H U p The 3 laws of thermodynamics ：The increase inernal energy of a closed system is equal to the difference of the heatd to the system and the work done by it， ： ， ， ， 。（ H ） （ ） U H S G1. Chemical thermodynamics 。理想氣體狀態(tài)方程 The followingse functions 。 。 H H ： “” Heat cannot spontaneously flow from

2、a colder location to a hotter location. entropy（ ）V Zn +Cu2+ Zn2+ Cu The zinc electrode is dissolved and copper is deited on the copper electrode.zB:entropy of the room has decreased as some of its energy has been dispersed to the ice and water.In anisolated systemsuch as the room and ice water take

3、n together, the dispersal of energy from warmer to cooler always results in a net increase in entropy. Thus, when the universe of the room and ice water system has reached a temperature equilibrium, the entropy change from the initial se is at aum.The entropy of thethermodynamic systemis a measure o

4、f how far the equalization has progressed.Entropy is equally essential in predicting the extent and direction of complex chemical reactions.Third law of thermodynamics: As a system approaches absolute zero the entropy of the system approaches a minimum value.The entropy of rfect crystal, at absolute

5、 zero (zero kelvins), is exactly equal to zero.Absolute zero is 273.15C (degrees Celsius), or 459.67F (degrees Fahrenheit) or 0 K (kelvin).簡單計算：2.electrochemistry Galvanic cellIn its simplest form, ahalf-cellconsists of a solid metal (called anelectrode)t is submerged in a solution; the solution con

6、tainscationsof the electrode metalandanionsto balance the charge of the cations.A galvanic cell consists of two half-cells。heDaniell cell， the anode iszincand the cathode iscopper, and the anions in the solutions aresulfatesof the respective metals.the electrochemical reaction is:cCell voltageThe st

7、andard electrical potential of a cell can be determined by use of atablefor the twohalf cellsinvolved。standard potential standard electrode potential：E0, involts, for each of the twohalf reactions. The standard potential for the cell is equal to the more itiveE0value minus the more negativeE0value.s

8、tandard se, solutes at an effective concentration of 1moldm3,gases at a prere of 1 atm.The values are most often tabulated at 25 C.E E standard E E standard R R T a a a a c F F z Q ： for a cell at 25 C electrolytic cell 。 ： （ 陰極 ）Polychlorinated henyl Polychlorinated henyls (PCBs) have been concerns

9、 for decades due to their potential toxicity to human health. To trace the PCBs efficiently and sensitively, many detection methods have been manyysis methods have been reported. his thesis，aptamer witha specific recognition capability was combined with otoelectrochemical detection method with high

10、sensitivity. A kind of label-free aptamer-based otoelectrochemical biosensor was established, which combined the advantages of otoelectrochemical detection technology wiptamers technology.his pros, of all, the Ti substrate was treated by anodic oxidation he nitrogen doped precursor solution, then ni

11、trogen doped TiO2 nanotubes(N-doped TiO2 NTs)was obtained. By chitosan-glutaraldehyde crosslinking agent anti-PCB77 aptamer was fixed on the electrode surface ,DNA functionalized-CdS quantum dots formed on the complementary strands of aptamer and was connected to the surface ofthe biosensor.Through

12、these operations a kind of simple, ra and label-free aptamer-based otoelectrochemical biosensor was constructed, which realized the detection of pollutants PCB77 with high sensitivity and high specificity, and won the wide linear range from 8.010-10 to 1.010-7 g/L,the minimum detection limit up to 3

13、.010-11 g/L. Briefly, a new type of otoeletrochemical biosensing technology for the detection of polychlorinated henyl compounds was established，which has a widebroad application prospect.Polychlorinated henyls (PCBs)：1.Apolychlorinatedhenyl(PCB) is a syntheticanic chemical compoundofchlorine attach

14、ed torings.henyl, which is a molecule comed of twobenzene 2.persistentanic pollutants，Due to their lowvapour prere, PCBs accumulate primarilyhehydrosere,heanic fraction ofsoil, and inanisms.（oil symptoms， was a mass poisoning bypolychlorinated henyls(PCBs) which occurredinJapan in 1968.）To trace the

15、 PCBs efficiently and sensitively, many ysis methods have been reported. In this thesis，aptamer wi specific recognition capability was combined with otoelectrochemical detection method with high sensitivity.1. aptamer：（specific recognition）（ bio-recognitionelement 識別元件） They consist of strands of ol

16、igonucleotides（a base sequent bind to a specific ）， molecule. through literature ，we get the specificsequenceofanti-PCB77 aptamer.2.semiconductormaterial：（used asotoresistors，he visible light，the materialgive a current。）Cadmium sulfide quantum dots：smaller sizenNano-particle5-10nm，currentis high。Tit

17、anium dioxide nanotubes：a goodcurrent stability3.how to bild the biosensor（theworking electrode）his pros, of all, the Ti substrate was treated by anodic oxidation he nitrogen doped precursor solution, then nitrogen doped TiO2 nanotubes(N-doped TiO2 NTs)was obtained.By chitosan-glutaraldehyde crossli

18、nking agent anti-PCB77 aptamer was fixed on the electrode surface ,DNA functionalized-CdS quantum dots formed on the complementary strands of aptamer and was connected to the surface of the biosensor.4.working mechanismworkable。5.equipmentElectrochemical worksionexists，irecord the light current he v

19、isible light（），then make the concentration-light current line。According to the linear relationship betnconcentration andlight current，ivedetermination of PCB77 is傳感器的工作基理：當(dāng) PCB77 存在時，傳感器在可見光下進(jìn)行工作，由于適配體與靶物 PCB77 親和力更高，更傾向于與 PCB77 結(jié)合，CdS QDs 及適配體互補(bǔ)鏈部分被待測物取 代。一 方面，N-doped TiO2 NTs 修飾電極失去了 CdS QDs 提供的光電

20、流，光電流變?。涣硪环矫妫m配 體與靶物 PCBB77 特異性結(jié)合，在電極表面形成配合物，抑制了電子的擴(kuò)散，同樣使光電流變小。 故隨著 PCB77 濃度增大，被取代下的 CdS QDs 增多，傳感器光電響應(yīng)逐步減小，創(chuàng)建了電流抑 制型檢測模式。傳感器將 PCB77 濃度變化反映為電流變化，通過對光電流的監(jiān)測，建立 PCB77 濃度與光電流的線性關(guān)系，完成對 PCB77 的定量分析。 wheB77 exists，he visible light，the biosensor works。because the affinity betn the aptamer and PCB77 is highe

21、r，the aptamer will be combined withPCB77，at the sametime theDNA functionalized-CdS quantum dotswill be replaced。，the work electrose the light current given by the cds qds，secondly，the aptamer and the pcb77 form a kind of complex，understericeffects，itinhibits thediffu ofelectrons。in a word，the concen

22、tration of PCB77 is higher，the light current is lower。 he three-electrode system，wheB77 （of diffrent concentration）光譜紫外（激發(fā) 應(yīng)用（共軛）定量 定律裝置實(shí)驗） 范圍： 可見光區(qū)（）：近紫外光區(qū)：TheBeer-Lambert law AU AU 。 spectrootometer 應(yīng)用裝置：鎢：濾光片：單色光源 ：劈分器 ：光敏二極 管例子： transmittance aseriesof光譜-紅外Infrared spectroscopyInfrared spectrosc

23、opy(IR spectroscopy) is thespectroscopyt deals withtheinfraredregion of theelectromagnetic spectrum。The mid-infrared, approximay4000400cm1(2.525m) may be used to study the fundamental vibrations and assotedroional-vibrationalstructure.Infrared spectroscopyexploits the factt molecules absorb specific

24、 frequenciest are characteristic of theirstructure. These absorptions areresonant frequencies, i.e.the frequency of the absorbed radiation matches the transition energy of the bondroupt vibrates.the frequency of the vibrations are assoted wiparticular normal mode of motion and a particular bond type

25、.functional groups、inferA molecule can vibrateany ways, and each way is called avibrational mode.For molecules with N number of atomshem, linear molecules have 3N 5 degrees of vibrational modes, whereas nonlinear molecules have 3N 6 degrees of vibrational modes (also called vibrational degrees of fr

26、eedom). As an ex leH2O, a non-linear molecule, will have 3 3 6=3 degrees of vibrational freedom, or modes.A basicIR spectrumis essentially a graof infraredlightabsorbance(ortransmittance)，the abscissa axis is wave number ,the ordinate axis is absorbance .like the absorption peak of ethene located in

27、 1680-1620cm-1,he experiment course, we used the ultraviolet absorption spectrometry to measure the Vc content in Vitamin C Tablets. C6H8O6.,repared the solution of CH3COOH, CH3COONa and EDTA-2Na, because the Vc is stablehis kind solution. Then we make up the solutions containing 4,6,8,10,12ug/ml Vc

28、.(standard solution) Then we tested the absorbancehe wavelength of 265.4nm. we got the datas and then draw the line of A=abc. The next stst we prepared the solution of the Vitamin C Tablets. We get the A of the solution and findout the che line.IR spectroscopy apparatusmolecular vibration or the mol

29、ecular roion pro例子Hydroxyl、carboxylicacid、absorbtion bandcarbonyl transmittance 羧基 carboxyl Nuclearmagneticresonancespectroscopy,mostcommonlyknownasNMR spectroscopy, is a research techniquet exploits themagneticproperties of certainatomic nuclei. It res on theenomenon ofnuclear magnetic resonance， T

30、he frequency, thus giving acs to details of the electronic structure of a molecule.When placedin a magnetic field, NMR active nuclei (such as1H or13C) absorbelectromagnetic radiationat a frequency characteristic of theisotope.Suitable s les range from small compoundsyzed with 1-dimen al proton or ca

31、rbon-13 NMRspectroscopy to large proteins or nucleic acids using 3 or 4-dimen al techniques.inanic chemistry practice, NMR ysis is used to confirm the identity of a substance. Different functional groups are obviously distinguishable, and identical functional groups with differing neighboring substi

32、tuents still give distinguishable signals.The NMR sle is prepared in a thin-walled glass tube - anNMR tube.（ it is applicable toany kind of slet contains nucleisessingspin.）DieKernspinresonanzspektroskopie(NMR-Spektroskopievonenglischnuclear magnetic resonance) ist einespektroskopische Methodezur Un

33、tersucg der elektronischen Umgebung einzelner Atome und der Wechselwirkungen mit den Nachbaratomen. Dies ermglicht die Aufklrung der Struktur und der Dynamik von Molek len sowie Konzentrationsbestimmungen.Die Methode beruht auf dermagnetischen Kernresonanz,einerresonantenWechselwirkung zwischen demm

34、agnetischenMomentvonAtomkernendrobe, die sich in einem starken sischen Magnetfeld befindet, mit einem hochfrequenten magnetischen Wechselfeld. Es sind nursolcheIsotopeder Spektroskopie zugnglich, die im Grundzustand einen von NullverschiedenenKernspinund damit eagnetisches Moment besitzen.ramolecula

35、r magnetic field around an atom in a molecule changes the resonanceChemical shiftThe chemical shift provides information about the structure of the molecule. The converof the raw data to this information is calledassigningthe spectrum. For exle, forthe1H-NMR spectrum for enol (CH3CH2OH),ould expect

36、signals at each of threespecific chemical shifts: one for theCH3group, one for theCH2group and one for theattached to an OH has aOHgroup. A typical CH3grouas a shift around 1 ppm, a CH2shift of around 4 ppm and an OH has a shift anywhere from 26 ppm depending on the solvent used and the amount ofhyd

37、rogen bonding.炔烴氫 1.6-3.4ppm4.5-7.5ppm9-10.5ppm 0.5-5.5ppm烯烴醛基羥基J-couplingSome of the most useful information for structure determination in a one-dimenspectrum comes fromJ-coupling（ spin-spin coupling）。al NMRFor exle,he proton spectrum for enol described above, the CH3group is splitoatripletwinensi

38、ty ratio of 1:2:1 by the two neighboring CH2protons. Similarly,the CH2is splito aquartetwinCH2ensity ratio of 1:3:3:1 by the three neighboringCH3protons. In principle, the twoprotons would also be split againoadoubletto form adoublet of quartetsby the hydroxyl proton, butermolecularexchange of the a

39、cidic hydroxyl proton often results in a loss of coupling information.例子In HNMR,the abscissa is chemical shift represent the location of absorption peak ,theordinate is the strength of absorption peak.three groupsof peaks=three kinds of Hrroundingsthe nummber of peaks splitting=the nummber ofneighbo

40、ring H（n+1）chemical shift=炔烴氫 1.6-3.4ppmsible chemical surroundings of the H4.5-7.5ppm9-10.5ppm 0.5-5.5ppm烯烴醛基羥基操作：The NMR sle is prepared in a thin-walled glass tube - anNMR tube.solution：氘代氯仿、CDCl3、Chloroform-d。（0.1-0.01 mol/L）譜圖Mass spectrometryMass spectrometry(MS) is anytical chemistrytechnique

41、t measuresthemass-to-charge ratioand abundance of gas-aseions.The spectra are used todetermine the elementalof a sle, the masses of particles and ofmolecules, and toelucidate the chemical structures of molecules。Mass spectrometry works byionizingchemical compounds to generate chargedmolecules or mol

42、ecule fragments and measuring their mass-to-charge ratios.1.In a typicaprocedure, a sle, whiay be solid, liquid,as, iized, forexbreaky bombarding it with electrons.This may cause some of the so charged fragments.les molecules to2.These ions are then separated according to their mass-to-charge ratio,

43、 typically byaccelerating them and subjecting them to an electric or magnetic field: ions of the samemass-to-charge ratio wildergo the same amount of deflection.3.A mass spectrometer consists of three components: an ion source, a massdetector.yzer, and aTheionizerconverts a portion of the sleoions.A

44、nextraction systemremoves from the sle, which are then trajected throughthe massyzer and onto thedetector.The differenasses of the fragments allows themassyzertosort theionsby their mass-to-charge ratio。Thefordetectormeasures the value of an indicatorty and thus provides datacalculating the abundano

45、f each ionpresent。Lorentz force lawIn high vacuum system ,test the ssure the relative molecular mass of sles of molecular ion and fragment ion mass ,to makeles and molecular struchture。例子：They are used inotogray, i.e., AgBr forms a soluble complex withsodiumClassical：Ligands in classical coordinatio

46、n chemistry bind to metalsanometallic Chemistry: Ligands areanic (alkenes, alkynes, alkyls)Bioinanic Chemistry: Ligands are those provided by nature, espe lly including the side chains of amino acids, and manycofactorch asporyrins.Cluster Chemistry: Ligands are all of the above also include other me

47、tals as ligands.配位化學(xué)The study of coordination chemistry is the study of in anic chemistry of all alkali and alkaline earth metals, transition metals, lan nide inides, and metalloids. Thus, coordination chemistry is the chemistry of the majority of the periodic table. Metals and metal ions exist, he

48、condensed ases east, only surrounded by ligands.1. In chemistry, a coordination complex or metal complex consists of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, t are in turn known as ligands or complexin

49、g agents。In coordination chemistry, a structure isdescribed by its coordination number, the number of ligands attached to the metal (more specifically, the number of donor atoms). Coordination numbers are normally bet n two and nine, （but large numbers of ligands are notmon for the lan nides and act

50、inides）. The number of bonds depends on the size, charge, and electron configuration of the metal ion and the ligands. Metal ions may have more n one coordination number.Typically the chemistry of transition metal complexes is dominated by eractions bet n s and p molecular orbitals of the ligands an

51、d the d orbitals of the metal ions. The s, p, and d orbitals of the metal canmodate 18 electrons (see 18-Electron rule).The areas of coordination chemistry can be classified according to the nature of the ligands。鹵代烴 halohydrocarbon CH3CH2CL:64=CH2=CL+:49=CH3-CH2+:29配位 構(gòu)型圖形3D實(shí)例數(shù)直線HgCl2、Ag(NH3)2+、2型A

52、u(CN)2Dh平面 三角HgI 、Pt(P) 、333 3形FeN(Si(CH ) ) 3 3 2 3四面 Ni(CO)4、MnO4、S體nCl44平面 正方cisPt(NH3)2Cl2、Pt形Cl42、Ni(CN)42三角 雙錐Fe(CO)5、CdCl535四方 錐InCl52、SbF52thiosulfateinotogray.electrosic repulOctahedralCrystal Field Theory(CFT) Highspin and lowspinThe octahedral ion Fe(NO2)63, which has 5delectrons, would h

53、ave the octahedral splitting diagram shown at right will five electronshet2glevel.the ion FeBr63, again with fivedelectrons, would have an octahedral splitting diagram where all five orbitals are singly occupied.Ti(H2O)63+、Co(e八面 6n)33+、Cu(NH3)6體2+五角ZrF72、UO2F537雙錐complementarycoloursIsomerismCispla

54、tinancer drugs首先移除一個環(huán)戊二烯基負(fù)離子，得到含有 12 個價電子的正離子。每個羰基給出 2個電子，因此根據(jù) 18 電子規(guī)則，以下正離子應(yīng)該是穩(wěn)定的：CpFe(CO)3+事實(shí)上，該配合物以另式滿足 18 電子規(guī)則，即生成環(huán)戊二烯基羰基鐵Fe(5-C5H5)(CO)22，參見#衍生物。在算這個化合物中一個鐵原子的價電子數(shù)時，可認(rèn)為另一個鐵原子貢獻(xiàn)了一個電子：Cp 5 + Fe 8 + 2 CO 2 + Fe 1 = 18此外，用另一個單負(fù)離子配體也可使其達(dá)到 18 電子：CpFe(CH3)(CO)2Cp 5 + Fe 8 + CH3 1 + 2 CO 2 = 18Isolobal

55、 principle有機(jī)金屬the goal of this kurs ist， know some basic and simple theory ofanometallic chemistry，and ourlecturerroduome famousliterature，and some classical reactions。anometallic chemistryis the study ofchemical compoundscontainingeastonebondbetn acarbonatom of ananic compound and ametal.M-L， now，

56、most study of this chemistry is about the trasition metalThe18-electron ruleis a rule used for predictingstability ofmetal complexes.The rule is based on the factt thevalensoftransition metalsconsist of nine valence orbitals, which can hold 18electronsas either bonding or nonbonding electron pairs.W

57、hen a metal complex has 18 valence electrons, it meanst is the same electron configuration as thenoble gashe period.例如在判斷是否可以將中一個（Cp）用羰基替換時，有機(jī)實(shí)驗：乙酸乙酯的（Preparation of ethyl acee）main reaction / side reaction:TheSuzuki reactionis theanic reactiont is classified as acoupling reactionwhere the coupling

58、partners are aboronic acidwithahalidecatalyzed by apalladium(0) complex.Teral scheme for the Suzuki reaction is shown below where you form a carbon-carbon sing ond by couplinrganoboron species (R1-BY2) with a halide (R2-X) using a palladium catalyst and a base.its a reversible reaction and esterific

59、ation reaction, so it need to putexs acid or remove the water.mechanism：dehydrated alcohol無水乙醇glalaceticacid冰醋酸concentrated sulfuric acid濃硫酸Saturated sodium carbonate飽和碳酸鈉Saturatedsodium chloride飽和氯化鈉Saturated calcium chloride飽和氯化鈣anhydrous magnesium sulfate無水硫酸鎂refluxdevice回流distillation蒸餾1. put 9.

60、5ml anhydrous alcohol，6ml glal acetic acid in a round-bottomed flask，then put2.5 ml concentrated sulfuric acid。shake it，then put 1/2 zeolits in。connect it wicondensipe to bild a reflux device。2.heat it in water bath for 0,5 H。change the device to a distillation。get the crude product 。3. put saturate