变温红外光谱研究多嵌段聚氨脂脲的微相分离行为

用傅里叶变换红外光谱方法研究了热处理对由聚环氧丙烷聚醚多元醇、３．５－二乙基甲苯二胺和４，４－二苯基甲烷二异氰酸酯组成的多嵌段聚氨酯脲（ＳＰＵＵ）的微相分离行为的影响．从室温逐步升温到３１０℃的过程中，氨基甲酸酯键（ＵＴ）之间形成的氢键大量解离，而脲键（ＵＡ）之间形成的、具有平面状双分叉结构的氢键在１３０～２００℃范围却大量生成；从３１０℃缓慢冷却到室温后，部分游离的ＵＴ重新形成氢键，而硬段之间形成的ＵＡ氢键的含量又有所增加．结果表明：高温热处理可以有效地提高ＳＰＵＵ的微相分离程度．     

3—吡唑基—6—取代均三唑并[3,4—6]—1,3,4—噻二唑的合成及生物活性

以１－甲基－３－乙基（４－氯）－５－哟唑甲作原料，经两步得到４－氨基－３－（１－甲基－３－乙基（４－氯）－５－吡唑基）－１，２，４－三唑－５－硫酮（３），３再与取代酸反应，得到一系列３（１－甲基－３－，乙基（－４－氯）－５－吡唑基）－６－取代均三并「３，４－ｂ」－１，３，４－噻二唑（４，５，６），元素分析、ＨＮＭＲ、ＩＲ和ＭＳ确定了它们的结构，初步生侧结果表明，３具有植物生长调节活性，４ｂ、４ｄ、     

对称三唑Schif碱和氯化铜配合物的研究

本文介绍水 杨醛与４－氨基－３，５－二乙基－１，２，４－三唑缩合而成对称三唑Ｓｃｈｉｆｆ碱与氯化铜形成一种新的配合物Ｃｕ（ＳＡＥＴＺ）２（ＳＡＥＴＺ＝４－（邻羟苯基亚甲基）－亚胺－３，５－二乙基－１，２，４－三唑）。     

3-吡唑基-6-取代均三唑并[3,4-b]-1,3,4-噻二唑的合成及生物活性

以１－甲基－３－乙基（－４－氯）－５－吡唑甲酰肼作原料，经两步得到４－氨基－３－（１－甲基－３－乙基（－４－氯）－５－吡唑基）－１，２，４－三唑－５－硫酮（３），３再与取代羧酸反应，得到一系列３－（１－甲基－３－乙基（－４－氯）－５－吡唑基）－６－取代均三唑并［３，４－ｂ］－１，３，４－噻二唑（４、５、６）．元素分析、１ＨＮＭＲ、ＩＲ和ＭＳ确定了它们的结构．初步生测结果表明：３具有植物生长调节活性，４ｂ、４ｄ、６具有杀菌活性．     

对称三唑Schif碱和氯化铜配合物的研究

本文介绍水杨配合与４－氨基－３，５－二乙基－１，２，４－三唑缩合而成对称三唑Ｓｃｈｉｆ碱（ＳＡＥＴＺ）与氯化铜（ＣｕＣｌ２）形成一种新的配合物Ｃｕ（ＳＡＥＴＺ）２（ＳＡＥＴＺ＝４－（邻羟苯基亚甲基）－亚胺－３，５－二乙基－１，２，４－三唑）。配合物的晶体结构表明，分子中两个偶氮甲碱的Ｎ原子及两个酚氧原子与中心Ｃｕ原子形成规则的平面配位结构。晶体属单斜晶系，空间群Ｐ２１／ｎ，ａ＝８．６８８（２），ｂ＝９．３１４（１），ｃ＝１６．５１５（４），β＝９４．３４（２）。，Ｖ＝１３３２．５（７）３，Ｚ＝２。     

RIM聚氨酯脲的微相分离的DSC研究──硬段结构和含量对微相分离的影响

用ＤＳＣ法研究了二乙基甲苯二胺和４，４＇－氨基二苯基甲烷（ＭＤＡ）扩链的硬段含量为２７％～６０％的两个系列的反应注射成型（ＲＩＭ）聚氨酯脲（ＰＵＵ）弹性体的微相分离。聚合反应动力学对ＲＩＭＰＵＵ的微相分离有很大影响．随着硬段浓度的增加微相分离程度下降，ＭＤＡ扩链系列聚合总反应速度快，微相分离驱动力弱，在硬段生成反应比软段生成反应快的条件下，该系列的微相分离程度较低。聚合总反应快，且硬段间氢键化作用很强的性质造成ＲＩＭＰＵＵ非平衡的形态。聚合总反应速度的增加相当于微相分离驱动力的下降。     

3,4—二乙酰基—2,5—己二酮与取代苯胺及水合肼的反应

以乙酰丙酮（１）的电氧化偶联产物３，４－二乙酰基－２，５－己二酮（２）为原料，在酸性介质中与取代苯胺（３ａ￣３ｇ）作用，得到１，４－二羰基的缩合产物２，５－二甲基－３，４－二乙酰基－１－芳基吡咯（４ａ￣４ｇ）。在相似的条件下，２与水合肼作用，则得到１，３－二羰基的缩合产物３，３＇，５，５＇－四甲基－１，１＇－二氢－４，４＇－联吡唑（５）。     

双（取代环戊二烯基）二氯化锆的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了双［１－苄基－１－乙基丙基环戊二烯基］二氯化锆［η５－Ｃ５Ｈ４Ｃ（Ｃ２Ｈ５）２ＣＨ２Ｃ６Ｈ５］２ＺｒＣｌ２（Ｉ）及（１，２－二异丁基－１，２－甲基－乙基桥联）双环戊二烯基二氯化锆［η５－Ｃ５Ｈ４Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ５Ｈ４－η５］ＺｒＣｌ２（Ⅱ）的结构。二者皆为单斜晶系，（Ｉ）的空间群为Ｐ２／ｎ，ａ＝１２．５８２（３），ｂ＝７．９９２（２），ｃ＝１４．９７９（３）Ａ，β＝１０１．６８（１）°，Ｖ＝１４７４．９（９）Ａ３，Ｍｒ＝６１２．８４，Ｚ＝２，Ｄｘ＝１．３８ｇ／ｃｍ３，μ＝５．６９ｃｍ（－１），Ｆ（０００）＝６４０，Ｒ＝０．０３３，Ｒω＝０．０３６。（Ⅱ）的空间群为Ｃｃ，ａ＝１３．３０９（３），ｂ＝９．５９１（１），ｃ＝１６．４４９（８）Ａ。β＝４．８３（３）°，Ｖ＝２０９．２（２）Ａ３，Ｍｒ＝４５８．６３，Ｚ＝４，Ｄｘ＝１．４５６ｇ／ｃｍ３，μ＝７．７７ｃｍ（－１），Ｆ（０００）＝９５２，Ｒ＝０．０５１，Ｒω＝０．０６１。化合物（Ｉ）以重叠式存在，两个苄基处于反式。晶体（Ⅱ）以交叉式存在，甲基、异丁基以反式构象存在。     

2－乙基－3，5－二甲基吡啶合成新工艺

２－乙基－３，５－二甲基吡啶合成新工艺肖国民，吴平东（浙江大学二次资源化工国家专业实验室，杭州３１００２７）２－乙基－３，５－二甲基吡啶（ＥＤＰ）是合成２，３，５－三甲基吡啶［１］、３，５－二羧基吡啶和２－乙烯基－３，５－二甲基吡啶［２，３］等的重要...     

RIM聚氨酯脲的微相分离的DSC研究—硬段结构和含量对微相…

用ＤＳＣ法研究了二乙基甲苯二胺和４，４＇－二氨基二苯基甲烷扩链的硬段含量为２７％－６０％的两个系列的反应注射成型聚氨酯脲弹性体的微相分离，聚合反应动力学对ＲＩＭ ＰＵＵ的微相分离有很大影响，随着硬段浓度的增加微相分离程度下降，ＭＤＡ扩链系列聚合总反应速度快，微相分离驱动力弱，在硬段生成反应比软段生成反应快的条件下，该系列的微相分离程度较低，聚合总反应快，且硬段间氢键化作用很强的性质造成ＲＩＭ ＰＵ     

Raman spectroscopy of urea and urea-intercalated kaolinites at 77 K

The Raman spectra of urea and urea-intercalated kaolinites have been recorded at 77 K using a Renishaw Raman microprobe equipped with liquid nitrogen cooled microscope stage. The NH2 stretching modes of urea were observed as four bands at 3250, 3321, 3355 and 3425 cm(-1) at 77 K. These four bands are attributed to a change in conformation upon cooling to liquid nitrogen temperature. Upon intercalation of urea into both low and high defect kaolinites, only two bands were observed near 3390 and 3410 cm(-1). This is explained by hydrogen bonding between the amine groups of urea and oxygen atoms of the siloxane layer of kaolinite with only one urea conformation. When the intercalated low defect kaolinite was cooled to 77 K, the bands near 3700 cm(-1) attributed to the stretching modes of the inner surface hydroxyls disappeared and a new band was observed at 3615 cm(-1). This is explained by the breaking of hydrogen bonds involving OH groups of the gibbsite-like layer and formation of new bonds to the C=O group of the intercalated urea. Thus it is suggested that at low temperatures two kinds of hydrogen bonds are formed by urea molecules in urea-intercalated kaolinite.     

Orbital interactions in Fe(II)/Co(III) heterobimetallocenes: single versus double bridge

Ferrocenyl cobaltocenium hexafluorophosphate (1) and ferrocenylene cobaltocenylenium hexafluorophosphate (2) are investigated by a range of spectroscopic methods. Both compounds are diamagnetic, in contrast to an earlier report indicating a temperature-dependent paramagnetism of 2. Electronic absorption spectra of 1 and 2 are presented and fully assigned up to 50 000 cm(-1) on the basis of electronic structure (DFT) calculations and spectral comparisons with ferrocene and cobaltocenium. The lowest-energy bands, I, of both 1 and 2 correspond to metal-to-metal CT (MMCT) transitions; further intermetallocene charge-transfer bands are identified at higher energy (bands III and V). On the basis of the spectroscopic properties, a trans geometry and a twisted structure are derived for 1 and 2, respectively, in solution. Analysis of the I bands gives orbital mixing coefficients, alpha, electronic-coupling matrix elements, V(AB), and reorganization energies, lambda. Importantly, alpha and V(AB) are larger for 1 than for 2 (0.07 and 1200 cm(-1) vs 0.04 and approximately 600 cm(-1), respectively), apparently in contrast to the presence of one bridge in 1 and two bridges in 2. This result is explained in terms of the respective electronic and geometric structures. Reorganization energies are determined to be 7600 cm(-1) for 1 and 4600 cm(-1) for 2, in qualitative agreement with the analogous Fe(II)-Fe(III) compounds. The general implications of these findings with respect to the spectroscopic and electron-transfer properties of bimetallocenes are discussed.     

Non-destructive rapid analysis discriminating between chromium(VI) and chromium(III) oxides in electrical and electronic equipment using Raman spectroscopy.

The European Union has banned chromium(VI) compounds in electrical and electronic equipment (EEE), such as chromate conversion coating films. Chromium(III) compounds are not banned. Using Raman spectroscopy without any preparation, we distinguished chromium(VI) oxide from chromium(III) oxide and chromium(III) hydroxide in chromate conversion coating films. Raman bands of chromium(VI) oxide were detected in films at around 1000 and 500 cm(-1), while chromium(III) compounds generated no bands in the region between 2000 and 200 cm(-1). The analysis took about 1 min, whereas the usual diphenylcarbazide-colorimetric method for analyzing chromium(VI) compounds takes about 10 h.     

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds in Scots pine (Pinus sylvestris) wood. Part II. Hydrophilic compounds

Hydrophilic extracts of Scots pine (Pinus sylvestris) heartwood and sapwood and a solid Scots pine knotwood sample were studied by UV resonance Raman spectroscopy (UVRRS). In addition, UVRR spectra of two hydrophilic model compounds (pinosylvin and chrysin) were analysed. UV Raman spectra were collected using 244 and 257 nm excitation wavelengths. The chemical composition of the acetone:water (95:5 v/v) extracts were also determined by gas chromatography. The aromatic and oleophilic structures of pinosylvin and chrysin showed three intense resonance enhanced bands in the spectral region of 1649-1548 cm(-1). Pinosylvin showed also a relatively intense band in the aromatic substitution region at 996 cm(-1). The spectra of the heartwood acetone:water extract showed many bands typical of pinosylvin. In addition, the extract included bands distinctive for resin and fatty acids. The sapwood acetone:water extract showed bands due to oleophilic structures at 1655-1650 cm(-1). The extract probably also contained oligomeric lignans because the UVRR spectra were in parts similar to that of guaiacyl lignin. The characteristic band of pinosylvin (996 cm(-1)) was detected in the UVRR spectrum of the resin rich knotwood. In addition, several other bands typical for wood resin were observed, which indicated that the wood resin in the knotwood was resonance enhanced even more than lignin.     

Investigation of Syntheses and Spectra (UV,IR,CV) of Some Fe3S3 Cluster Compounds

1　INTRODUCTIONIron- sulfurproteins are found in mostofthe life forms,yetitisnotuntilaround1 96 0 that there are iron- sulfur proteins in photosynthetic organism〔1〕,nitrogen- fix-ing bacteria〔2〕,and submitochondrial fractions of mammalian origin〔3〕,etc〔4 ,5〕,it isoxidoreductive systems.There are various kinds of iron- sulfur clusters active posi-tions in these proteins,they play an important role in transmitting electrons.Bymany kinds and complex properties of biology,different iro…     

Synthetic deuterated erythrite--a vibrational spectroscopic study

A comparison of deuterated and non-deuterated erythrite has been made using a combination of infrared and Raman spectroscopy. Infrared spectrum shows bands at 3442, 3358, 3194 and 3039 cm(-1). The band at 3442 cm(-1) is attributed to weakly hydrogen bonded water and the band at 3039 cm(-1) to strongly hydrogen bonded water. Deuteration results in the observation of OD bands at 2563, 2407 and 2279 cm(-1). The ratio of these bands change with deuteration. Deuteration shows that the strongly hydrogen bonded water is replaced in preference to the weakly hydrogen bonded water. Three HOH bending modes are observed at 1686, 1633, 1572 and DOD bending modes at 1236, 1203 and 1176 cm(-1). Deuteration causes the loss of intensity of the bands at 841, 710 and 561 cm(-1) and new bands are observed at 692, 648 and 617 cm(-1). These three bands are attributed to the water librational modes. Deuteration results in an additional Raman band at 809 cm(-1) with increasing intensity with extent of deuteration. Deuteration results in the shift of Raman bands to lower wavenumbers.     

A Raman spectroscopic study of the uranyl sulphate mineral johannite

Raman spectroscopy at 298 and 77K has been used to study the secondary uranyl mineral johannite of formula (Cu(UO2)2(SO4)2(OH)2 x 8H2O). Four Raman bands are observed at 3593, 3523, 3387 and 3234cm(-1) and four infrared bands at 3589, 3518, 3389 and 3205cm(-1). The first two bands are assigned to OH- units (hydroxyls) and the second two bands to water units. Estimations of the hydrogen bond distances for these four bands are 3.35, 2.92, 2.79 and 2.70 A. A sharp intense band at 1042 cm(-1) is attributed to the (SO4)2- symmetric stretching vibration and the three Raman bands at 1147, 1100 and 1090cm(-1) to the (SO4)2- anti-symmetric stretching vibrations. The nu2 bending modes were at 469, 425 and 388 cm(-1) at 77K confirming the reduction in symmetry of the (SO4)2- units. At 77K two bands at 811 and 786 cm(-1) are attributed to the nu1 symmetric stretching modes of the (UO2)2+ units suggesting the non-equivalence of the UO bonds in the (UO2)2+ units. The band at 786cm(-1), however, may be related to water molecules libration modes. In the 77K Raman spectrum, bands are observed at 306, 282, 231 and 210cm(-1) with other low intensity bands found at 191, 170 and 149cm(-1). The two bands at 282 and 210 cm(-1) are attributed to the doubly degenerate nu2 bending vibration of the (UO2)2+ units. Raman spectroscopy can contribute significant knowledge in the study of uranyl minerals because of better band separation with significantly narrower bands, avoiding the complex spectral profiles as observed with infrared spectroscopy.     

An ATR-FTIR study of different phosphonic acids in aqueous solution

An ATR-FIR study of the vibrational spectra of 1-hydroxyethane-1,1'-diphosphonic acid (HEDP), nitrilotris(methylenephosphonic acid) (NTMP) and N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid (BHAMP) in aqueous solution is presented. The study was performed in the range of pH from 5 to 9, and bands assignments are given in the 2000-890 cm(-1) range. However, as phosphonates display bands due to the PO stretching vibration mainly in the 900-1200 cm(-1) range, the study is focused in this midinfrared region, which shows important changes as the pH changes, specially the nu(POH) at approximately 925 cm(-1) and nu(PO(3)(2-)) at approximately 970 cm(-1) vibrations. IR analyses give also evidences for the zwitterionic nature of BHAMP and NTMP in solution with a strong indication that the zwitterion in both compounds remains intact throughout the pH range investigated. The successive protonation steps with the decrease of pH were evidenced in the IR spectra of the three studied phosphonates.     

Luminescence properties of C-diazaborolyl-ortho-carboranes as donor-acceptor systems

Seven derivatives of 1,2-dicarbadodecaborane (ortho-carborane, 1,2-C(2)B(10)H(12)) with a 1,3-diethyl- or 1,3-diphenyl-1,3,2-benzodiazaborolyl group on one cage carbon atom were synthesized and structurally characterized. Six of these compounds showed remarkable low-energy fluorescence emissions with large Stokes shifts of 15100-20260 cm(-1) and quantum yields (Φ(F)) of up to 65% in the solid state. The low-energy fluorescence emission, which was assigned to a charge-transfer (CT) transition between the cage and the heterocyclic unit, depended on the orientation (torsion angle, ψ) of the diazaborolyl group with respect to the cage C-C bond. In cyclohexane, two compounds exhibited very weak dual fluorescence emissions with Stokes shifts of 15660-18090 cm(-1) for the CT bands and 1960-5540 cm(-1) for the high-energy bands, which were assigned to local transitions within the benzodiazaborole units (local excitation, LE), whereas four compounds showed only CT bands with Φ(F) values between 8-32%. Two distinct excited singlet-state (S(1)) geometries, denoted S(1)(LE) and S(1)(CT), were observed computationally for the benzodiazaborolyl-ortho-carboranes, the population of which depended on their orientation (ψ). TD-DFT calculations on these excited state geometries were in accord with their CT and LE emissions. These C-diazaborolyl-ortho-carboranes were viewed as donor-acceptor systems with the diazaborolyl group as the donor and the ortho-carboranyl group as the acceptor.     

The infrared and Raman spectra of trans- and cis-tetrachloro-tetramethylbicyclopropylidene

The title compounds trans- and cis-2,2,2',2'-tetrachloro-3,3,3',3'-tetramethyl-bicyclopopylidene were synthesized, and their infrared and Raman spectra were recorded. Non-coincidence between the IR and Raman bands of the trans compound suggested C(2h) symmetry and a planar ring system. In the cis compound most of the IR and Raman bands coincided and a C(2v) symmetry seems likely. The exocyclic CC double bond gave rise to a medium/weak Raman band at 1,847 cm(-1) in the trans compound. In the cis derivative IR and Raman bands both at 1,825 cm(-1) were observed. From similarities with related molecules, the ring breathing, the antisymmetric ring stretch, the CCl(2) out-of-phase and in-phase stretch and the out-of-plane ring bending modes have been tentatively assigned for the trans and cis compounds.