低能铁离子束辐照氨基酸衍生物的红外光谱结构表征

利用傅里叶变换红外光谱 (FTIR)技术研究了能量为 110keV的Fe+离子束辐照L(+) 半胱氨酸盐酸盐单晶水合物固态样品的结构变化情况。对辐照样品的两次红外光谱分析结果有所不同 ,表明固态样品不同部位受低能铁离子束作用后可发生不同的分子改性 ;但二者又具有一定的相似性 ,都反映了原分子中氨基、羧基和巯基等基团的受损及硝基和酰胺基团等的生成。

玉米品种和淀粉老化处理对其红外光谱结构与体外发酵参数的影响

本试验旨在研究不同玉米品种[普通玉米和高直链淀粉玉米(简称高直玉米)]和淀粉老化处理对其营养成分、傅里叶变换红外光谱(FTIR)分子结构以及体外发酵参数的影响,并探索玉米FTIR分子结构参数与体外发酵特征的相关关系。结果表明,玉米品种和淀粉老化处理对部分FTIR结构参数、体外发酵总挥发性脂肪酸(VFA)含量和丁酸占比存在显著交互作用(P<0.05),老化前高直玉米β-葡聚糖峰高、纤维化合物面积和峰高以及碳水化合物Ⅲ区面积显著高于普通玉米(P<0.05);老化后高直玉米的丁酸占比显著低于普通玉米(P<0.05),老化后高直玉米总VFA含量和丁酸占比显著低于老化前普通玉米(P<0.05),但是老化后高直玉米与普通玉米在FTIR分子结构方面没有显著差异(P>0.05)。高直玉米丙酸占比显著高于普通玉米(P<0.05),而总产气量、甲烷产气量和氢气产气量显著低于普通玉米(P<0.05);淀粉老化处理显著降低了总产气量、甲烷产气量、氢气产气量、干物质降解率和丙酸占比(P<0.05),而显著提高了乙酸占比(P<0.05)。相关性分析结果显示,总产气量与酰胺Ⅰ区峰高、酰胺Ⅰ区与酰胺Ⅱ区峰高比、纤维化合物峰高以及总碳水化合物区域结构呈显著负相关(P<0.05),与酰胺Ⅱ区面积和峰高呈显著正相关(P<0.05);干物质降解率与酰胺Ⅱ区峰高、酰胺Ⅰ区与酰胺Ⅱ区峰高比、纤维化合物峰高、碳水化合物Ⅰ区面积、碳水化合物Ⅰ区与Ⅱ区峰高呈显著负相关(P<0.05);乙酸占比与酰胺Ⅰ区峰高、酰胺Ⅰ区与酰胺Ⅱ区峰高比、纤维化合物峰高和总碳水化合物区域结构呈显著正相关(P<0.05),与β-葡聚糖面积和峰高呈显著负相关(P<0.05);总VFA含量与酰胺Ⅱ区面积和峰高呈显著正相关(P<0.05),与酰胺Ⅰ区峰高、酰胺Ⅰ区与酰胺Ⅱ区面积比和峰高比、纤维化合物峰高以及总碳水化合物区域结构呈显著负相关(P<0.05)。综上所述,不同玉米品种和淀粉老化处理改变了FTIR分子结构以及体外发酵参数;体外发酵总VFA生成、干物质降解率和气体产气量与FTIR分子结构(除酰胺Ⅱ区外)呈负相关,而与酰胺Ⅱ区呈正相关。

红外光谱分析木质素在漆酶酶法改性中的反应性

随着非水酶学的发展,木质素的酶法催化改性得到日益广泛的运用。文章主要考察了漆酶酶法改性反相微乳液体系中云杉碱木质素、乙醇水溶液中乙醇木质素、缓冲液体系中木质素磺酸盐、以及碱溶液中汽爆麦草碱木质素的反应。通过红外光谱对各反应体系中,漆酶催化改性后的木质素结构特点进行分析,结合凝胶色谱法考察木质素的分子量及其分布,结果表明经过YY-5漆酶处理后各种木质素的分子量分布均趋向于高分子区域,且分子量分散性降低,各种木质素的红外光谱结构也发生了明显的变化。初步确定了木质素在漆酶催化改性中存在的反应位点,主要是酚羟基、苯环侧链取代基、羰基等。在四种木质素中,漆酶对碱木质素的改性反应性要高于其他类型的木质素,这可能与碱性溶液体系中漆酶的活性较高有关。

Structure and Vibrational Spectroscopy of 2-Methylallyl Alcohol

The intramolecular O−H…πhydrogen bond has garnered significant research interest in recent decades.In this work,we utilized the infrared(IR)-vacuum-ultraviolet(VUV)nonresonant ionization detected IR spectroscopy(NRID-IR)method to study the molecular structure of neutral and cationic 2-methylallyl alcohol(MAA,CH_(2)=C(CH_(3))−CH_(2)−OH).Density functional theory calculations revealed five stable neutral and three stable cationic MAA conformers,respectively.Two neutral MAA conformers are expected to have an O−H…πintramolecular hydrogen bond interaction,based on the structural characterization that the OH group is directed toward the C=C double bond.The IR spectra of both neutral(2700−3700 cm^(−1))and cationic MAA(2500−7200 cm^(−1))were measured,and the anharmonic IR spectra were calculated at the B3LYP-D3(BJ)/def2-TZVPP level.The OH stretching vibration frequency of neutral MAA was observed at 3656 cm−1,slightly lower than those of methanol and ethanol.In contrast,the OH stretching vibration of cationic MAA was red-shifted by about 140 cm^(−1)compared to neutral MAA.The interaction region indicator and natural bond orbital analysis suggest that the O−H…πinteraction in neutral MAA is weak,and may not play a major role in stabilizing the neutral MAA.

Influence of thermal history on conversion of aluminate species in sodium aluminate solution

It is necessary to clarify the influence of thermal history on the conversion of aluminate species in sodium aluminate solution in order to optimize Bayer alumina production. The interconversion of various solution species in the systems was investigated by measuring the infrared spectra of sodium aluminate solution with different compositions after separate heat treatment, dilution and concentration. The results show that increasing temperature or prolonging holding time favors the transformation of Al2O（OH）2- to Al—OH vibration（condensed Al O4 tetrahedral aluminate ion） at about 880 cm-1 and Al（OH）-4. A12O（OH）2-66 and Al—OH tetrahedral dimer ions convert rapidly to Al（OH）-4 during the dilution process; however, the back transformation of Al（OH）-4 to the Al—OH tetrahedral dimer ions can occur in diluted sodium aluminate solution. As for the concentration process, the transformation of Al（OH）-4 to A12O（OH）2-6 and Al—OH tetrahedral dimer ions can take place, while it is relatively difficult to transform to A12O（OH）2-6.

SiBN(C)陶瓷纤维先驱体的表征及熔融纺丝

以B(NHCH_3)_3和Si(NHCH_3)_4为小分子先驱体,在一定条件下通过共缩聚反应得到聚硅硼氮烷,经熔融纺丝得到SiBN(C)陶瓷先驱体纤维;采用红外光谱、核磁共振、元素分析等手段研究了小分子先驱体的配比对聚硅硼氮烷结构的影响。结果表明:聚硅硼氮烷存在B—N六元环、Si—N、Si—N—B、N—H等主要官能团,熔融纺丝实验表明Si(NHCH_3)_4与B(NHCH_3)_3体积比为1:1.3的聚硅硼氮烷具有良好的可纺性,可得到连续可卷绕的聚硅硼氮烷纤维,其纤维表面光滑,直径为50～60μm。

Computational Exploration of Conformations of Glycine-Arginine and a Deduced Model on Global Minimum Configurations of Dipeptides in Gas Phase

An extensive computational study on the conformations of gaseous dipeptide glycine- arginine, GlyArg, has been performed. A large number of trail structures were generated by systematically sampling the potential energy surface （PES） of OlyArg. The trial structures were successively optimized with the methods of PM3, HF/3-21G＊, BHandHLYP/6-31G＊ and BHandHLYP/6-311＋＋G＊＊ in order to reliably find the low energy conformations. The eonformational energies were finally determined with the methods of BHandHLYP, cam- B3LYP, B97D, and MP2 using the basis set of 6-311＋＋G（3df,3pd）. The results establish firmly that gaseous GlyArg exists primarily in its canonical form, in sharp contrast with ArgGly that adopts the zwitterionic form. Important data such as the rotational constants, dipole moments, vertical ionization energies, temperature distributions and IR spectra of the low energy conformers are represented for the understanding of the future experiments. Moreover, considering the global minima of all amino acids and many dipeptides, combined with the hydrophobicities of amino acids, a model predicting whether the global minimum configuration of a dipeptide is canonical or zwitterionic is developed.

The relationship between IR characteristic peak and microstructure of the glass used as optical fiber

Based on the harmonic vibration equation, the relationship between IR characteristic peak of fiberglass and Si-O-Si bond angle was deduced, and 1 100 cm^-1 characteristic peak was specifically studied. It is found that 1 100 cm^-1 characteristic peak shifts to higher wave number when Si-O-Si bond angle increases. Taking fused biconical taper （FBT） coupler as an example, the microstructures of the fiber coupler manufactured at different draw- ing speeds were tested with micro infrared spectrum. According to the test results, it is found that the bond angle at the taper region is the largest, the one at the fused region is the second largest, and the one of bare fiber is the smal- lest. The characteristic peaks of fused-taper region shift to higher wave number when drawing speed increases.

FTIR Characterization of the Secondary Structure of Insulin Encapsulated within Liposome

Aim To determine the secondary structure of insulin encapsulated withinliposome. Methods The secondary structure of native insulin, mixture of insulin with liposome(sample Ⅰ) and insulin encapsulated within liposome( sample Ⅱ) were determined by FTIR (FourierTransform Infrared) spectroscopy. Results The secondary structure of insulin encapsulated withinliposome(Ⅱ) are similar with the secondary structure of native insulin. The difference existed inthe amount of α-helices (from 36% of insulin to 31% of sample Ⅱ) and β-sheet(from 48% of insulinto 51% of sample Ⅱ). The content of α-helices and β-sheet of insulin in sample Ⅰ was found to bevery close to that of sample Ⅱ. The results revealed that the insulin encapsulated within liposomepossibly spread on the surface of liposome, without inserting into the liposome membrane.Conclusion The secondary structure of insulin encapsulated within liposome is similar with thenative insulin.

Conformations and Metal Ion Affinities of Glutamine Binding with Alkali and Alkaline Earth Metal Cations： an ab initio Study

Conformations and reaction energetics are important for understanding the interactions be- tween biomolecules and metal ions. In this work, we report a systematic ab initio study on the conformations and metal ion affinities of glutamine （Gln） binding with alkali and alkaline earth metal ions. An efficient and reliable method of searching low energy conformations of metalated Gln is proposed and applied to the complexes of Gln.Gln.M^＋/＋＋（M＋/＋＋=Li^＋、Na^＋、K^＋、Rb^＋、Cs^＋、Be^＋＋、Mg^＋＋、Ca^＋＋、Sr^＋＋ and Ba^＋＋）.. In addition to all conformers known in literatures, many new important conformations are located, demonstrating the power of the new method and the necessity of the conformational search performed here. The metal coordination modes, relative energies, dipole moments, and equilibrium distributions of all important conformations of Gln.M^＋/＋＋ are calculated by the methods of B3LYP, BHandHLYP, and MP2. IR spectra and metalation enthalpies and free energies are also presented and compared with the available experiments. The results form an extensive database for systematic examination of the metalation properties of Gln.

Preparation and Characterization of Tungsten-substituted Molybdophosphoric Acids and Catalytic Cyclodehydration of 1,4-Butanediol to Tetrahydrofuran

A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differential scanning calorimetry(TG-DSC),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),and FTIR pyridine adsorption.The as-prepared heteropoly acids have a Keggin type structure.The synthesis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten-substituted molybdophosphoric acids as catalysts.The results of catalytic test indicated that the catalytic activity increased with the increase in the substitution number(n) of tungsten atom in H3PMo12-nWnO40·xH2O and was constant as the substitution number(n) was more than 8.The catalytic activity increased with the increase in the catalyst loading and the selectivity of tetrahydrofuran was nearly 100%.

Ultrafast Infrared Spectroscopic Study of Microscopic Structural Dynamics in pH Stimulus-Responsive Hydrogels

Hydrogels show versatile properties and are of great interest in the fields of bioelectronics and tissue engineering.Understanding the dynamics of the water molecules trapped in the three-dimensional polymeric networks of the hydrogels is crucial to elucidate their mechanical and swelling properties at the molecular level.In this report,the poly(DMAEMA-co-AA)hydrogels were synthesized and characterized by the macroscopic swelling measurements under different pH conditions.Furthermore,the microscopic structural dynamics of pH stimulus-responsive hydrogels were studied using FTIR and ultrafast IR spectroscopies from the viewpoint of the SCN-anionic solute as the local vibrational reporter.Ultrafast IR spectroscopic measurements showed the time constants of the vibrational population decay of SCN-were increased from 14±1 ps to 20±1 ps when the pH of the hydrogels varied from2.0 to 12.0.Rotational anisotropy measurements further revealed that the rotation of SCNanionic probe was restricted by the three-dimensional network formed in the hydrogels and the rotation of SCN-anionic probe cannot decay to zero especially at the pH of 7.0.These results are expected to provide a molecular-level understanding of the microscopic structure of the cross-linked polymeric network in the pH stimulus-responsive hydrogels.

Infrared Spectroscopy of Neutral Clusters Based on a Vacuum Ultraviolet Free Electron Laseri

Spectroscopic characterization of clusters is crucial to understanding the structures and reaction mechanisms at the microscopic level,but it has been proven to be a grand challenge for neutral clusters because the absence of a charge makes it di伍cult for the size selection and detection.Infrared(IR)spectroscopy based on threshold photoionization using a tunable vacuum ultraviolet free electron laser(VUV-FEL)has recently been developed in the lab.The IR-VUV depletion and IR+VUV enhancement spectroscopic techniques open new avenues for size-selected IR spectroscopies of a large variety of neutral clusters without confinement(i.e.,an ultraviolet chromophore,a messenger tag,or a host matrix).The spectroscopic principles have been demonstrated by investigations of some neutral water clusters and some metal carbonyls.Here,the spectroscopic principles and their applications for neutral clusters are reviewed.

Synthesis and Properties of Dendritic Long-Chain Esters as Crude Oil Flow Improver Additives

The efficiencies of 6 kinds of macromolecules with dendritic structure in improving the flow properties of crude oil were investigated. The dendritic additives were synthesized using low-generation dendritic poly(amidoamine) and alkyl longchain acrylic esters as starting materials, and their structures were characterized by the Fourier transform infrared spectroscopy, 1H-nuclear magnetic resonance and elemental analysis. The effects on the pour point and rheological properties of crude oil samples were studied. Efficiencies of dendritic long-chain esters were not only influenced by the alky chain length, but also by the generation of dendrimer. The longer the alkyl chain of dendritic long-chain ester was, the better the effect in the reduction of pour point and apparent viscosity was. Efficiencies of 1.5 generation dendritic long-chain ester with 8 branched chains for the reduction of pour point and apparent viscosity were superior to those of 0.5 generation dendritic long-chain ester with 4 branched chains. Under the same conditions, efficiencies of 1.5 generation dendritic eighteen ester were superior to those of other 1.5 generation dendritic long-chain esters for the reduction of pour point and viscosity of crude oil.

Thermal-induced Unfolding of β-Crystallin and Disassembly of its Oligomers Revealed by Temperature-Jump Time-Resolved Infrared Spectroscopy

β-Crystallins are the major structural proteins existing in the vertebrate lens, and their conformational stability is critical in maintaining the life-long transparency and refraction index of the lens. Seven subunits of β-crystallins naturally assemble into various heteroge- neous oligomers with different sizes. Here, we systematically investigated the thermal sta- bility of the different secondary structures present in β-Crystallins and then the dynamic process for the thermal-induced unfolding of β-crystallins by Fourier transform infrared spectroscopy-monitored thermal titration and temperature-jump nanosecond time-resolved IR difference absorbance spectra. Our results show that the N-terminal anti-parallel β-sheets in β-crystallin are the most unstable with a transition midpoint temperature at 36.0-2.1℃, leading to the formation of an intermediate consisting vastly of random coil structures. This intermediate structure is temporally assigned to that of the monomer generated by the thermal-induced disassembly of β-crystallin oligomers with a transition midpoint tempera- ture of 40.4-0.7℃. The global unfolding of β-crystallins that leads to denaturation and aggregation indicated by the formation of intermolecular anti-parallel β-sheets has a transi- tion midpoint temperature determined as 72.4-0.2 ℃. Temperature-jump time-resolved IR absorbance difference spectroscopy analysis further reveals that thermal-induced unfolding of β-crystallins occurs firstly in the anti-parallel β-sheets in the N-terminal domains with a time constant of 50 ns.

Solid State Synthesis and Structural Characterization of Binuclear Cu(I) SbPh 3 Complex 〔Cu(SbPh 3) 2I〕 2

Dimeric complex 〔Cu(SbPh 3) 2I〕 2 has been synthesized by a solid state reaction at a low heating temperature and its crystal structure has been analyzed by X ray crystallography. The crystal is monoclinic, space group P2 1/a (#14), a = 20 436(5), b=14.125(3), c=24.683(3) , β=110.67(1)°, Z=4, V =6666(2) 3; C 72 H 60 Sb 4I 2Cu 2, M r = 1792, D c = 1.787 g·cm -3 , μ (Mo Kα ) = 31.88 cm -1 , F(000)=3440, R= 0.038 and R w= 0.043 for 5632 observed reflections ( I≥3.0σ(I) ) and 361 refined parameters. The result reveals the copper and the bridging iodide atoms form an approximately planar rhomboid array. Effects of the bulkiness of the ligands upon the structures of the analogous complexes are discussed.\;

Direct Synthesis of Amine-functionalized Mesoporous Silica for CO_2 Adsorption

Amine-functionalized mesoporous silica was prepared by using lauric acid and N-stearoyl-l-glutamic acid as structure directing agents via the S-N+-I- mechanism and applied to CO2 adsorption at room temperature. With γ-aminopropyltriethoxysilane as co-structure directing agent and due to the direct electrostatic interaction with anionic surfactant, most of the amino groups were uniformly distributed at the inner surface of pores and the per- formance was stable. The amine-functionalized mesoporous silica was characterized by Fourier transform infrared spectrometer, X-ray diffraction, nitrogen physisorption and thermogravimetric analysis. The CO2 adsorption capacity was measured by digital recording balance. At the room temperature and under the atmospheric pressure, the adsorption capacity of LAA-AMS-0.2 for CO2 and N2 is 1.40 mmol·g-1 and 0.03 mmol·g-1, respectively, indicating high separation coefficient of CO2/N2.

Reaction of C2HCl2＋O2： Combined TR-FTIR Spectroscopy and Electronic Structure

The product channels and mechanisms of the C2HC12＋O2 reaction are investigated by step-scan time-resolved Fourier transform infrared emission spectroscopy and the G3MP2// B3LYP/6-311G（d,p） level of electronic structure calculations. Vibrationally excited products of HCI, CO, and CO2 are observed in the IR emission spectra and the product vibrational state distribution are determined which shows that HCI and CO are vibrationally excited with the nascent average vibrational energy estimated to be 59.8 and 51.8 kJ/mol respectively. In combination with the G3MP2//B3LYP/6-311G（d,p） calculations, the reaction mechanisms have been characterized and the energetically favorable reaction pathways have been suggested.

Synthesis and Structure of Chromium Complexes with New Tetradentate Schiff Base N202-Type Ligand

In this research two chromium（II][） and （VI） complexes of tetradentate Schiff bases have been prepared by condensing of salicylaldehyde with 4-methyl 1,2-phenylenediamine. Schiff base complexes of chromium（Ill） have been employed to design and synthesize polynuclear complexes. So they have played an important role in molecular magnetism. Synthesized complexes were characterized by elemental analysis, IR, molar conductivity and NMR. The free ligands were alsc characterized by 1H, 13C NMR spectra. The 13C NMR and IR spectra of free ligand and the complexes are compared and discussed.

Influence of Filtration Processes on Aqueous Nanostructures by NIR Spectroscopy

Filtration processes are worldwide used for sterilizing solutions and substrates. Filtration seems to induce the formation of aqueous nanostructures. The aim of this work was to verify the influence of filtration processes on water structure detected by spectral variations in NIR region. Samples of ultrapure water （MilliQ-Millipore, Vimodrone, Milan, Italy） before and after iterated filtrations were analyzed. NIR spectra were collected in transmission mode in the whole NIR range, by using NIRFIex N500 spectrometer at constant temperature （40 ± 1 ℃）. NIR data were processed using Unscrambler software v. 9.2 in evaluating qualitative differences between filtered and not filtered samples. The information related to possible solvent physical stresses were highlighted in the range 6500-7500 cm^-1. The shifts observed were ascribable to a different distribution of the number of water molecules involved in hydrogen bonds in filtered and not filtered water samples, at constant temperature. NIR spectroscopy, commonly used to study relationship between spectral changes and hydrogen bonds in water at increasing temperature values, was applied to evaluate effects of filtration processes on water structure. The obtained results are in agreement with literature data and allowed the improvement of the knowledge about pure water characteristics when some mechanical perturbations are applied.