新型非线性光学杂化材料结构与性能的研究

由硅烷染料ASD与钛酸四正丁酯在酸性条件下共水解、缩合得到杂化材料,利用透射电镜(TEM)和X射线能量色散谱仪(EDS)进行分析,结果表明,杂化溶胶粒子是由硅和钛的化合物组成的球形纳米粒子.由一维刚性取向气体模型计算杂化材料膜再极化后的二阶非线性光学系数χ⁽²⁾为1.43×10^-7esu.差示扫描量热法(DSC)测得杂化材料的玻璃化温度可达469K;用紫外-可见光谱对杂化膜在极化前后的取向及取向稳定性进行了研究.用原子力显微镜(AFM)和X射线衍射(XRD)研究了材料在极化过程中的结晶行为和微观结构对生色团取向稳定性的影响,初次在这种极化后的膜中观察到了介观结构.     

On the affinities of ammonia and water for Li, Na and K

The affinities of ammonia for Na⁺ and K⁺, recently determined experimentally, have been computed by the ab initio SCF method using ended polarized gaussian basis sets and shown to be satisfactory Furthermore, the corresponding values computed at the same level of accuracy for the three cations Li⁺, Na⁺, K⁺ and the two ligands NH₃ and H₂O are shown to yield the order Li⁺ > Na⁺ > K⁺ for each ligand and NH₃ > H₂O for each ion, in agreement with experiment. An analysis of the factors involved in the binding provides a consistent rationalization of these regularities and of some observed correlations.     

Bi2Sn2o7的不同水热法制备及其可见光光催化除As(Ⅲ)性能分析

利用微波和普通水热法合成出了具有可见光响应的Bi₂Sn₂o₇纳米光催化剂,并用X射线衍射(XRD)、氮气吸脱附、紫外-可见漫反射光谱(UV-Vis DRS)、扫描电镜(SEM)、透射电镜(TEM)、电子顺磁共振谱(ESR)、X射线光电子能谱(XPS)等技术对样品的晶相、比表面积、光吸收性能、形貌、光催化活性物种等结构与性质进行了系统表征,比较微波水热Bi₂Sn₂o₇(MH-BSo)与普通水热Bi₂Sn₂o₇(TH-BSo)形貌和微结构,并考察两者在可见光光照下光催化氧化As(Ⅲ)的性能差别。实验结果表明, MH-BSo具有更细小的粒径和更大的比表面积,而在可见光照射下, MH-BSo样品比TH-BSo样品具有更好的As(Ⅲ)的光催化氧化能力(可达98.7%)。此外,对Bi₂Sn₂o₇纳米光催化剂氧化去除As(Ⅲ)的光催化机理进行初步探索,结果表明超氧自由基(o₂^-•)和空穴(hVB+)是主要起作用的中间反应活性物种。     

Synthesis,characterization, and phase transition of an inorganic-organic hybrid compound,[(3-nitroanilinium+) (18-crown-6)] [IO4-](CH3OH)

A novel inorganic-organic hybrid supramolecular compound,[(3-nitroanilinium~+)(18-crown-6)][IO_4](CH_3OH)(1),was discovered as phase-transition materials displaying dielectric anomalous behaviors.The yellow block crystal formed by N-H…O hydrogen bonding that made contact through the cavity of 18-crown-6 was characterized by single-crystal X-ray diffraction,elemental analysis,infrared analysis,thermogravimetric analysis,differential scanning calorimetry,and potential-energy calculations.Differential scanning calorimetry measurements indicate that the compound experiences a reversible phase transition at around 220 K.Temperature-dependent dielectric measurements further confirm the phase transitions.Potential-energy calculations demonstrate that the phase transition occurs due to the molecular order-disorder rotation of CH_3OH,whereas the space grouping of the crystal remains unchanged.     

Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification

Crystal engineering, as a burgeoning technology, has been widely used to construct metalloporphyrins biomimetic catalysts. Herein, a bimetallic metal-organic framework (MOF) was constructed by 4-(4-carboxyphenyl)-1,2,4-triazole ligand, Co²⁺ and Zr⁴⁺ metal ions by solvothermal reaction(named PFC-88). A N,N-chelation site was found between the two adjacent ligands in PFC-88, consequently a porphyrin-like structure was obtained through chelating Fe³⁺ in this site by post-modification, named PFC-88-Fe. The result of a single crystal X-ray technology verified that Fe ions were successfully metalated in the N,N-chelation site of PFC-88, which is assisted by the X-ray absorption near-edge structure(XANES) spectra. An o-phenylenediamine oxidation reaction was applied to assessing the catalytic activity of PFC-88-Fe, in which the absorbance increases of phenazine-2,3-diamine at λ=418 nm were recorded by absorption spectroscopy in kinetic mode, exhibiting the application potential as a biomimetic catalyst.     

PANI-SnP复合膜电极在镍镉废水中电控离子交换性能

采用滴涂法在铂基底制备了电活性聚苯胺-磷酸锡(PANI-SnP)复合膜电极,考察了该电极在Ni²⁺、Cd²⁺溶液的电控离子交换性能. 用傅立叶变换红外光谱和扫描电镜分析观察复合膜的组成及表面形貌;在0.1 mol·L^-1 Ni(NO₃)₂、Cd(NO₃)₂溶液,通过循环伏安法比较了PANI膜、SnP膜及PANI-SnP复合膜电极的电化学性能,并结合电化学石英晶体微天平技术重点考察了PANI-SnP复合膜的离子交换机制;同时,通过循环伏安法调控复合膜电极的氧化还原电位,结合X射线能谱和X射线光电子能谱分别测定了其氧化和还原状态的元素组成. 结果表明,PANI-SnP复合膜电极在Ni²⁺、Cd²⁺溶液均有良好的氧化还原电活性和可逆离子交换性能,其Cd²⁺离子选择性优于Ni²⁺离子,通过电控离子交换可使Cd²⁺离子从镍镉废水高效分离.     

DFT法研究离子液中EMIM+催化丁烯双键异构反应机理(II)

用密度泛函理论(DFT)在B3LYP/6-31G(d, p)的计算水平上研究了离子液中1-乙基-3-甲基咪唑阳离子(EMIM⁺)的4-H和5-H原子催化丁烯双键异构反应的可能途径，优化了反应体系的平衡态和过渡态的几何构型，分析了反应过程中键参数的变化，通过振动分析对平衡态和过渡态进行了验证. 计算结果表明, 离子液中的EMIM⁺首先通过4-H和5-H原子吸附丁烯, 进而催化丁烯的双键异构反应, EMIM⁺的4-H和5-H催化1-丁烯异构为2-丁烯的正反应活化能分别为204.2和207.3 kJ•mol^-1，逆反应活化能约为220.9和223.8 kJ•mol^-1， 反应为基元反应.     

A New Tubular Borate Built by[B14O24(OH) 6]12- Cluster Units

Anew mixed alkali and alkaline-earth metal borate Na₄Ca₂[B₁₄O₂₂(OH)₆]·2H₂O(1) has been made under a mild solvothermal condition and characterized by single-crystal X-ray diffraction, infrared(IR) spectroscopy, UV-Vis diffuse reflectance spectroscopy, powder X-ray diffraction and thermogravimetric analysis, respectively. Compound 1 features a 1D tube based on[B₁₄O₂₄(OH)₆]^12-({B₁₄}-1) oxo-boron clusters. Such a tube built by {B₁₄}-1 units has been discovered for the first time in borate system. These tubes are arranged orderly to generate 2D layers and a further 3D supramolecular network through hydrogen bond interactions. UV-Vis diffuse reflectance spectrum reveals that compound 1 is a wide band-gap semiconductor and has potential application in UV region.     

Synthesis of Phosphorus Derivatives of Pyrazolo[3,4-d]pyrimidine

Pyrazolo[3.4-d]pyrimidines are of considerable chemical and pharmacological importance as purine analogs^[1]. Various related compounds of these also show anti-tumor, anti-leukemic and antiviral activities^[2,3]. In addition,α-aminoalkylphosphonic acid are well known for their wide range of biological activities. They serve in agrochemistry as antifungal agents, herbicides and plant regulators^[4]. Recently, it was discovered that some derivatives of α-aminoalkylphosphonic acid also exhibit good antiphytoviral activity^[5]. As an extension of our studies on plant virucides, we now wish to report the synthesis of some novel phosphorus derivatives of pyrazolo[3,4-d]pyrimidine-6-ones 4,which may have antiviral activity.     

Fabrication and In vitro Bioactivity of Robust Hydroxyapatite Coating on Porous Titanium Implant

Compared witli the traditional dental implant, TixOs■ manufactured by direct laser metal forming(DLMF) technology exhibits improved capability for bone osteointegration due to its porous surface structure, and has achieved remarkable clinical effect. However, like the traditional titanium and other alloyed implants, the porous titanium implant TixOsR also has relatively weak bioactivity. To address this issue, a proper surface modification method may be needed. Hydroxyapatite(HA) has been widely used in implant surface coating for its similar chemical composition to bone tissue and its osteoconductive properties. Thus, combining TixOs■ implants with hydroxyapatite can be an efficient way to enhance their bioactivity. We herewith reported a competent pulsed laser deposition(PLD) method of coating nano-sized HA thin film onto the porous TixOs■ implant. The HA coatings were characterized by means of scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS), X-ray photoelectron spectroscopy(XPS) and focused ion beam(FIB) method, and nanocrystal sized thin HA films were identified on the surface of TixOs■ implants. The low cytotoxicity and improved cell proliferation ability of HA coated implants were further tested and verified using MC 3T3 E1 cells with the consideration of the controlling group. Our results show that a stable and bioactive HA tliin film is able to form on the surtace of the porous titanium implant by PLD method.This may benefit the fiirther clinical application of TixOs■ implants.     

α-MnO_2纳米管自组装微球的可控制备及电化学性能

以KMnO_4、HCl为反应物,H_2SO_4、NH_4Cl为助剂,利用水热法成功合成了α-MnO_2纳米管自组装微球。并采用X射线晶体衍射(XRD)、场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及X射线光电子能谱(XPS)表征手段对产物进行了形貌和结构表征,发现H~+与Cl-离子浓度对产物的晶型有很大影响:单一增加H+或Cl-离子浓度可以使纳米管管径减小、长度增加;同时增加两种离子浓度则产物从α相转化为β相;NH4+可以起到维持产物晶型(α相)以及管状形貌的作用。电化学性能测试表明,具有独特形态的α-MnO_2纳米管微球作为锂电负极具有高容量(20 m A·g-1电流密度下首周放电比容量达1783.5 m Ah·g-1)与良好的倍率性能,是具有广阔应用前景的锂离子电池材料。     

电沉积制备MnO2催化剂及其在微生物燃料电池中的应用

通过电沉积的方法获得了一种具有均匀孔隙结构的海绵状二氧化锰催化剂,结合扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)等手段表征了所制备材料的表面形貌、结构及元素构成和赋存价态,采用线性伏安扫描(LSV)法对电沉积材料的电化学性能进行分析,考察其催化氧还原反应的活性,最后以合成的材料为阴极催化剂,构建微生物燃料电池系统,考察其在微生物燃料电池中的应用效果。结果表明,以电沉积二氧化锰为阴极催化剂的微生物燃料电池最大功率密度为975.6 mW/m~2,是以商业二氧化锰为阴极催化剂的电池的1.7倍;这表明作为一种经济、高效、环境友好的阴极氧还原催化剂,电沉积法制备的二氧化锰为实现阴极催化剂的低成本制备以及微生物燃料电池放大化推进提供了新的研究途径。     

A Selective and Sensitive Fluorescence Probe for Se(Ⅳ) Based on Fluorescence Quenching of Gatifloxacin

A novel high selective and sensitive fluorescence probe termed gatifloxacin was discovered based on fluorescence "on-off" phenomenon in the presence of Se(Ⅳ). In the Tris-HCl/acetonitrile(3:7, volume ratio, Tris-HCl 0.05 mol/L, pH=7.3) sys-tem, the fluorescence intensity of gatifloxacin was linearly decreased with the concentration increase of Se(Ⅳ) in a range of 1.0×10^-5-5.0×10^-5 mol/L with a correlation coefficient of 0.9979(R²=0.9958) and in a range of 5.0×10^-5-1.0×10^-4 mol/L with a correlation coefficient of 0.9973(R²=0.9946). The detection limit of Se(Ⅳ) was 1.70×10^-6 mol/L.     

RbCl和CsCl水溶液结构的X射线散射及经验势结构精修模拟

采用X射线散射法研究了RbCl和CsCl水溶液的结构,利用基于经验势的结构精修(EPSR)方法获得了溶液中的水合Cl^-、Rb⁺、Cs⁺、离子缔合及本体水的对径向分布函数、配位数分布及空间密度分布(3D结构)等结构信息。在水溶液中,Cl^-具有相对稳定的6水合结构,其水合距离为0.321 nm,外加阳离子对其水合作用的影响不明显。7.3 ± 1.4个水分子与Rb⁺水合,其特征水合距离为0.297 nm,8.4 ± 1.6个水分子与Cs⁺水合其水合距离为0.312 nm。Cs⁺不具有第二水合层,而Rb⁺表现出了更强的水合能力,具有较明显的第二水合层。Cl^-、Rb⁺及Cs⁺常被认为是“结构破坏”型离子。从微观角度来看这种所谓的“结构破坏”主要体现在破坏了本体水分子的第二水合层保持四面体构型的趋势。RbCl和CsCl水溶液中部分存在着Rb-Cl和Cs-Cl直接接触离子对,在1.0 mol·dm^-3的溶液中Rb-Cl及Cs-Cl的特征距离分别为0.324和0.336 nm,溶剂分割离子对的距离则都在0.6 nm左右。相对于Cs⁺,Rb⁺与Cl^-离子之间表现出了更强的缔合能力。     

“Weakley型稀土多金属氧酸盐的制备与发光性质”在无机化学实验教学中的应用

采用理论与实验相结合的方法对稀土多金属氧酸盐的发光性质进行探究。首先,通过常规水溶液法合成了一系列稀土多金属氧簇Na₉LnW₁₀O₃₆ (Ln³⁺=Sm³⁺、Eu³⁺、Tb³⁺、Dy³⁺);其次,利用粉末X射线衍射、红外光谱、拉曼光谱对簇合物的结构进行表征;最后,利用紫外-可见光谱、荧光光谱对簇合物的光学性质进行考查。通过系统性的实验使学生对稀土簇合物的结构表征以及发光性质有全面、深刻的认识。     

糖基MOF-5@介孔碳纳米纤维的制备及修饰电极检测木犀草素的研究

以MOF-5为前驱体,葡萄糖为额外碳源,采用静电纺丝技术,将糖基MOF-5纳米颗粒和聚丙烯腈混纺,经过高温碳烧,成功合成糖基MOF-5碳纳米纤维(Glc-MOF-5/MCNFs)。采用场发射扫描电镜(Scanning Electron Microscopy,SEM)、透射电子显微镜(Transmission Electron Microscope,TEM)、全自动比表面及孔隙度分析仪(Brunner Emmet Teller,BET)、X射线衍射(X-ray Diffraction,XRD)、X射线光电子能谱(X-Ray photoelectron spectroscopy,XPS)对材料进行表征。采用差分脉冲伏安法(DPV)对木犀草素的电化学行为进行研究,优化影响木犀草素电化学行为的修饰剂用量、富集电位、富集时间、pH。在最优条件下,木犀草素在Glc-MOF-5/MCNFs/GCE上的检测范围为9.0×10^-9~5.0×10^-6 mol·L^-1,相关系数为R²=0.9954,检出限为5.2×10^-9 mol·L^-1,将此传感器用于实际样品检测,回收率为96.34%~100.58%。     

Sterically demanding cyclopentadienyl chemistry: synthesis of iron and zirconium complexes of 1-phenyl-3-methyl-4,5,6,7-tetrahydroindenyl

Reaction of phenyl magnesium bromide with the ,β-unsaturated ketone 3-methyl-2,3,4,5,6,7-hexahydroind-8(9)-en-1-one, followed by an aqueous work-up, generates the pro-chiral tetra-substituted cyclopentadiene, 1-phenyl-3-methyl-4,5,6,7-tetrahydroindene, Cp^‡H, a precursor to the η⁵-cyclopentadienyl ligand in (Cp^‡)₂Fe and [(Cp^‡)Fe(CO)]₂(μ-CO)₂. Both complexes were generated as mixtures of rac-(RR and SS)- and meso-(RS)-isomers, and in either case pure meso-isomer was isolated by crystallisation and characterised by single crystal X-ray structure, both molecules having crystallographic C_i symmetry. Reduction with Na/Hg cleaves meso-(RS)-[(Cp^‡)Fe(CO)]₂(μ-CO)₂ and the resulting mixture of (R)- and (S)-[(Cp^‡)Fe(CO)₂]⁻ anions reacts with MeI to give racemic (Cp^‡)Fe(CO)₂Me, which was characterised by the X-ray crystal structure. The Cp^‡ ligand is more electron donating than (η-C₅H₅) as revealed by the reduction potential of the (Cp^‡)₂Fe⁺/(Cp^‡)₂Fe couple, E°=−0.127 V (vs. Ag  AgCl). Reaction of LiCp^‡ with ZrCl₄ yields the zirconocene dichloride [Zr(Cp^‡)₂Cl₂] as mixture of rac- and meso-isomers, from which pure rac-isomer is obtained as a mixture of RR and SS crystals by recrystallisation. The reaction of rac-[Zr(Cp^‡)₂Cl₂] with LiMe gives rac-[Zr(Cp^‡)₂Me₂]. The structures of RR-[Zr(Cp^‡)₂Cl₂] and rac-[Zr(Cp^‡)₂Me₂] have been determined by X-ray diffraction. The structural studies reveal the influence of the bulky substituted cyclopentadienyl ligand on the metal---Cp^‡ distances and other metric parameters.     

新型Lewis固体酸Ce~(3+)-Ti~(4+)-SO_4~(2-)/MWCNTs制备及催化酯化反应合成生物柴油性能研究

采用高温浸渍法,通过Ce~(3+)、Ti~(4+)和浓硫酸磺化反应对多壁纳米碳管进行了改性处理,制备了Lewis酸型固体酸催化剂Ce~(3+)-Ti~(4+)-SO_4~(2-)/MWCNTs,并采用透射电镜、拉曼光谱、X射线光电子能谱、吡啶吸附红外光谱、X射线荧光光谱、X射线衍射光谱和NH_3程序升温脱附等多种测试技术对催化剂的物理化学特性和结构特征进行了表征。以Ce~(3+)-Ti~(4+)-SO_4~(2-)/MWCNTs为油酸与甲醇经酯化反应合成生物柴油的催化剂,对其催化性能进行了研究。结果表明,当醇油物质的量比为12∶1,催化剂与反应物质量比为1%,反应温度为65℃,反应5 h,油酸转化率为93.4%。催化剂Ce~(3+)-Ti~(4+)-SO_4~(2-)/MWCNTs在重复使用八次后,油酸的转化率仍为80.8%,由此表明其具有较高的催化活性和稳定性。高催化活性和稳定性是因为,纳米碳管的C 1s结合能较一般炭材料低,使得电子在其管状结构中的流动和逃逸非常容易,从而有助于负载于纳米碳管之上的活性组分之间发生强烈的相互作用,最终促使Ce~(3+)和Ti~(4+)分别与SO_4~(2-)形成稳定的配位键,增大催化剂的晶化程度,并使SO_4~(2-)与纳米碳管结合的更加牢固,增强了催化剂的稳定性,减少了催化剂中活性组分的流失。最后,由于SO_4~(2-)与Ce~(3+)的强相互作用,在不增加纳米碳管表面缺陷的情况下,改变了Ti~(4+)-SO_4~(2-)中表面原子的化学状态,使得S~(6+)离子和Ti~(4+)离子的吸电子能力增加,使催化剂以Lewis酸性活性位为主,避免了SO_4~(2-)/MWCNTs因为以Brnsted酸位为主,而在富含水的反应介质中,由于水合反应而降低其催化活性的现象发生。     

镧系元素杂多钨砷酸盐的合成与性质研究

本文报道了镧系元素的杂多钨砷酸钾K₁₁[Ln(AsW₁₁O₃₉)₂]·xH₂O(Ln:La、Ce、Pr、Nd、Sm)的合成方法和X-射线粉末衍射、红外及拉曼光谱、X-光电子能谱及有效磁矩的研究结果。     

Ag+掺杂聚苯胺的制备及其电容特性研究

以苯胺为单体,采用界面聚合法合成了不同浓度的Ag⁺掺杂的聚苯胺(PANI/Ag⁺),使用傅里叶变换红外光谱（FT-IR）、X射线衍射（XRD）和场发射扫描电镜（SEM）等手段对其结构和形貌进行了分析和表征. 在0.5 mol•L^-1 Na₂SO₄电解液中,通过循环伏安（CV）、恒流充放电（CP）以及电化学阻抗（EIS）等技术研究了其电化学性能. 结果表明,当电流密度为5 mA•cm^-2时,PANI/0.12mol•L^-1 Ag⁺的比电容达529 F•g^-1,循环1000次后比电容保持51%,相对于无Ag⁺掺杂的PANI,表现出更优良的电化学电容特性.