沙蚕磷草酸盐的合成与光谱表征

用１－二甲氨基－２,３－二氯丙烷和Ｏ,Ｏ－二甲基－二硫代磷酸盐反应合成了一种新的有机磷杀虫剂沙蚕磷,还制备了它的草酸盐。用１Ｈ、１３Ｃ核磁共振波谱、红外光谱及质谱法表征了沙蚕磷草酸盐的分子结构,结果表明反应产物是１,３－二取代产物。沙蚕磷的分子结构为（ＣＨ３）２Ｎ＋ＨＣＨ［ＣＨ２ＳＰ（Ｓ）（ＯＣＨ３）２］２Ｃ２Ｏ４Ｈ－［Ｏ,Ｏ,Ｏ′,Ｏ′－四甲基－Ｓ,Ｓ′－（２－Ｎ,Ｎ－二甲氨基丙撑）－双－二硫代磷酸酯草酸盐］。     

超分子化合物邻苯二胺草酸盐的合成及结构表征

邻苯二胺与草酸反应合成了一种新的化合物邻苯二胺草酸盐,采用元素分析,IR,对产物进行了表征,并采用X射线单晶衍射仪测定了该化合物的晶体结构,该化合物属单斜晶系,空间群P21/c,晶胞参数a=1.1428(2)nm,b=0.62170(12)nm,c=1.2845(3)nm,a=90°,β=103.50(3)°,γ=90°;V=0.8874(3)nm,Dc=1.483g/cm3,Z=4,F(000)=416,μ=0.121mm-1.该晶体结构的一个显著特点是:邻苯二铵的N(1)和N(2)原子各结合了一个氢质子H ,从而形成质子化阳离子,另一个特点是:邻苯二铵质子化阳离子与草酸根阴离子之间通过分子间氢键形成-维网状结构.     

磷硅酸盐微结构及其拉曼光谱的量子化学计算

构建了系列典型的磷硅酸盐团簇结构模型,应用量子化学从头计算方法研究了磷硅酸盐的精细结构,选用Restricted Hartree-Fock(RHF)方法以及6-31G(d)基组优化空间几何构型,并计算了其拉曼光谱,同时引入硅氧四面体应力指数(SIT)分析和讨论了磷氧四面体对硅氧四面体微环境的影响。研究表明,磷硅酸盐高频区硅氧四面体非桥氧的对称伸缩振动频率不仅与非桥氧所处的硅氧四面体本身的种类有关,同时也与其邻接四面体种类及成环状况有关;磷氧四面体具有较强的键角调节和应力传导能力,使得硅氧四面体的振动频率相对键角不敏感;硅氧四面体非桥氧的对称伸缩振动频率随硅氧四面体应力指数(SIT)的增加而增加,并呈线性关系。     

具有Keggin结构的多元杂多化合物的合成与光谱研究

本文合成了一些具有Ｋｅｇｇｉｎ结构的Ｐ－Ｖ－Ｍｏ－Ｗ四元杂多阴离子「ＰＶｘＭｏｙＷ１２－ｘ－ｙＯ４０」＾（３＋ｘ）－的化合物（其中,ｘ＝１,２和３）,并对其进行红外和拉曼光谱研究,可看到化合物的νａｓ（Ｍ＝Ｏｄ）、νａｓ（Ｍ－Ｏｂ－Ｍ）和νａｓＭ－Ｏｃ－Ｍ）的红外伸缩振动峰随着Ｖ原子数目的增加而红移;而钨原子数目的增加一般使之蓝移,但在所研究的ＰＶ２Ｍｏ９Ｗ和ＰＶ３Ｍｏ８Ｗ杂多化合物却出现略为反常     

具有Keggin结构的多元杂多化合物的合成与光谱研究Ⅱ

本文合成了一些具有Keggin结构的Si-V-Mo-W四元杂多阴离子[SiVxMoyW12-x-6O40]^(4 x)-的化合物（其中，x=1,2和3），并对其进行了红外光谱研究，可看到化合物的M＝Od，M－Ob-M和M－Oc－M的红外伸缩振动峰随着V原子数目的增加而红移；而钨原子数目的增加一般使之蓝移，因此推测出杂多化合物的酸性随着V数目的增加而减, 应性能则相反。这种变化规律与[PVxMoyW12-x-yo40]^(3 x)-相似。另外，可看到P系列的多元杂多酸（或杂多化合物）的配性大于相应的Si系列的酸性。     

本征及掺杂磷烯对2,3,7,8-TCDD吸附机理的计算模拟研究

2,3,7,8-四氯二苯并对二噁英(2,3,7,8-TCDD)是二噁英家族中危害人类和环境最显著的一种.设计一种高效,灵敏的吸附剂来检测和去除2,3,7,8-TCDD对人类和环境的影响是亟需解决的问题.本研究利用基于密度泛函理论(DFT)的计算模拟方法探索了本征磷烯对2,3,7,8-TCDD的吸附机理,并详细考察了掺杂Ti, Fe, Ca, Al金属原子后磷烯对2,3,7,8-TCDD吸附的影响.研究结果表明2,3,7,8-TCDD初始构型会影响磷烯对其吸附,当平躺于磷烯表面时有较大的吸附.而且掺杂金属原子的磷烯对2,3,7,8-TCDD的吸附也存在较大的影响,掺杂金属原子均增大了磷烯对2,3,7,8-TCDD的吸附,其中Ca掺杂磷烯>Fe掺杂磷烯>Ti掺杂磷烯>Al掺杂磷烯.研究结论对于2,3,7,8-TCDD的处理带来了新的思考方向,有望为二噁英的检测和去除提供有用的理论指导.     

拉曼光谱与拉曼效应的量子模型结构分析

散射光谱这种新谱线对应于散射分子中能级的跃迁,为研究分子结构提供了一种重要手段,引起学术界极大兴趣,拉曼也因此荣获1930年诺贝尔物理学奖。并称这种谱线为拉曼光谱。介绍了拉曼光谱的基本原理、拉曼光谱的应用以及其发展,由于拉曼光谱非常弱,实验要求比较高,最后介绍了实验仪器及利用拉曼光谱研究分子的结构。     

复混肥中磷元素的激光诱导击穿光谱多元线性定量分析

复混肥成分的快速、原位检测对化肥的生产过程、产品质量控制具有重要的意义。在化肥企业生产中,实验室进行分析,检测时间长,无法实现线上检测。与复混肥成分现有检测方法相比,激光诱导击穿光谱(LIBS)检测时间只需几分钟、一次测量可完成复混肥成分检测、几乎无需样品预处理,将该技术用于复混肥成分快速、现场检测非常合适。搭建LIBS系统, 激光器(100 mJ, 1 064 nm, 1 Hz)输出的激光束经45°反射镜由水平转为垂直方向,经焦距为40 mm的透镜聚焦至旋转台上的复混肥样品表面,产生激光等离子体。激光器的调Q信号控制光纤光谱仪(Avantes, 195～500 nm)采集信号,设置光谱延迟时间为1.28 μs,采集时间为1.05 ms,最终获取复混肥样品LIBS光谱。20个复混肥样品由安徽徽隆集团提供,磷元素的参考值由企业采用国家标准方法测量。将复混肥样品粉碎过筛取3 g,采用压片机在8 MPa下压制成形。实验中,使用小型风扇吹扫复混肥样品表面,形成稳定气流,每个样品重复测量10次,每次测量平均20个脉冲,以减小样品不均匀性。其中,15个样品用于定标回归模型的建立,五个样品用于检验定标模型的适用性。复混肥是一种成分复杂的混合物,其中氮、磷、钾均以化合物存在。传统的LIBS定量方法是基于待测元素单条谱线强度,未考虑其他元素影响,降低了定量结果的准确性。将LIBS技术和多元线性回归法结合用于分析复混肥中磷元素浓度。选取磷元素的三条特征谱线即213.6,214.9和215.4 nm。磷矿中硅元素含量基本不变,且硅元素在磷的谱线附近存在多条谱线,如212.4,220.8,221.1和221.7 nm。分别采用一元、二元、三元和四元线性回归法建立校准曲线。结果表明,采用P Ⅰ: 214.9 nm谱线强度作自变量建立一元线性回归,LIBS预测值与参考浓度的相关系数仅为0.083,无法满足磷元素的定量分析要求。当采用P Ⅰ: 214.9 nm谱线强度和三条特征谱线之和(P Ⅰ: 213.6, 214.9和215.4 nm)作自变量建立二元线性回归拟合时,相关系数提高到0.856,平均绝对误差由1.32%减小到0.16%。在二元线性回归中引入Si Ⅰ: 212.4 nm谱线强度,建立三元线性回归,相关系数为0.869。为进一步提高磷元素浓度测量的准确性,建立四元线性回归方程,将Si Ⅰ: 212.4,220.8,221.1和221.7 nm谱线强度之和作为自变量加入三元线性回归,相关系数提高到0.980,且15个定标样品的相对误差范围为0.06%～1.31%,而验证样品为0.13%～1.26%,这说明采用四元线性回归定标法可提高复混肥中磷元素浓度测量的准确性。     

西维因和蝇毒磷的同步荧光光谱解析及应用研究

研究了西维因、蝇毒磷的荧光行为,发现在pH 3.0的Britton-Robinson缓冲介质中,两种农药均能产生较强的的荧光,但光谱相互重叠,当以波长差Δλ=60 nm进行同步荧光扫描,它们的同步荧光光谱得到较好的分离,同步荧光峰(以激发波长表示)分别位于280和322 nm,可同时分别对其进行定量测定。西维因和蝇毒磷的线性范围分别为0.016～0.384 μg· mL-1和0.016～0.320 μg· mL-1;检出限分别为0.015和0.010 μg· mL-1。混合样本分析无需分离,方法简单、快速,用于蔬菜、水果、大米和水样等测定,结果满意。     

Synthesis and Raman spectroscopic characterisation of the oxalate mineral wheatleyite Na2Cu2+(C2O4)2·2H2O

The mineral wheatleyite has been synthesised and characterised by Raman spectroscopy complimented with infrared spectroscopy. Two Raman bands at 1434 and 1470 cm⁻¹ are assigned to the ν_{(C O)} stretching mode and implies two independent oxalate anions. Two intense Raman bands observed at 904 and 860 cm⁻¹ are assigned to the ν(C C) stretching mode and support the concept of two non‐equivalent oxalate units in the wheatleyite structure. Two strong bands observed at 565 and 585 cm⁻¹ are assigned to the symmetric CCO in plane bending modes. The Raman band at 387 cm⁻¹ is attributed to the CuO stretching vibration and the bands at 127 and 173 cm⁻¹ to OCuO bending vibrations. A comparison is made with Raman spectra of selected natural oxalate bearing minerals. Oxalates are markers or indicators of environmental events. Oxalates are readily determined by Raman spectroscopy. Thus, deterioration of works of art, biogeochemical cycles, plant metal complexation, the presence of pigments and minerals formed in caves can be analysed. Copyright © 2008 John Wiley & Sons, Ltd.     

配合物[Zn(PSA)2(H2O)2]的合成及其晶体结构研究

合成了配合物单晶[Zn(PSA)2(H2O)2],其中PSA-为4-苯基丁酸根.配合物为单斜晶系,Cc空间群,a=3.8340(11)nm,b=0.51865(15)nm,c=1.0734(3)nm.a=90°,β=103.064(4).,r=90°,C20H26O6Zn.Mr=427.79,Z=4,V=2.0791(10)nm3,D=1.212g/cm3,F(000)=900,-46≤h≤43,-4≤k≤6,-13≤l≤13,R1=0.0780,wR2=0.2029.PSA-以两个氧原子与中心离子Zn(Ⅱ)离子形成四元螯合环,PSA与PSA反式构型.配合物分子之间存在氢键弱相互作用.     

Synthesis,crystal structure,spectroscopic characterization and optical properties of bis(4-acetylanilinium) tetrachlorocobalt (II)

The chemical preparation, crystal structure, spectroscopic investigations and optical features are given for a novel organic–inorganic hybrid material [C₈H₁₀NO]₂CoCl₄.The compound is crystallized in the orthorhombic space group Cmca, with the following unit cell parameters: a=19.461(2) Å, b=15.523(2) Å, c=13.7436(15) Å, and Z=8. The atomic arrangement shows an alternation of organic and inorganic layers along the b-axis. The cohesion between these entities is performed by N–H…Cl and N–H…O hydrogen bonds and π–π stacking interactions.Infrared and Raman spectra at room temperature are recorded in the 4000−400 and 4000−0 cm⁻¹ frequency regions, respectively and analyzed on the basis of literature data. This study confirms the presence of the organic cation [C₈H₁₀NO]⁺ and of the [CoCl₄]²⁻ anion. UV–vis spectroscopy results showed the indirect transition with band gap energy 2.98 eV.     

2,3-二羟基萘钼多酸有机衍生物的合成及1H NMR和IR谱学研究

本文对二种新合成的2，3－二羟基萘二钼和四钼多酸有机衍生物[n-Bu)4N]2[Mo2O5(OC10H6O)2](Ⅰ）和[n-Bu)4N]2[Mo4O10(OC10H6O)2(OCH3)2](Ⅱ)进行了红外光谱与核磁共振波谱研究，发现[Mo2O5]^2 中钼氧多桥键的红外振动频率较[Mo4O10(OCH3)2]^2 中钼氧多桥键的红外振动频率红移，而在配合物Ⅱ中2，3－二羟基中芳环的^1H化学位移较配合物Ⅰ中向低场移动。同时还发现含二钼配位中心[Mo2O5]^2 的[Mo2O5(OC10H6O)2]^2-与含四钼配位中心[Mo4O10(OCH3)2]^2 的[Mo4O10(OC10H6O)2(OCH3)2]^2-生成条件的差异仅仅只在反应体系的pH值的微小变化，说明钼多酸有机衍生物阴离子是对体系酸碱度极为敏感的物质。     

Raman spectroscopic study of the uranyl mineral,compreignacite, K2[(UO2)3O2(OH)3]2·7H2O

Raman spectra of the uranyl oxyhydroxy‐hydrated mineral compreignacite, K₂[(UO₂)₃O₂(OH)₃]₂·7H₂O, were measured and interpreted. Observed bands were attributed to the stretching and bending vibrations of uranyl units, molecular water and hydroxyl ions. U O bond lengths in uranyl and O HO hydrogen bond lengths were inferred from the spectra and compared with those from the X‐ray single crystal structure data. The importance of this spectroscopic study rests with the ability to analyze very small amounts of the mineral. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis,structural characterization,spectroscopic, thermal,dielectric and Hirshfeld surface analysis of 1-(2-methoxyphenyl)piperazinium chloranilate

The new compound 1-(2-methoxyphenyl)piperazinium chloranilate (MPP.CA) was synthesized and studied by the single crystal X-ray diffraction method. Its structure was confirmed by infrared spectroscopy. The crystal structure consists of ribbons of chloranilate anions and 1-(2-methoxyphenyl)piperazinium cations linked together by NH…O hydrogen bonds. Two protons are transferred from a chloranilic acid molecule to the nitrogen of the piperazine in this structure. Measurements of AC conductivity as a function of frequency at different temperatures indicated the hopping conduction mechanism; in addition, the variation of dielectric constant as a function of T confirmed the transition phase indicated by the differential scanning calorimetry (DSC). The physico-chemical properties, UV-Vis, DSC and dielectric properties are described. Hirshfeld surface analyzes all the intermolecular interactions involved within the structure, which are important to stabilize the structure.     

Raman spectroscopic study of the antimonate mineral lewisite (Ca,Fe, Na)2(Sb,Ti)2O6(O,OH)7

The mineral lewisite, (Ca, Fe, Na)₂(Sb, Ti)₂O₆(O, OH)₇, an antimony-bearing mineral, has been studied by Raman spectroscopy. A comparison is made with the Raman spectra of other minerals, including bindheimite, stibiconite, and roméite. The mineral lewisite is characterised by an intense sharp band at 517 cm^?1 with a shoulder at 507 cm^?1 assigned to SbO stretching modes. Raman bands of medium intensity for lewisite are observed at 300, 356, and 400 cm^?1. These bands are attributed to OSbO bending vibrations. Raman bands in the OH stretching region are observed at 3200, 3328, 3471 cm^?1, with a distinct shoulder at 3542 cm^?1. The latter is assigned to the stretching vibration of OH units. The first three bands are attributed to water stretching vibrations. The observation of bands in the 3200–3500 cm^?1 region suggests that water is involved in the lewisite structure. If this is the case then the formula may be better written as (Ca, Fe²⁺, Na)₂(Sb, Ti)₂(O, OH)₇ xH₂O.     

配合物La（C5O3H3）3·C12H8N2·H2O的合成和表征

本以α－呋喃甲酸（Ｃ５Ｏ３Ｈ４）和邻菲罗啉（Ｃ１２Ｈ８Ｎ２）为配体,在乙醇８溶剂中与硝酸镧反应,合成了与稀土离子Ｌａ（Ⅲ）的三元混配配合物。经元素分析确定其配合物的组成为Ｌａ（Ｃ５Ｏ３Ｈ３）·Ｃ１２Ｈ８Ｎ２·Ｈ２Ｏ,同时还通过了ＩＲ、＾１ＨＮＭＲ、ＵＶ、ＴＧ－ＤＴＡ等谱光的测试与分析,表征了配合物的组成结构和性质。ＩＲ、＾１ＨＮＭＲ和ＵＶ谱的分析结果表明配体羧酸是以脱质子的酸根形式与中心稀土离子     

Eu（C8H7O3）3·C12N2·H2O配合物的合成与表征

合成了新的Eu(C8H7O3)3·C12H8N2·H2O配合物.并经元素分析、摩尔电导、IR、UV、1H NMR等表征,初步确定配体3-甲氧基苯甲酸以桥式双齿形式和Eu(Ⅲ)配位.