Synthesis and spectral characterization of mercury(II) complexes with the bidentate Schiff base ligand N,N′-bis(2,3-dimethoxybenzylidene)-1,2-diaminoethane: The crystal structures of [Hg((23-MeO-ba)2en)I2] and [Hg((23-MeO-ba)2en)Br2]

Three mercury(II) complexes, [Hg((23-MeO-ba)₂en)X₂] (X = I (1), Br (2) and Cl(3)), and the ligand (23-MeO-ba)₂en ((23-MeO-ba)₂en = N,N′-bis(2,3-dimethoxybenzylidene)-1,2-diaminoethane) have been synthesized and characterized by elemental analyses, FT-IR and ¹H NMR spectroscopy. The crystal and molecular structures of 1 and 2 were determined by X-ray crystallography from single-crystal data. The metal-to-ligand ratio was found to be 1:1. The mercury(II) center in 1 and 2 has a distorted tetrahedral geometry with HgN₂I₂ and HgN₂Br₂ chromophores, respectively. The Schiff base ligand (23-MeO-ba)₂en acts as a chelating ligand, coordinating via the two nitrogen atoms to the mercury(II) center, and it adopts an E,E conformation. The coordination sphere of the mercury(II) center in 1 and 2 is completed by the two I and Br atoms, respectively. In complex 1 an inter-molecular non-classical hydrogen bond of the type C-H?O was found, while in complex 2 inter- and intra-molecular non-classical hydrogen bonds of the type C-H?X (X = O and Br) were found. The ¹H NMR spectra of the complexes exhibit downfield as well as upfield shifts of the free ligand resonances, reflecting changes in the ligand’s geometry during its coordination.     

The synthesis and spectroscopic characterisation of hydrotalcite formed from aluminate solutions

Raman spectroscopy has been used to characterise nine hydrotalcites prepared from aluminate and magnesium solutions (magnesium chloride and seawater). The aluminate hydrotalcites are proposed to have the following formula Mg(6)Al(2)(OH)(16)(CO(3)(2-))·xH(2)O, Mg(6)Al(2)(OH)(16)(CO(3)(2-),SO(4)(2-))·xH(2)O, and Mg(6)Al(2)(OH)(16)(SO(4)(2-))·xH(2)O. The synthesis of these hydrotalcites using seawater results in the intercalation of sulfate anions into the hydrotalcite interlayer. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structures. The spectra have been conveniently subdivided into spectral features based upon the carbonate anion, the hydroxyl units and water units. This investigation has shown the ideal conditions to form hydrotalcite from aluminate solutions is at pH 14 using a magnesium chloride solution at a volumetric ratio of 1:1. Changes in synthesis conditions resulted in the formation of impurity products aragonite, thenardite, and gypsum.     

基于光谱学分析的聚氨酯弹性体/聚磷酸铵/氢氧化铝复合材料阻燃机理研究

采用熔融共混技术,将聚磷酸铵(APP)和氢氧化铝(ATH)引入到聚氨酯弹性体(TPU)中,制备了一系列热塑性聚氨酯/聚磷酸铵/氢氧化铝(TPU/APP/ATH)复合材料。采用傅里叶红外光谱(FTIR)、X-射线光电子能谱(XPS)、扫描电镜(SEM)、激光拉曼光谱研究了TPU和阻燃TPU(FR-TPU)复合材料燃烧后炭渣的微观形貌、表面结构、元素组成、键合状态和石墨化程度,结合阻燃性能测试,揭示APP和ATH的协同阻燃机制。SEM分析表明相较于APP与ATH单独使用,TPU/APP/ATH炭层的空洞结构更少,炭渣的致密性更高。XPS分析表明FR-TPU的炭渣中C元素含量相比于纯TPU有所降低,O元素的含量有所上升,其中TPU/APP10/ATH10的C元素含量从88.2%降至69.24%,O元素的含量从8.07%升至17.78%,P和Al元素含量相较于单独添加分别从11.74%和16.36%下降至3.91%和3.31%。在此基础上,通过对C元素的分峰拟合发现TPU炭渣中C—C/C—H,C—O/C—N和CO/CN含量分别为61.05%,35.65%和3.30%;TPU/APP10/ATH10炭渣中三种结构含量分别为45.38%,45.00%和9.63%,说明ATH和APP复配使用有利于C元素形成酯、醚、羰基、羧酸（盐）、酯基等结构。通过对O元素的分峰拟合发现,TPU炭渣中O₂/H₂O,—O—,O三种结构含量分别为28.75%,44.36%和26.89%;TPU/APP10/ATH10炭渣中O₂/H₂O,—O—,O三种结构含量分别为44.33%,32.78%和22.89%,说明APP和ATH的加入有利于炭渣中O元素形成O₂/H₂O结构。通过对N元素的分峰拟合发现,TPU炭渣中—NH—,N结构的N元素含量分别为40.93%和59.07%;TPU/APP10/ATH10中—NH—,N结构的N元素含量分别47.17%和52.83%,说明ATH与APP复配使用促进了—NH—结构的形成。拉曼测试表明,相比于单独使用,APP和ATH复配使用,炭层的石墨化程度更好,致密性更高。以上分析结合阻燃测试可以得出TPU/APP/ATH复合材料阻燃机制：ATH受热分解生成氧化铝,吸收热量并释放大量水蒸气,有效促进APP降解,生成不燃性的氨气和聚磷酸,氨气和水蒸气稀释可燃性气体的浓度。随着温度继续升高,氧化铝可继续与聚磷酸反应生成偏磷酸铝[Al(PO₃)₃],同步催化聚氨酯基体成炭,形成高度石墨化炭层,石墨化炭层与偏磷酸铝一起覆盖在基体表面,有效抑制燃烧区域物质以及能量的输运,从而达到阻燃目的。     

可见-近红外光谱的模型转移分类方法

基于光谱技术建立的多元校正模型通常条件下只适用于同一台仪器、相同的测试条件及同批次或同类别的样品。在仪器、测试环境、样品发生变化后,已建光谱模型不再适配,需要进行模型转移。模型转移是限制光谱技术推广应用的关键技术瓶颈,模型转移是否成功直接影响到可见-近红外光谱技术的推广应用,为此,综述了其研究现状,并探讨了其未来发展方向。首先,将模型转移问题分成了两类：第一类是相同样品在不同仪器或不同测试环境（不同温度/不同湿度）等条件下产生的模型不适配问题;第二类是不同批次、不同物理形态、不同种类间产生的模型不适配问题。这两类问题性质不同,解决第一类模型转移,能够保证同源样品的准确性和稳定性;解决第二类,能够实现光谱模型在不同样品间的自动传递和匹配应用。然后,梳理了常用的模型转移算法并进行了分类,包括模型更新、基于光谱校正算法、基于结果校正算法等,并列举了每个类别的模型转移算法的应用。模型更新是一种重新计算模型系数最直接的方法,通过扩展和调整模型来满足新的变化;基于光谱校正算法是通过算法计算转移矩阵,实现对光谱的校正;基于结果校正算法是通过算法计算预测结果和实际结果系数,从而实现预测结果的校正。最后,指出未来应着重研究第二类模型转移问题,并且要寻找能够实现机器自动校正的模型转移,从根本上解决模型转移这一限制光谱速测应用的主要技术瓶颈。     

基于光腔衰荡光谱的便携式呼气异戊二烯分析仪性能评估

呼气异戊二烯是一种内源性代谢产物,其含量与人体血液中的胆固醇水平存在关联。但人体呼气影响因素众多,寻找其与胆固醇水平诊断参数的定量相关性,需要对选取的特定人群进行有效的呼吸气体分析（实时、在线、高灵敏度、高选择性、高精度的大量呼气数据获取）。光腔衰荡光谱（CRDS）是一种具有极高灵敏度、稳定性和选择性的光谱技术。采用目前市场在售的单波长紧凑型半导体紫外激光器,搭建了一套基于CRDS的呼气异戊二烯分析仪,该分析仪主要由激光系统、真空腔体、光电探测模块以及数据采集模块构成。线性拟合的结果显示所获得的衰荡信号接近单指数衰减（R2=0.998 39）,符合朗伯-比尔定律。探究了不同信号平均次数对衰荡信号稳定性的影响,综合考虑衰荡信号的稳定性和分析仪的响应时间,采用128次作为实验过程中的信号平均次数。对呼气异戊二烯分析仪的性能进行了测试,为了表征分析仪的稳定性,持续测量了分析仪16 min的真空衰荡时间。使用氮气、空气和呼吸样本,测量了呼气异戊二烯分析仪的重复性和响应速度。为了测试分析仪的线性度,测量了不同粒子数密度的异戊二烯标准气体（10×10-9,30×10-9,50×10-9,100×10-9,200×10-9）的衰荡时间。最后分析了在224 nm测量异戊二烯存在的光谱干扰问题（NO,N₂O和丙酮）。实验表明：分析仪具有高的灵敏度（检测极限为0.49×10-9）、良好的重复性、稳定性（0.48%）、近实时的响应速度（1秒测量一个数据）和良好的线性度（R2=0.993 13）,将检测极限提高至现有水平的1/1 000。研究证明基于CRDS的便携式呼气异戊二烯分析仪可实现对人体呼气异戊二烯的有效分析。     

1H NMR Studies on the Methylation,Protonation, and Hydration Sites in Some Benzo[b]Naphthyridines (Azaacridines)

Abstract

The 300.13 MHz ¹H NMR spectra of the methylated and protonated 6(9)-methylbenzo[b][1,x] naphthyridines (x=5, 6, 7, 8) (5-methylazaacridines) were collected at 298 K in deuterated dimethyl sulfoxide and chloroform, respectively. The methylation and protonation sites were assigned by comparisons of these data with those of the free bases. The results were compared with similar data for related heterocycles and showed that both methylation and protonation occur at the nitrogen in the outer pyrido ring in all four series.

The hydration site in some 2-and 3-azaacridines was determined by specific line broadening in their ¹H NMR spectra to be the same nitrogen as that involved in methylation and protonation. Variable temperature ¹H NMR demonstrated that the specific line broadening results from some changes of ¹⁴N quadrupolar relaxation produced by the slow chemical exchange between unhydrated and hydrated species. Deuterium exchange experiments indicated that the direct spin-spin interaction of a water proton and the protons alpha to the hydrated nitrogen may also have some contribution.     

Contactless Spectroscopy of Deep Levels in Semiconducting Materials: Gaas

Abstract

The surface photo voltage (SPV) and photocurrent (PC) transients as a result of the excitation by the short high-intensity light pulses from semiconductor's intrinsic absorption spectral region are investigated in semi-insulating GaAs. It is shown that the mathematical convolution of SPV transients and arbitrary form double-pulse integrator (lock-in, double-boxcar) in a wide temperature range allows to receive the deep-level (DL) spectrum without the need to form electrical contacts to the crystal investigated. The use of such a procedure while scanning the crystal surface with a light spot at a temperature, corresponding to some DL maximum in the spectrum, makes possible the con tactless determination of this DL density distribution profile along the scanning direction.     

A Direct Experimental Evidence of Collective Electron Resonance Mechanism of Surface Enhanced Infrared Spectroscopy (Seirs)

Abstract

We report here the preliminary results of the surface enhanced transmission infrared spectra of CH₃(CH₂)₇Azo(CH₂)₃COOH monolayers on CaF₂ substrate which was coated by silver island films with different size and distribution. The larger enhancement of absorbance of v(C=O) in COOH residing between silver island gap and small enhancement of absorbance of vibration mode of COO^? located on the silver islands are observed. It give us a direct experimental evidence of the collective electron resonance mechanism of surface enhance infrared spectroscopy (SEIRS), i.e. the decrease of the electromagnetic (EM) coupling reduces the enhancement factor of SEIRS.     

Study on Adsorption States by Surface-Enhanced Raman Spectroscopy

Abstract

SERS has been used as a state-resolving probe to study the adsorption states. in the case of pyridine (Py) adsorbed on the Ag electrode surface, the equilibrium and transition between two adsorbed states, i.e., the perpendicular mode adsorbed through the nitrogen lone-pair electrons and the flat mode through the π electrons of the aromatic ring, were studied. It was found that in the low pyridine concentration or the initial stage of adsorption, the flat mode was favored. While the concentration became higher and the adsorption tended to equilibrium, the adsorbed molecules would transit to the perpendicular mode. The similar phenomenon was also observed when changing the applied electric potential and the pH value of the solution. In the case of the adsorption of Methylene Blue (MB) on the HNO₃-etched silver surface, the influence of Cl^? ions on the adsorption states of MB was investigated. It showed that MB molecules adsorbed on the silver surface tended to transform from the “lying-down” state to the “end-on” state while adding Cl^? ions.