颜料层微观形貌对古代壁画褪色及显现影响

文物壁画在自然环境下产生褪色现象具有复杂性,严格意义上讲,人们无法重现自然环境下这种褪色发生的条件,但这并不妨碍人们研究其褪色原因的可能性和途径。通过实验来验证所提出机制的合理性,这也符合自然科学普遍采用的研究方法。提出颜料层微观形貌变化是引起壁画褪色的一种重要原因。胶料作为颜料层的连续相,当胶料分解时,颜料层微观形貌必然产生变化,为证明这种变化会引起颜料层褪色,而非颜料变化所致。建立了以具有较高热稳定性的赭石为颜料,以明胶作为粘接剂制成模拟的壁画颜料层。然后通过加热处理使胶料发生氧化分解,从而造成颜料层微观形貌发生变化,但赭石颜料依然稳定,期望证明在颜料赭石不发生变化时,由于颜料层微观形貌变化也可引起颜料褪色。实验通过煅烧壁画颜料层模拟样获得胶料降解的壁画模型,分别以SEM及多角度反射率光谱等技术,考察模拟样胶料降解前后表面微观形貌和光学性质变化。结果表明：壁画模拟样煅烧后,颜料层表面产生空隙结构,样品表面多角度反射率光谱表明煅烧后样品颜料层对可见光的反射增加而吸收降低,并观察到模拟样颜色淡化。以无色,难挥发,且不与颜料层发生化学反应的离子液体涂覆褪色样品表面,以上述技术表征涂覆处理前后颜料层表面微观形貌和表面光学性质变化,结果表明：离子液体填充了褪色样品表面颗粒间空隙,检测到样品表面对可见光的反射降低而吸收增加,观察到褪色样品的颜色加深。以上实验结果证明了推测合理性,即微观形貌变化确实会引起颜色变化。依据此原理以唐代墓室褪色壁画为例,进行了显现修复应用研究,其颜色显现效果显著。     

绿色植被可见-近红外反射光谱模拟材料研究进展

成像光谱技术能够同时获取目标的图像特征和光谱特征,很容易识别与背景环境光谱特征区别较大的传统伪装材料。近年来,成像光谱得到了迅速发展,经历了多光谱技术到高光谱技术的跨越,传感器的探测波段数、光谱分辨率、空间分辨率的显著提高。得益于各国ISR无人机技术的应用,高光谱传感器由星载拓展到机载,可以在更近距离对军事伪装目标进行识别,对具有重要价值的军事目标的生存能力构成巨大挑战。目前,应对高光谱的伪装材料主要设计思路是,选择材料或材料体系具有与环境背景相似的颜色和光谱反射特征（传感器探测范围内）进行复合,目的是与环境背景达到“同色同谱”来躲避高光谱侦察。绿色植被是最常见的伪装背景,也是本领域绝大部分研究的光谱模拟对象,其反射光谱曲线在可见近红外波段具有：“绿峰”、“红边”、“近红外高原”和“水吸收带”四个主要特征,分别由叶片的组织结构以及叶绿素和水分产生。离体叶绿素光热稳定性较差,不能直接用作伪装材料,所以寻找和合成稳定性好、具有类叶绿素结构及光谱特征的分子是当前的研究热点之一。此外,铬绿和钴绿是常用的伪装颜料,具有类似绿色植被“绿峰”、“红边”和“近红外高原”光谱反射特性,研究者将其与高吸水填料复合来引入“水吸收峰”,大致模拟出绿色植被反射光谱,但是想要实现精确模拟,仍存在一些难以解决的问题。从绿色植被光谱特征出发,分别阐述了模拟绿色植被可见光区和近红外光区光谱特征的材料选择依据及体系;同时介绍了它们在精确模拟植被光谱时存在的问题,以及通过改性和复合来提升光谱相似度和耐候性的相关研究工作,总结并展望了绿色植被光谱模拟材料要解决的重难点问题和发展方向。     

近红外特征光谱的羊肉TVB-N浓度预测模型

为提高生鲜羊肉储存期内（4,8和20 ℃环境）挥发性盐基氮（TVB-N）的近红外光谱（NIR）检测的稳定性和准确性,选取特征光谱和预测模型是关键步骤。以121个羊肉样品为实验对象,采集生鲜羊肉680~2 600 nm波段的近红外光谱。以多元散射校正（MSC）、标准正态变换（SNV）等散射校正方法,Savitzky-Golay卷积平滑（SGS）、移动平均平滑（MAS）等平滑处理方法,以及归一化（Normalization）、中心化（Centering）、标准化（Autoscaling）等尺度缩放方法分别预处理光谱数据后建立偏最小二乘法（PLS）预测模型。比较发现SGS处理的光谱建模效果最好。利用蒙特卡洛采样（MCS）法及马氏距离法（MD）消除了羊肉光谱的5个异常数据。运用光谱-理化值共生距离（SPXY）算法划分总样本的75%（87个）为校正集样本,剩余29个为验证集样本,利用竞争性自适应重加权法（CARS）、无信息变量消除法（UVE）、改进的无信息变量消除法（IUVE）和连续投影算法（SPA）提取特征光谱得到的波长个数分别为14,713,144和15。将全光谱和4种方法提取的特征波长作为输入变量建立预测模型,CARS提取的波长所建立模型的性能优于UVE、IUVE和SPA提取的波长所建立模型的性能,表明CARS方法可以有效简化输入变量并提高预测模型的性能。改进后得到的IUVE法相比于UVE法,筛选出的波长数更少且模型性能有所提升。以提取的特征波长建立PLS,支持向量机（SVM）和最小二乘支持向量机（LS-SVM）预测模型,SVM模型得到最优的校正集预测结果,其中CARS-SVM预测模型的校正决定系数（R2_C）和校正均方根误差（RMSEC）分别为0.939 1和1.426 7,最优的验证集预测效果为LS-SVM预测模型得到,其中IUVE-LS-SVM预测模型的验证决定系数（R2_V）和验证均方根误差（RMSEV）分别为0.856 8和1.886 2。基于近红外特征光谱建立简化、优化的生鲜羊肉储存期TVB-N预测模型,为实现快速无损检测生鲜羊肉中的TVB-N浓度提供技术支持。     

In First Time:Synthesis and Spectroscopic Interpretations of Manganese（Ⅱ）,Nickel（Ⅱ）and Mercury（Ⅱ）Clidinium Bromide Drug Complexes

Clidinium is a synthetic anticholinergic agent which has been shown in experimental and clinical studies to have an antispasmodic and antisecretory effect on the gastrointestinal tract. Inhibits the muscarinic effects of acetylcholine at neurotransmitter sites after parasympathetic ganglia. It is used to treat peptic ulcer disease and to help relieve stomach or stomach cramps or cramps due to abdominal cramps, diverticulitis, and irritable bowel syndrome. Mononuclear complexes of the manganese(Ⅱ), nickel(Ⅱ) and mercury(Ⅱ) with clidinium bromide drug (C₂₂H₂₆NO₃) types [M(C₂₂H₂₅NO₃)₂(H₂O)₄] and [Hg(C₂₂H₂₅NO₃)₂(H₂O)₂] where M=Mn (Ⅱ) and Ni(Ⅱ), have been synthesized and characterized on the basis of elemental analysis, conductivity measurements, magnetic, electronic, 1H-NMR and infrared spectral studies. The complexes confirm to 1∶2 stoichiometry and are non-electrolytes. The clidinium drug ligand (C₂₂H₂₆NO₃) act as a deprotonated monovalent monodentate chelate coordinating through hydroxyl oxygen where IR spectral bands of clidinium bromide shows a band at 3 226 cm-1 assigned to the OH group stretching frequency, this band ν(O-H) stretching vibration motion is disappeared in case of the infrared spectra of the Mn(Ⅱ), Ni(Ⅱ), and Hg(Ⅱ) complexes suggesting the involvement of the oxygen atom of the deprotonated OH group of clidinium ligand in complexation. The band for the ν(C-O) of alcoholic group of clidinium that appears at 1 240 cm-1 has blue shifted after complexity, indicating the participation of the alcoholic group in the coordination . 1H NMR spectrum for clidinium bromide show a singlet peak at 3.65 ppm due to proton of OH group which isn’t observed in the spectrum of mercury(Ⅱ) complex referring to the deprotonation of OH group and participated in the complexation. Based on electronic spectra, IR spectra and magnetic moment measurements; six coordinated octahedral structures have been proposed for the manganese and nickel(Ⅱ) complexes, while mercury(Ⅱ) complex has a four coordinated geometry. Thermogravimetric analyses studies revealed the presence of coordinated water molecules. For instance the X-ray powder diffraction pattern and scanning electronic microscopy for the Hg(Ⅱ) complex deduced that it was isolated in nanostructured with crystallinity form.     

Luminescence in trivalent rare earth activated Sr4Al2O7 phosphor

In this paper we report the combustion synthesis of trivalent rare-earth (RE³⁺ = Dy, Eu and Ce) activated Sr₄Al₂O₇ phosphor. The prepared phosphors were characterized by the X-ray powder diffraction (XRD) and photoluminescence (PL) techniques. Photoluminescence emission peaks of Sr₄Al₂O₇:Dy³⁺ phosphor at 474 nm and 578 nm in the blue and yellow region of the spectrum. The prepared Eu³⁺ doped phosphors were excited by 395 nm then we found that the characteristics emission of europium ions at 615 nm (⁵D₀?⁷F₂) and 592 nm (⁵D₀?⁷F₁). Photoluminescence (PL) peaks situated at wavelengths of 363 and 378 nm in the UV region under excitation at around 326 nm in the Sr₄Al₂O₇:Ce³⁺ phosphor.     

Comparative Study of the Ratio Spectra Derivative Spectrophotometry,Derivative Spectrophotometry and Vierordt's Method Appued to the Analysis of Lisinopril and Hydrochlorothiazide in Tablets

Abstract

Three new spectrophotometric methods are described for the determination of lisinopril and hydrochlorothiazide in their binary mixturer: First derivative spectrophotometry ratio spectra derivative and Vierordt's method. The procedures do not require any prior separation. In the derivative spectrophotometry, the dA/dλ values in the first derivative spectra of the mixture were measured at 269.6 nm for lisinopril and at 279.8 nm for hydrochlorothiazide. The calibration graphs were linear in the range 25.56–129.50 μg.ml^?1 for lisinopril and 10.60–139.80 μg.ml^?1 for hydrochlorothiazide. In ratio spectra derivative spectrophotometry, the calibration graphs for 15.68–129.50 μg.ml^?1 lisinopril and for 5.98–139.80 μg.ml^?1 hydrochlorothiazide were obtained by measuring the signals at 253.7 nm and 243.6 nm for lisinopril and at 280.1 nm and 270.8 nm for hydrochlorothiazide. In Vierordt's method, A¹ ₁ (1 %, 1 cm) values of lisinopril and hydrochlorothiazide were determined at 259.8 nm and 272.7 nm in the zero-order spectra. The quantity of both compounds were calculated by using the A¹ ₁ (1 %, 1cm) values. The methods were successfully applied to a pharmaceutical formulation for determination of both active compounds.     

Preparation,characterization and electroluminescence studies of copper doped zinc sulfide nanocrystals

Copper doped zinc sulfide nanoparticles were prepared by chemical precipitation method. The size of the particles was varied by changing the concentration of capping agent. The XRD studies indicate that most of the samples are cubic in nature. The broadening of peaks tends to increase with increasing capping agent concentration showing decrease in particle size. The crystalline size computed using Scherrer formula is found to be in range of 3–10 nm. Absorption spectra show absorption edge in UV region. The edge was found to shift towards shorter wavelength as the capping agent concentration is increased. This indicates increased effective band gap and hence reduced particle size. The nanoparticle size has been estimated in the range 5–10 nm using effective mass approximation model. For electroluminescence (EL) study of ZnS:Cu nanocrystals, the EL cells were prepared by placing ZnS:Cu nanoparticles between SnO₂ coated conducting glass plate and aluminum foil. Alternating voltage of various frequencies was applied and EL brightness (B) at different voltages (V) was measured and reported in this paper.     

Transmission characteristics simulation of an erbium-doped lithium niobate film photonic crystal slab

A photonic crystal slab (PhC slab) which was constructed as a 2D hexagonal lattice with a finite depth was etched into an Er:LiNbO₃ film waveguide. The band diagrams and transmission spectra were simulated by plane wave expansion (PWE) and the finite-difference time-domain (FDTD) method. A high refractive index contrast of 0.5 enables strong light confinement in the vertical direction and a broad band gap. The simulated transmittance spectra indicate that the stop band is determined by lattice constant. The transmission spectra along ΓM of the PhC slab with a lattice constant 500 nm show a 250-nm broad stop band in the wavelength range from 1.33 to 1.58 μm and sharp band edge.