我国主要育珠贝(蚌)贝壳珍珠层及珍珠的激光拉曼光谱研究

本文对我国四种主要育珠贝(蚌)贝壳珍珠层拉曼光谱进行了系统研究,结果表明1)大珠母贝贝壳珍珠层中未观察到有机质的任何拉曼峰;2)三角帆蚌及马氏珍珠贝贝壳珍珠层及其养殖珍珠的拉曼光谱中除由文石矿物引起的拉曼峰外,还可观察到明显的由全反式结构的类胡罗卜素引起的拉曼峰,根据其峰位推断分子中的CC双键的数目为10;3)企鹅珍珠贝贝壳珍珠层的拉曼光谱中可观察到较复杂的有机质的拉曼峰,推测可能是由金属卟啉化合物引起的,但尚需进一步工作证实;4)珍珠层中类胡罗卜素及金属卟啉类化合物的相对浓度与珍珠层的颜色密切相关.贝壳珍珠层中有机质的拉曼光谱研究可为珍珠漂白及在食品、化妆品等领域的应用提供科学的依据.     

不同处理工艺对珍珠的紫外可见漫反射光谱的共性影响研究

主要基于紫外可见（UV-Vis）漫反射光谱首次对比研究了经过热处理、有机或无机染料改色或钴-60产生的γ射线辐照三种不同处理工艺对同为珍珠质的淡水与海水珍珠及贝壳珍珠层的漫反射光谱的影响机制。结果表明：（1）在不同颜色、淡海水属性的珍珠与贝壳珍珠层的UV-Vis反射光谱的紫外区皆存在约280 nm 处的吸收峰,上述吸收峰位归属于珍珠层中自身存在的有机质所致,而非珍珠的致色色素。（2）以上三种不同的处理工艺对上述280 nm处的吸收峰位存在一致的影响行为,即随着不同的处理工艺强度的增大,处理样品对应的反射谱图中约280 nm处吸收峰的强度逐渐降低直至消失。与此同时,珍珠的反射谱图中紫外区的反射主波长的反射强度也随之减弱,且反射主波长的峰位向可见光区发生显著红移。研究工作可为珍珠及珍珠的优化处理的鉴定筛选及其珍珠颜色的形成属性判定提供检测依据与理论支撑。     

淡水养殖珍珠中有机物的激光共振拉曼光谱分析

采用3个不同的激发波长λ=514,633和785 nm对淡水养殖珍珠进行了较为系统的原位拉曼光谱研究,且与相同条件下测定的苹果蜗牛卵壳拉曼光谱进行对比,结果表明:(1)珍珠中所探测到的有机物拉曼峰频率色散明显,推测为聚乙炔类物质,而非前人所认为的类胡萝卜素;(2)苹果蜗牛卵壳中有机物为典型的类胡萝卜素,当λ变化时其拉曼峰基本无频率色散现象;(3)根据拉曼峰位置推测珍珠中聚乙炔类物质共轭C=C双键的数目约为10和16,蜗牛卵壳中类胡萝卜素的共轭C=C双键的数目约为13.     

常见灰色珍珠的紫外可见漫反射光谱类型及其灰色成因

基于紫外可见（UV-Vis）漫反射光谱就当前市售流通领域常见的灰色珍珠品类进行表征并依据样品的反射谱图的类同特征予以分类,并初步探究了灰色珍珠的颜色成因。研究表明：(1)基于灰色珍珠的UV-Vis 漫反射光谱中约280 nm 处吸收峰的有无,首次将灰色珍珠分为Ⅰ型（存在明显的吸收）与Ⅱ型（无吸收或仅存在较弱的吸收）。并据Ⅰ型珍珠在其紫外可见光区的反射峰形与其反射主波长位置的差异进一步分为Ⅰn, Ⅰp与Ⅰf三个亚型,上述Ⅰ型珍珠均为有核珍珠。其中Ⅰp型珍珠的内核为白色、内核与珍珠层之间较多存在褐色、黑褐色的过渡层,该过渡层可能是导致珍珠呈灰色的直接原因。与此同时,上述Ⅰp型珍珠在宝玉石鉴定领域一般认为是未经处理的。（2）结合前人就珍珠辐照的相关工作及本工作中贝壳珍珠层辐照前后颜色的改变及UV-Vis反射光谱的变化特征, 推断辐照仍是人工处理导致珍珠呈现灰色主要原因之一。基于样品对应的UV-Vis反射光谱中约280 nm吸收峰的消失或仅呈现一吸收肩可初步定性该类珍珠经优化处理。同时,从Ⅱ类灰色珍珠的断面结构看,当前灰色珍珠并不仅局限于有核珍珠,无核灰色珍珠同样存在于流通领域。课题研究工作可为灰色珍珠及其优化处理品的鉴定提供理论与技术支撑。     

彩色珍珠致色成分的拉曼光谱研究

对多种彩色珍珠样品进行了可见光光谱和拉曼光谱测试,研究了珍珠致色成分的种类及其与颜色的关系。研究结果表明：(1) 彩色淡水珍珠和海水珍珠样品均会在1 121～1 132和1 506～1 524 cm-1范围出现强峰,该特征峰归属于多烯化合物的C—C和CC伸缩振动;(2) 随着珍珠颜色的加深,样品位于1 117～1 132,1 502～1 524和2 000～3 500 cm-1范围的峰逐渐增强,特征峰所代表的有机质与珍珠颜色有关;(3) 深紫色淡水珍珠和深橘红色海水珍珠样品在1 475～1 575 cm-1范围的包络峰可分成8～10个次级峰,计算可知多烯化合物CC双键数目分别为N=9～27和N=7～27。珍珠中不同种类和含量的多烯化合物,可能是彩色珍珠的致色原因。     

光谱学在金黄色海水珍珠鉴定中的应用

为了有效鉴别区分金黄色海水珍珠(简称金珠)和改色金珠,通过拉曼光谱和紫外可见吸收光谱对二者进行了检测分析.结果表明,拉曼光谱中,金珠的谱线稳定杂峰少,荧光背景弱,改色金珠的谱线杂峰多,荧光背景很强.0～1000 cm-1拉曼位移内金珠的光谱基线强度在1000以下,改色金珠的光谱基线强度在2000以上;金珠在拉曼位移275 cm-1处出现明显的拉曼特征峰,改色金珠275 cm-1处的拉曼特征峰基本被荧光谱线覆盖而变弱或消失;紫外可见吸收光谱中,金珠在200 nm～400 nm的近紫外区有284 nm,357 nm两个明显的紫外吸收峰.由于颜色处理过程中对珍珠表面破坏程度的不同,导致改色金珠在近紫外区无特征吸收,吸收峰发生红移(408 nm)或消失.     

珍珠层独特的反射光谱特征及其成因

采用反射光谱、扫描电镜及理论模拟计算对大珠母贝珍珠层的结构色及微结构进行了系统的研究。结果表明:(1)大珠母贝珍珠层文石板片厚度从生长端到壳中区显著减小, 从540减至340 nm, 导致同级别反射峰波长呈现明显的蓝移现象;(2)大珠母贝珍珠层的结构色是由文石板片和蛋白质层构成的多层薄膜结构和黄色素的共同作用决定的。     

显微拉曼光谱在珍珠鉴定中的应用

本文用显微拉曼对三种珍珠 (天然海水珍珠、人工养殖海水珍珠、人工养殖淡水珍珠 )做了测试与分析。结果表明 :虽然主峰相同 ,然而这三种珍珠的拉曼谱有不可置疑的差别。另外 ,珍珠粉和整粒珍珠也有明显差异。测试中还发现 ,与拉曼谱同时记录到的光荧光谱也是有关珍珠的宝贵信息。因此 ,显微拉曼光谱仪记录到的材料振动谱和荧光谱为珍珠的分析研究及日常鉴定提供了可靠的信息资料。     

珍珠和贝壳珍珠层的傅里叶变换红外光谱研究

本文通过高分辨率傅里叶变换红外光谱法和Ｘ射线衍射技术研究了三角帆蚌生长的珍珠和壳珍珠层粉末在１６０℃热处理前后谱图的变化。     

基于色度学与拉曼光谱的安徽淡水养殖白色珍珠研究

珍珠的颜色是影响其品质最关键因素之一.目前珍珠颜色的研究大多集中在不同颜色珍珠的组成元素、致色机理及结构差异,但对于如何直观分辨同种颜色珍珠的研究却很少.选用三批产自安徽不同时期的淡水养殖白色珍珠,对其进行色度学、激光拉曼光谱测试及宝石显微镜观察,建立白色系淡水养殖珍珠的白度值与拉曼光谱的关系并结合宝石显微镜的观察对其...     

基于拉曼光谱和DCGAN数据增强的珍珠粉掺伪检测研究

珍珠粉和珍珠层粉化学成分相似,但是珍珠层粉的药用价值远低于珍珠粉,并且珍珠层粉制备容易,成本底,常被不法商家用于冒充或掺入珍珠粉中流入市场,谋取利益.因此,对珍珠粉掺伪鉴别和纯度检测具有重要的意义.采用激光拉曼光谱结合深度学习研究珍珠粉掺伪快速鉴别和纯度分析.将纯珍珠粉和珍珠层粉按一定比例混合,制成珍珠粉质量百分数分别...     

Modeling red coral (Corallium rubrum) and African snail (Helixia aspersa) shell pigments: Raman spectroscopy versus DFT studies

Pigments from red coral (Corallium rubrum) and African snail (Helixia aspersa) shell were studied non‐invasively using Raman spectroscopy with 1064‐nm laser beam. The two observed bands because of organic pigments confined in biomineralized CaCO₃ matrix at about 1500 and 1100 cm⁻¹ were assigned to ν(CC) and ν(C―C), respectively. Both signals originate from polyene(s) of largely unknown structure, containing several conjugated CC bonds. The small peak at 1016 cm⁻¹ in the Raman spectrum of coral pigment was assigned to in‐plane ―CH₃ rocking or structural deformation of polyene chain because of spatial confinement in the mineral matrix. The organic pigments in red coral and snail shell were present in inorganic matrix containing aragonite (shell) and calcite (coral). In addition, using Raman spectroscopy, it was observed that aragonite was replaced by calcite as result of healing damaged parts of snail shell. This is an important finding which indicates a great potential of nondestructive Raman spectroscopy instead of X‐ray technique, as a diagnostic tool in environmental studies. To support analysis of the observed Raman spectra detailed calculations using density functional theory (DFT with B3LYP and BLYP density functionals) on structure and vibrations of model all‐trans polyenes were undertaken. DFT calculated CC and C―C stretching frequencies for all‐trans polyenes containing from 2 to 14 CC units were compared with the observed ν(CC) and ν(C―C) band positions of the studied coral and shell. Individual correction factors were used to better match theoretical wavenumbers with observed band positions in red coral and African snail. It was concluded that all‐trans polyene pigments of red coral and dark parts of African snail shell contain 11–12 and 14 CC double bond units, respectively. However, Raman spectroscopy cannot produce any clear information on the presence and nature of the end‐chain substituents in the studied pigments. Copyright © 2016 John Wiley & Sons, Ltd.     

Raman scattering in the Bi2TeO5 single crystal

Polarized Raman spectra of the Bi₂TeO₅ single crystal have been investigated for the first time. The group-theoretic analysis of the first-order vibrational spectra is performed. The number of the experimentally observed bands is less than the predicted number of normal modes. The spectral ranges with similar bands are revealed. Some ranges in the spectra of Bi₂TeO₅ are identified from the spectral data for the materials containing bismuth-oxygen and tellurium-oxygen complexes.     

Determination by Raman scattering of the nature of pigments in cultured freshwater pearls from the mollusk Hyriopsis cumingi

The nature of pigments in naturally colored pearls is still under discussion. For this study, Raman scattering measurements were obtained for 30 untreated freshwater cultured pearls from the mollusk Hyriopsis cumingi covering their typical range of colors. The originality of this work is that seven different excitation wavelengths (1064 nm, 676.44 nm, 647.14 nm, 514.53 nm, 487.98 nm, 457.94 nm, 363.80 nm) are used for the same samples at the highest possible resolution. All colored pearls show the two major Raman features of polyenic compounds assigned to double carbon–carbon (CC) – at about 1500 cm⁻¹ – and single carbon–carbon (C C) – at about 1130 cm⁻¹ – bond stretching mode, regardless of their specific hue. These peaks are not detected in the corresponding white pearls, and therefore seem directly related to the major cause of body color. Additionally, the exact position of CC stretching vibration shows that these compounds are not members of the carotenoid family. Moreover, some changes are observed in intensities, shape and positions of the two main characteristic polyenic peaks from one sample to the next. Similar changes are observed also using several excitation wavelengths for the same point of the same pearl. The exact position of C C stretching vibration of polyenic molecules depends strongly on the number of double bonds (N) contained in their polyenic chain. Hence, using a constrained decomposition of this band for different excitation wavelengths, up to nine different pigments may be detected in the same pearl. Their general chemical formula is R‐( CHCH )_N‐R′ with N = 6–14. All our colored samples contained at least four pigments (N = 8–11). Different colors are explained by different mixtures, not by a simple change of pigment. The chemical nature of the chain ends is still unknown, because it cannot be detected with Raman scattering. However, it is possible that these polyenes are complexed with carbonate molecules of the nacre. Similar coloration mechanisms are found in products from other living organisms (e.g. parrots feathers). Moreover, it seems that a similar series of pigments is found in other pearls also, as well as in some marine animals living in similar environments (e.g. corals). Copyright © 2006 John Wiley & Sons, Ltd.     

翡翠贻贝珍珠层的光子彩虹色表征及理论模拟

利用光纤光谱仪、扫描电镜及理论模拟软件对翡翠贻贝珍珠层的彩虹色及微结构进行系统的研究。结果表明,珍珠层具有由文石板片与有机质交替排列形成的典型的一维光子晶体结构;其中文石板片的厚度从生长区的392nm逐渐增大到壳中区的537nm,导致反射光谱中同级别光子带隙出现明显的红移现象;珍珠层彩虹色的主波长从480nm(蓝色)增大到527nm(绿色)。反射光谱测定及理论模拟表明,该珍珠层的2～4级光子带隙位于紫外区、蓝色和红色范围,从而导致珍珠层具有复杂的彩虹色。     

Chemical-mechanical stability of the hierarchical structure of shell nacre

The hierarchical structure and mechanical property of shell nacre are experimentally investigated from the new aspects of chemical stability and chemistry-mechanics coupling. Through chemical deproteinization or demineralization methods together with characterization techniques at micro/nano scales,it is found that the nacre of abalone,haliotis discus hannai,contains a hierarchical structure stacked with irregular aragonite platelets and interplatelet organic matrix thin layers. Yet the aragonite platelet i...