流沙湾养殖珍珠微观结构研究

用扫描电子显微镜（ SEM）观察紧贴流沙湾珍珠珠核表面的有机质层、棱柱层、珍珠质层结构。结果表明,有机质层呈不规则球状、纤维丝状并伴有疏松多孔结构。有机质层中观察到碳酸钙晶体存在;棱柱层和珍珠质层之间观察到厚度约为1?73μm的“拟过渡层”。用红外光谱分析紧贴珍珠珠核表面的有机质层成分,结果表明有机质中有蛋白质和文石晶体存在。对珍珠剖面用5％的乙二胺四乙酸（ ethylene diamine tetraacetic acid,EDTA）溶液腐蚀,利用SEM观察去钙化后的文石片层,结果表明,层与层之间的有机质呈裸露处理纤维状或多孔状的网络结构形态,文石晶体通过有机质孔隙生长,结果进一步支持了矿物桥说;对比EDTA腐蚀后的棱柱层和文石层,观察到两层存在的有机质有差异。     

基于体外仿生的海水珍珠矿化机制初步研究

珍珠的珍珠质层是一种复杂的自组装有机-无机杂化结构,具有优异的综合性能,但其形成机制还不甚明了,仿生制备面临挑战.本研究选用马氏珠母贝贝肉含有的17种氨基酸作为有机质,碳酸铵提供CO2.研究不同氨基酸体系诱导下,对碳酸钙结晶形貌的影响.扫描电镜研究表明:碳酸钙在不同氨基酸诱导下呈现不规则纳米片状文石,枝状文石、颗粒状球文石以及立方柱状和四方柱状方解石型形貌,XRD和傅里叶红外光谱分析进一步证实以上结果.初步研究结果表明:各氨基酸均能诱导方解石的形成,但丙氨酸、亮氨酸、酪氨酸和谷氨酸不能诱导文石的形成,组氨酸、异亮氨酸、脯氨酸、蛋氨酸和缬氨酸条件下发现文石较多,混合氨基酸作用下得到了文石层和方解石的互层结构.据此,提出了两种类珍珠质层晶体的生长模式.     

流沙湾海水养殖劣质珍珠微观结构研究

为了探讨流沙湾海水养殖珍珠出现杂质的原因,利用扫描电子显微镜（SEM）对劣质珍珠外表面、纵截面及内表面的微观结构进行系统的观察研究;利用傅里叶变换红外光谱仪（FTIR）对劣质珍珠各层物质的结构和成分进行分析.结果表明：劣质珍珠层外表面凸凹不平、生长机理纹杂乱无章及文石晶体有序排列程度低,是造成珍珠质量差的重要原因之一.劣质珍珠的珍珠层厚度为130 ～240μm,其中珍珠质层厚度为120 ～ 220 μm,棱柱层的厚度为15 ～50 μm,杂质层厚度不均匀.珍珠质层是流沙湾劣质珍珠珠层的主要成分.珍珠杂质层呈黑色或者灰褐色,这也是劣质珍珠质量差的重要原因.珍珠杂质的红外光谱分析表明其主要为蛋白质类有机物质,并结合少量的碳酸钙成分.     

应用OCT成像技术对海水珍珠的无损测量研究

为探明两种不同大小的海水珍珠的内部结构差异,利用一种新型扫频光学相干层析（OCT）成像系统和Raman光谱仪,无损分析了中国南珠和南洋珠两类海水珍珠。Raman光谱分析表明,这批海水珍珠主体物相皆为文石,未检测到人工有机染色物和添加物。基于该OCT成像系统的测量和图形处理功能,对这批海水珍珠珠层厚度进行了快速、有效的测量,并根据珠层厚度,将其质量等级分成五等。对比分析了这批海水珍珠样品的厚度与直径,除少数样品外,这批海水珠层厚度与珍珠直径呈弱正相关。此外,通过OCT二维图像的纹理特征,对这批海水珍珠的珍珠层、过渡层、珠核层组织的均匀性等进行了归类和评估。OCT成像技术可为珍珠的珠层厚度和均匀性质量分级提供重要依据。     

海水珍珠微观结构研究进展

被称为"宝石皇后"的珍珠不仅美观高贵,而且具有药用价值,其原因归根到底取决于珍珠独特的微观结构。因此,研究珍珠的微观结构对无机-有机功能材料、药物、保健品的开发有着重要的意义。本文从珍珠的结构——珠核、无定型基质层和珍珠层(又分为棱柱层和文石层)三个方面综述了近几年国内外学者对海水珍珠微观结构的研究,手段包括光学显微镜、扫描电镜、X射线衍射、偏光显微镜、红外辐射显微镜、透射电镜和红外光谱等。     

马氏珠母贝(Pinctada martensii)珍珠囊层细胞电镜扫描及亚显微结构观察

马氏珠母贝(Pinctada martensii)是我国一种主要海产珍珠养殖贝。有关珍珠囊层细胞的形貌及亚显微结构,国内外很少报导。本文用临界点干燥及超薄切片法制成扫描及透射电镜样品。观察了手术后232天,在水温20℃取样的珍珠囊层细胞的形貌及亚显微结构。并开展对珍珠囊层细胞合成分泌活动规律的研究,对促进珍珠养殖会起一定的作用。     

缓冲层温度对Si(111)上GaN表面形貌影响

用不同温度的Al N缓冲层在Si(111)衬底上外延GaN薄膜。通过对薄膜表面扫描电子显微镜(SEM)和高分辨率双晶X射线衍射(DCXRD)的分析,研究了缓冲层生长温度对外延层表面形貌的影响,分析解释了表面形貌中凹坑的形成及缓冲层生长温度对凹坑的影响。结果表明:缓冲层生长温度通过影响缓冲层初始成核密度和成核尺寸来影响外延层表面形貌。较低温度下的Al N缓冲层,在衬底表面形成的成核颗粒因温度太低,无法运动到相邻的颗粒而结合成大的成核颗粒,因此成核密度高,成核尺寸小;高温生长的Al N缓冲层,成核颗粒有足够的能量运动到相邻的成核颗粒,因此使成核颗粒的尺寸增大,成核密度低。这种初始成核密度和尺寸的不同,造成外延层形貌的差异,如表面形貌中凹坑的密度和大小就是受初始成核的直接影响。通过实验和分析,提出了外延生长的物理模型。     

应用于珍珠检测的光学相干层析技术

珍珠质的内部微观分辨和测量是珍珠产业发展和学术研究的核心难题.光学相干层析(OCT)高清晰深度分辨技术通过探测珍珠质的光学反射散射特性,提供了研究其结构形态和分布规律的新途径.阐述了对珍珠质进行成像扫描的原理和实验装置,以光纤迈克尔逊干涉仪为主体,利用中心波长1310 nm的宽带光源和傅里叶域光学延迟线实现了扫描速度1 frame/s,纵向分辨率15μm,成像深度3 mm的光学相干层析成像系统.实验结果验证了光学相干层析检测方法适用于珍珠质的定量检测和定性分辨的可行性,初步的报道包括珍珠质层和珠核贝壳层的分辨鉴别,珍珠质层平均测量误差在20μm以内,珍珠质内部各种反常生长分布信息也清晰可见.     

金刚石膜过渡层及其初始形核过程的TEM研究

金刚石薄膜在电子器件应用方面具有广泛前景。其表面与界面研究,具有重要意义。本文用高分辨电子显微学研究了金刚石薄膜生长初期,金刚石微晶与Si衬底之间的界面形态和初始形核生长特征。研究表明:在金刚石晶粒与Si衬底之间,存在一种非晶过渡层界面。该过渡厚度约为二十纳米。X射线能谱(EDS)表明,该非晶态过渡层主要由Si构成,过渡层内存在少量β-SiC纳米晶粒。金刚石晶粒在过渡层底部形核,并以孪晶方式生长。金刚石晶粒形核前,在过渡层内孕育形成大原子团和超微粒子,它们是SiC或富集碳的原子团。金刚石晶     

GaN薄膜表面形貌与AlN成核层生长参数的关系

采用金属有机物化学气相淀积技术生长了以AlN为成核层的GaN薄膜,研究了成核层生长时三甲基铝(TMAl)流量对最终GaN薄膜表面形貌的影响.研究结果表明,高质量GaN薄膜只能在高TMAl流量下获得,采用充足的TMAl源才能形成满足需要的AlN成核点,这是生长高质量GaN薄膜的一个先决条件.     

Silk Fibroin‐Regulated Crystallization of Calcium Carbonate

Mollusk shell is one of the best studied of all calcium carbonate biominerals. Its silk‐like binder‐matrix protein plays a pivotal role during the formation of aragonite crystals in the nacre sheets. Here, we provide novel experimental insights into the interaction of mineral and protein compounds using a model system of reconstituted Bombyx mori silk fibroin solutions serving as templates for the crystallization of calcium carbonate (CaCO₃). We observed that the inherent (self‐assembling) aggregation process of silk fibroin molecules affected both the morphology and crystallographic polymorph of CaCO₃ aggregates. This combination fostered the growth of a novel, rice‐grain‐shaped protein/mineral hybrid with a hollow structure with an aragonite polymorph formed after ripening. Our observations suggest new hypotheses about the role of silk‐like protein in the natural biomineralization process, but it may also serve to shed light on the formation process of those ‘ersatz’ hybrids regulated by artificially selected structural proteins.     

Toughness and Fracture Properties in Nacre‐Mimetic Clay/Polymer Nanocomposites

Nacre inspires researchers by combining stiffness with toughness by its unique microstructure of aligned aragonite platelets. This brick‐and‐mortar structure of reinforcing platelets separated with thin organic matrix has been replicated in numerous mimics that can be divided into two categories: microcomposites with aligned metal oxide microplatelets in polymer matrix, and nanocomposites with self‐assembled nanoplatelets—usually clay or graphene oxide—and polymer. While microcomposites have shown exceptional fracture toughness, current fabrication methods have limited nacre‐mimetic nanocomposites to thin films where fracture properties remained unexplored. Yet, fracture resistance is the defining property of nacre, therefore centrally important in any mimic. Furthermore, to make use of these properties in applications, bulk materials are required. Here, up to centimeter‐thick nacre‐mimetic clay/polymer nanocomposites are produced by the lamination of self‐assembled films. The aligned clay nanoplatelets are separated by poly(vinyl alcohol) matrix, with 10⁶–10⁷ nanoplatelets on top of each other in the bulk plates. Fracture testing shows crack deflection and a fracture toughness of 3.4 MPa m^1/2, not far from nacre. Flexural tests show high stiffness (25 GPa) and strength (220 MPa) that, despite the hydrophilic constituents, are not substantially affected by exposure to humidity.     

The Intrinsic Ability of Silk Fibroin to Direct the Formation of Diverse Aragonite Aggregates

As an analogue of the main protein contained in naturally formed nacre, reconstituted silk fibroin (SF) from the Bombyx mori silkworm silk shows a strong preference for the formation of the aragonite form of CaCO₃ crystals and allows fine control over their size and morphology. The aragonite phase could be generated via two different routes: direct growth or dissolution and recrystallization, depending on the concentration of Ca²⁺ and SF. Generally, lower concentrations of Ca²⁺ and SF favor the formation of aragonite needles and their aggregates, of which the lattice structure of the precursor is similar to that of the organic matrix in natural shell. Higher concentrations lead to the formation of aragonite aggregates via a dissolution and recrystallization process through intermediates of lens‐like vaterite. Molecular modeling shows that the β‐strand conformers of silk fibroin molecules has an excellent match with the ionic spacing in the aragonite (010) plane, which can promote growth along the (001) long axis of aragonite crystals. This synergy between silk fibroin and the aragonite phase may help our understanding of the function of organic matrices involved in the biomineralization process, and facilitate the fabrication of synthetic materials with the potential for high performance mechanical properties.     

The Coral Protein CARP3 Acts from a Disordered Mineral Surface Film to Divert Aragonite Crystallization in Favor of Mg‐Calcite

Stony corals construct their aragonite skeleton by calcium carbonate precipitation, in a process recently suggested to be biologically controlled. Amorphous calcium carbonate and small amounts of calcite are also reported recently, however, their functional role is unknown. Coral acid‐rich proteins (CARPs) are extracted from the coral skeleton and are shown to be active in calcium carbonate precipitation in vitro. However, individual function of these proteins in coral mineralization is not known. Here, the regulatory activity of the aspartate‐rich CARP3 protein is examined. The whole protein and two peptides representing its acidic domain and its variable domain are used in CaCO₃ precipitation reactions from Mg‐rich solutions. The biomolecules alter crystallization pathways, promoting Mg‐calcite in place of aragonite, with the acidic peptide capable of eradicating aragonite formation. The activity of CARP3 and its representative peptides is exerted from disordered CaCO₃ mineral phases, coating the crystals formed, as shown by 2D ¹H–¹³C heteronuclear correlation nuclear magnetic resonance (NMR) measurements, localizing organic protons in atomic proximity to disordered carbonate carbons. The structures of the protein and individual domains as derived from NMR measurements and folding calculations and their amino acid compositions are discussed in the context of their observed activity and its implication to mineralization in hard corals.     

Particle Accretion Mechanism Underlies Biological Crystal Growth from an Amorphous Precursor Phase

Many biogenic minerals are composed of aggregated particles at the nanoscale. These minerals usually form through the transformation of amorphous precursors into single crystals inside a privileged space controlled by the organism. Here, in vitro experiments aimed at understanding the factors responsible for producing such single crystals with aggregated particle texture are presented. Crystallization is achieved by a two‐step reaction in which amorphous calcium carbonate (ACC) is first precipitated and then transformed into calcite in small volumes of water and in the presence of additives. The additives used are gel‐forming molecules, phosphate ions, and the organic extract from sea urchin embryonic spicules ‐ all are present in various biogenic crystals that grow via the transformation of ACC. Remarkably, this procedure yields faceted single‐crystals of calcite that maintain the nanoparticle texture. The crystals grow predominantly by the accretion of ACC nanoparticles, which subsequently crystallize. Gels and phosphate ions stabilize ACC via a different mechanism than sea urchin spicule macromolecules. It is concluded that the unique nanoparticle texture of biogenic minerals results from formation pathways that may differ from one another, but given the appropriate precursor and micro‐environment, share a common particle accretion mechanism.