淡水珍珠的生物矿化机理研究进展

碳酸钙广泛存在于生物矿物中, 是地球上最普遍的生物矿物之一。贝壳和珍珠的主要组成部分为碳酸钙无机相。我国淡水养殖珍珠多数品质优异, 具有良好的珍珠光泽。该种珍珠以文石晶型碳酸钙为无机相, 称为文石珍珠。近年来, 在我国淡水养殖珍珠中发现了球文石的存在, 球文石的出现是导致珍珠失去光泽、降低质量的主要原因。本文对比阐述了淡水文石珍珠和球文石珍珠的微观结构与性能, 总结了与珍珠层有关的体外模拟碳酸钙生物矿化的实验结果, 提出了珍珠层生物矿化机理未来的研究方向。     

单分散纳米二氧化硅微球的制备及羧基化改性

采用改进工艺条件的Stober法制备纳米SiO_2微球.用场发射扫描电镜(FESEM)分析了纳米二氧化硅的形貌、粒径.结果表明,通过温度梯度法和控制氨水浓度变化制备出高圆度、单分散、粒径可控的纳米级二氧化硅微球.用KH-550硅烷偶联剂和丁二酸酐对纳米二氧化硅表面羧基化改性.采用X射线能谱仪(EDS)、热重(TGA)、傅里叶红外(FTIR)等手段对改性后纳米二氧化硅的结构、元素种类及含量进行了表征.结果表明,纳米二氧化硅表面成功接枝了羧基官能团.     

水性聚氨酯膜吸收CO2矿化形成复合膜及其防腐蚀性能

以异佛尔酮二异氰酸酯(IPDI)、聚醚二元醇(PPG)和N,N-二甲基-N’,N’-二(2-羟丙基)-1,3-丙二胺等为主要原料制备了聚氨酯预聚体,并利用乙酸、3-羧基-3-羟基戊二酸和2,2-二羟甲基丙酸(DMPA)为成盐剂与聚氨酯预聚体反应,产物经乳化得到3种阳离子水性聚氨酯胶乳(WPU1,WPU2和WPU3),并将其制膜后浸泡在模拟海水中。研究了3种水性聚氨酯膜吸收CO₂并矿化形成聚氨酯-碳酸钙(PU-CaCO₃)复合膜的过程及防腐蚀性能。红外光谱分析结果表明,成功合成了3种阳离子水性聚氨酯。粒径分析表明,WPU1,WPU2和WPU3胶乳粒径大小分别为19.38 nm,93.08 nm和84.33 nm。X射线衍射、扫描电镜和电化学测试结果表明,WPU2和WPU3膜经模拟海水浸泡后表面出现CaCO₃矿化层,WPU3膜表面形成的矿化层较致密,且具有优良的防腐蚀性能,其腐蚀速率和腐蚀电流密度分别为1.70×10^-3mm/a和1.44×10^-7A/cm²。     

不同端基官能团PEG与聚丙烯接枝马来酸酐的接枝反应

利用羟基与对甲苯磺酰氯和邻苯二甲酰亚胺钾的分步反应或者与二异氰酸酯的反应,将聚乙二醇单甲醚(MPEG)的端羟基分别转化为端氨基和端异氰酸酯基。将带有端羟基、端胺基和端异氰酸酯基的MPEG分别与聚丙烯接枝马来酸酐(MPP)反应,制备聚丙烯/聚乙二醇接枝共聚物,并比较不同体系的动力学。MPEG端基官能团与MPP链上马来酸酐的反应活性顺序为:-NCO>-NH2>-OH。在端异氰酸酯基MPEG与MPP反应体系中,随n(NCO)/n(MAH)增大,PEG接枝率增大;随MPEG分子量增大,接枝到PP链上的PEG支链数目减少。     

含聚甲基丙烯酸二甲氨基乙酯刷的羽毛接枝共聚物的制备及性能

采用电子转移活化再生催化剂原子转移自由基聚合(ARGET ATRP)的方法,以羽毛表面的溴为引发位点,引发甲基丙烯酸二甲氨基乙酯(DMAEMA)在羽毛表面自增长,制备含聚甲基丙烯酸二甲氨基乙酯刷的羽毛接枝共聚物(Feather-g-PDMAEMA)。再以溴乙烷为改性试剂,对其进行季铵化处理,制备具有抗菌性能的羽毛接枝共聚物。改性后羽毛的元素含量、官能团、热稳定性、结晶结构、表面形貌分别通过能谱仪(EDS)、傅里叶变换红外光谱仪(FT-IR)、热重分析仪(TGA)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)进行表征。FT-IR和SEM分析结果表明,甲基丙烯酸二甲氨基乙酯成功地接枝到羽毛的表面,所得羽毛接枝共聚物的接枝率最高可达84. 7%; XRD的分析结果显示,接枝聚合后的羽毛的结晶度降低; TGA分析结果显示,接枝聚合后的羽毛热稳定性降低;抗菌测试结果表明,季铵化处理后的Feather-g-PDMAEMA具有良好的抗菌效果。     

低温等离子体处理对纤维毡润湿性能的影响

通过低温等离子体技术对纤维毡进行表面改性,提高其表面润湿性。对未经过任何处理的熔喷聚乙烯纤维毡进行低温等离子体处理,通过接触角测量仪、红外光谱仪和扫描电镜对经过空气等离子体及丙烯酸气相等离子体处理的纤维毡进行表面接触角、官能团以及纤维表面形貌等特征进行表征。结果显示,随着放电时间和放电功率的增加,纤维毡表面亲水性得到了不断提升,改性后的纤维表面接枝了羟基(—OH)、醛基(—CHO)及羰基(C=O)等亲水性官能团,且表面形貌发生了一定的变化,表面微观粗糙度有所增大。这些一系列变化最终使纤维毡表面润湿性得到了有效改善。     

利用pH可控自组装法制备超疏水棉织物

利用水溶性耦合试剂N-(3-二甲氨基丙基)-N’-乙基碳二亚胺盐酸盐(EDC)和N-羟基琥珀酰亚胺(NHS)将小分子3-氨基苯硼酸(PBA)接枝到棕榈蜡乳液微球(PW)表面,成功制备了接枝苯硼酸官能团的改性棕榈蜡乳液微球(PW-PBA)。先将PW-PBA与聚乙烯醇(PVA)形成可逆硼酸酯,随后加入有机硅树脂,得到PW-PBA/PVA自组装超疏水棉织物。利用红外光谱、扫描电镜、粒度分析、接触角(CA)及强力机等测试手段研究了产物的结构形貌和性能。结果表明,接枝有苯硼酸官能团的棕榈蜡乳液微球与PVA多元醇的相互作用受pH控制;在pH条件(pH≥9)下,热熔处理后的PW-PBA/PVA自组装膜棉织物表面接触角显著增加,达到122°;当pH为9,有机硅树脂质量分数在3%以上时,热熔处理后的PW-PBA/PVA自组装膜棉织物表面接触角达到152°,此时达到超疏水效果,研究表明整理后的棉织物的物理力学性能有所提高。该方法制备过程绿色、环保、成本低,对于棉织物的性能改善有较好的效果。     

马来酸酐-烯丙氧基乙烯氧基羧酸共聚物去质子化程度对钙垢的影响

以马来酸酐和烯丙氧基乙烯氧基羧酸(APEA)为原料,通过自由基聚合法合成了含羧基和乙烯氧基的亲水性共聚物,通过红外光谱、核磁共振氢谱和凝胶色谱对其结构进行了表征。通过静态阻垢实验研究了聚合物的去质子化程度对抑制钙垢的影响,并通过扫描电镜和X射线衍射分析考察了聚合物的去质子化程度对碳酸钙晶体的形貌与晶型分布的影响。结果表明,随着去质子化程度的增加,聚合物对碳酸钙和硫酸钙垢的抑制效率逐渐降低,而对磷酸钙垢的抑制效率逐渐增加;阻垢剂去质子化程度的改变加速了文石和球霰石向方解石的转化,但这种转化并未明显影响碳酸钙晶体的形貌。     

以碳酸钙为模板制备空心羟基磷灰石微球及其表征

以碳酸钙为模板和钙源,与磷酸氢二铵通过水热反应,制备出尺寸均匀、形态规则的空心羟基磷灰石微球。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、扫描电镜(SEM)、透射电镜(TEM)测试制备的样品,结果显示,制备的空心羟基磷灰石微球具有与碳酸钙微球模板相似的形貌,空心,尺寸均匀且形貌规则。并通过改变水热反应时间探索了羟基磷灰石微球的形成机理。此羟基磷灰石空心微球在生物医学领域具有较大的应用前景。     

咪唑-1-乙酸改性壳聚糖仿生合成碳酸钙

以咪唑-1-乙酸改性壳聚糖(IACS)为生物模板仿合成碳酸钙,探讨了体系pH值和陈化时间等因素对碳酸钙的晶型和形貌的影响,利用场发射扫描电镜(FESEM)、X射线粉末衍射分析仪(XRD)、傅里叶红外光谱分析仪(FT-IR)对所合成的碳酸钙进行表征。结果表明,在纯水体系中所合成单一的立方体方解石晶型,而在组氨酸、咪唑-1-乙酸、咪唑-1-乙酸改性壳聚糖单独体系中则还有球状球霰石晶体呈现。在投加咪唑-1-乙酸改性壳聚糖有机基质体系中,当pH值从6.00升至9.00时,仿生合成球状球霰石的含量从75.9%缓慢降至54.6%;而缩小陈化时间,则有利于形成球霰石晶体。因此,利用IACS有机基质可以有效调控碳酸钙的晶型和形貌,也为仿生合成其它生物矿物提供借鉴。     

Charge-associated effects of fullerene derivatives on microbial structural integrity and central metabolism

The effects of four types of fullerene compounds (C60, C60-OH, C60-COOH, C60-NH2) were examined on two model microorganisms (Escherichia coli W3110 and Shewanella oneidensis MR-1). Positively charged C60-NH2 at concentrations as low as 10 mg/L inhibited growth and reduced substrate uptake for both microorganisms. Scanning electron microscopy (SEM) revealed damage to cellular structures. Neutrally charged C60 and C60-OH had mild negative effects on S. oneidensis MR-1, whereas the negatively charged C60-COOH did not affect either microorganism's growth. The effect of fullerene compounds on global metabolism was further investigated using [3-13C]L-lactate isotopic labeling, which tracks perturbations to metabolic reaction rates in bacteria by examining the change in the isotopic labeling pattern in the resulting metabolites (often amino acids).1-3 The 13C isotopomer analysis from all fullerene-exposed cultures revealed no significant differences in isotopomer distributions from unstressed cells. This result indicates that microbial central metabolism is robust to environmental stress inflicted by fullerene nanoparticles. In addition, although C60-NH2 compounds caused mechanical stress on the cell wall or membrane, both S. oneidensis MR-1 and E. coli W3110 can efficiently alleviate such stress by cell aggregation and precipitation of the toxic nanoparticles. The results presented here favor the hypothesis that fullerenes cause more membrane stress 4-6 than perturbation to energy metabolism.7.     

Surface characterization of aspirin crystal planes by dynamic chemical force microscopy

Tapping mode (TM) atomic force microscopy (AFM) has been applied in a novel fashion to characterize and distinguish the (001) and (100) surfaces of individual aspirin crystals. The surface characterization was achieved by amplitude-phase, distance (a-p,d) measurements employing gold-coated AFM probes functionalized with self-assembled monolayers (SAM). Experiments using model probes coated with -CH3 and -COOH terminated SAMs have been performed on the two aspirin crystal planes (001) and (100). Results indicate that the hydrophobic -CH3 terminated AFM probes had a greater degree of interaction with the crystal plane (001), whereas the -COOH terminated AFM probes had a larger interaction with the crystal plane (100). Interpretation of these data, based upon the chemistries of the probes, correlates with current understanding of the crystal surface chemistry derived from X-ray diffraction data and dissolution rate studies.     

Heterogeneous nucleation and growth mechanism on hydrophilic and hydrophobic surface

Heterogeneous nucleation and nucleation period of calcium carbonate on the mica and the highly oriented pyrolytic graphite (HOPG) substrate have been investigated. Calcium carbonate was prepared by the reaction of calcium nitrate solution with sodium carbonate solution. In the reaction crystallization of calcium carbonate, calcite and vaterite were nucleated on the both substrates. We counted the number of crystalline calcium carbonate on the substrates obtained from various initial supersaturations of calcium carbonate. The number of crystals on the mica surface was much higher than on the HOPG surface. Additionally, the number of crystals on the mica was greatly affected by changing of initial supersaturation. In order to explain the difference between the mica and the HOPG surface, a possible model for the nucleation period of calcium carbonate has been discussed. The surface crystallization on the mica and the HOPG could be described by considering the supersaturation in the bulk solution and in the vicinity of substrate, separately.     

A comparative study of natural, formaldehyde-treated and copolymer-grafted orange peel for Pb(II) adsorption under batch and continuous mode

Natural, formaldehyde-treated and copolymer-grafted orange peels were evaluated as adsorbents to remove lead ions from aqueous solutions. The optimum pH for lead adsorption was found to be pH 5. The adsorption process was fast, reaching 99% of sorbent capacity in 10 min for the natural and treated biomasses and 20 min for the grafted material. The treated biomass showed the highest sorption rate and capacity in the batch experiments, with the results fitting well to a pseudo-first order rate equation. In the continuous test with the treated biomass, the capacity at complete exhaustion was 46.61 mg g(-1) for an initial concentration of 150 mg L(-1). Scanning electronic microscopy and energy dispersive X-ray spectroscopy indicated that the materials had a rough surface, and that the adsorption of the metal took place on the surface. Fourier transform infrared spectroscopy revealed that the functional groups responsible for metallic biosorption were the -OH, -COOH and -NH(2) groups on the surface. Finally, the thermogravimetric analysis indicates that a mass reduction of 80% can be achieved at 600 degrees C.     

Various fates of neuronal progenitor cells observed on several different chemical functional groups

Neuronal progenitor cells cultured on gold-coated glass surfaces modified by different chemical functional groups, including hydroxyl (-OH), carboxyl (-COOH), amino (-NH₂), bromo (-Br), mercapto (-SH), -Phenyl and methyl (-CH₃), were studied here to investigate the influence of surface chemistry on the cells’ adhesion, morphology, proliferation and functional gene expression. Focal adhesion staining indicated in the initial culture stage cells exhibited morphological changes in response to different chemical functional groups. Cells cultured on -NH₂ grafted surface displayed focal adhesion plaque and flattened morphology and had the largest contact area. However, their counter parts on -CH₃ grafted surface displayed no focal adhesion and rounded morphology and had the smallest contact area. After 6 days culture, the proliferation trend was as follows: -NH₂>-SH>-COOH>-Phenyl>-Br>-OH>-CH₃. To determine the neural functional properties of the cells affected by surface chemistry, the expression of glutamate decarboxylase (GAD67), nerve growth factor (NGF) and brain-derived neurotrophic factor (BDNF) were characterized. An increase of GAD67 expression was observed on -NH₂, -COOH and -SH grafted surfaces, while no increase in NGF and BDNF expression was observed on any chemical surfaces. These results highlight the importance of surface chemistry in the fate determination of neuronal progenitor cells, and suggest that surface chemistry must be considered in the design of biomaterials for neural tissue engineering.     

Reduction of 3T3 Fibroblast Adhesion on SS316L by Methyl-Terminated SAMs

Inhibiting the non-specific adhesion of cells and proteins to biomaterials such as stents, catheters and guide wires is an important interfacial issue that needs to be addressed in order to reduce surface-related implant complications. Medical grade stainless steel 316L was used as a model system to address this issue. To alter the interfacial property of the implant, self assembled monolayers of long chain phosphonic acids with -CH(3), -COOH, -OH tail groups were formed on the native oxide surface of medical grade stainless steel 316L. The effect of varying the tail groups on 3T3 fibroblast adhesion was investigated. The methyl terminated phosphonic acid significantly prevented cell adhesion however presentation of hydrophilic tail groups at the interface did not significantly reduce cell adhesion when compared to the control stainless steel 316L.     

Statistical design of experiments: study of cross-linking process through the phase-resolved photoacoustic method as a multivariable response

This work presents an add-on result of cross-linking using photoacoustic spectroscopy (PAS) phases in a multivariable process using the phase-resolved photoacoustic (PRPA) method. The method is tested to separate contributions from groupings -OH, -CH(2)-, -CH(3), and Si-OH overtones in the range from 700 to 2600 nm. Samples of the copolymers ethylene vinyltrimethoxysilane (EVS) and grafted vinyltrimethoxysilane (VTS) on low-density polyethylene (LDPE) were prepared having concentrations (C) of 3, 5, and 7% of catalyst and temperatures (T) of 70, 80, and 90 degrees C. By considering the condensation reaction, the reduction of -OH groups is monitored. The PRPA analysis was carried out using the surface response methodology and results indicated the optimum point for both answers (signal and phase-resolved) and for both factors of interest (C, T). For the copolymers, it was found that C approximately (5.00 +/- 1.14)% and T approximately (82.4 +/- 4.3) degrees C, while for grafted LDPE PE(g) it was found that C approximately (4.92 +/- 0.85)% and T approximately (80.8 +/- 2.5) degrees C. These results agreed with the chemical analysis for gel content, which showed as the optimum point 5% of catalyst and temperature of 80 degrees C. Further, it is an advantage that the photoacoustic method allows one to per- form a nondestructive analysis.     

In vitro growth of calcium carbonate crystals on bivalve shells: Application of two methods of synthesis

The classic ammonium carbonate vapor diffusion method (VDM) and the coprecipitation method (CM) in its modified form were applied for in vitro growth of calcium carbonate crystals on glass substrate and on calcitic and aragonitic shell layers of blue mussel Mytilus edulis (L.) and Iceland scallop Chlamys islandica (M.). The experiments were carried out using large volumes of growth medium (250 ml and 1000 ml). Crystallization using the VDM is relatively slow, but faster with the CM. The formation of calcium carbonate polymorphs is strongly influenced by the mineralogical phase in the uppermost layer of the shell substrate bathed in the experimental solution, even if magnesium ions are added to solution with the CM. The morphology of calcium carbonate crystals clearly differs between methods, and is influenced by the type of substrate. The effect of biomacromolecules released from the shell substrate on morphology and organization of calcium carbonate crystals is clearly observed with both methods of crystallization.     

Collagen coating on hydroxyapatite surfaces modified with organosilane by chemical vapor deposition method

Type I collagen was coated onto the modified surfaces of hydroxyapatite (HAp) sintered body. The interfacial interaction between collagen and HAp in a nano-region was controlled by depositing the organosilane of n-octadecyltrimethoxysilane (ODS: -CH3) or aminopropyltriethoxysilane (APTS: -NH2) with a chemical vapor deposition method. The surfaces were elaborated by X-ray photoelectron spectroscopy, zeta-potential, and contact angle measurements; the Si and/or N peaks were detected, and the contact angles and surface energies were apparently different on the modified surfaces. The morphologies of collagen adsorbed on the surfaces of HAp and HAp deposited with APTS were similar, however that of the surface with ODS was apparently different, due to the hydrophobic interaction between the organic head group of -CH3 and residual groups of collagen.     

A test for mineralization inhibition for calcium salts using agarose hydrogels

Agarose hydrogel layers, containing dissolved calcium chloride, can be mineralized by immersion in sodium bicarbonate solution. Local injection of polyacrylic acid (PAA), a crystal growth inhibitor, into the gel results in a transparent zone, essentially free of calcium carbonate crystals. This effect is shown to be a true inhibition, not a reduction of calcium concentration due to chelation. This approach could be used to screen for the effect of mineralization inhibitors on mineralization and may prove to be more informative than studies carried out on mineralizing solutions.