生物矿化与植物体内的生物硅化

总结了硅在植物体内的沉积位点、存在形式、影响硅在植物体内沉积的因子以及生物硅化的作用,详细阐述了竹(木)材的生物硅化现象及其研究进展和展望。

丝素蛋白生物硅化材料在骨组织工程学中的应用

制备可生物降解并具有骨再生功能的支架材料是骨组织工程当前研究的重点领域。丝素蛋白具备可用作骨组织工程支架材料的许多要素,其中通过仿生方式生物矿化制备的丝素蛋白/无机复合材料与单纯丝素相比,由于具有较好的生物相容性、生物力学性能、可生物降解性以及骨诱导和传导特性,展现出更好的应用前景。本文综述了近年丝素蛋白生物硅化制备新型骨组织工程材料的研究进展,并展望了丝素蛋白生物硅化今后的发展方向。

海洋硅藻硅质细胞壁结构的形成机理研究概述

硅藻具有形态各异、结构复杂、精美绝伦的硅质细胞壁,是海洋中进行生物硅化最主要的生物体。硅质细胞壁的形成同样是一个错综复杂的过程,它涉及硅藻细胞将硅酸从胞外转运到胞内;硅酸在细胞内的转移;在硅沉积囊泡(SDV)中的浓缩沉积;最后合成具种类特异性的细胞壁。重点介绍硅酸转运基因(SITs)的分子特征与作用机制;与生物硅化相关的三种蛋白即硅体蛋白(frus-tulins)、亲硅蛋白(silaffins)和侧壁蛋白(pleuralins)的结构与功能;硅质结构如何在硅沉积囊泡内最终形成的模式。

硅质海绵骨针矿化机制及仿生应用研究进展

硅质海绵动物是地球上最简单、最古老的多细胞动物,它经几百万年的自然进化成就了适应自然和接近完美的技术蓝图,为人类利用纳米生物技术仿生合成生物无机矿物材料提供了一种崭新的节能和"环境友好"技术,在光纤、微电子和生物医学材料等领域具有广阔的仿生应用前景。生长在深海1000m以下水深的单根海绵动物的根须骨针长达3m,是世界上最长的生物硅,也是生物硅化机制和仿生应用研究不多见的载体。本文系统总结了我们在单根海绵动物根须骨针结构、组成、机械性能、光物理性能、生化特性和分子生物学基础、矿化机制和生物医学领域仿生应用等方面的研究成果。

Silicon limitation on primary production and its destiny in Jiaozhou Bay,China V:Silicon deficit process

Silicon is a necessary nutrient for diatoms, silicon uptake in diatom reproduction decreased sea- water silicon content. This paper clarified the characteristics of silicon transferring in the sea, which plays an important role in phytoplankton growth, zooplankton graze and marine ecosystem. Analysis revealed that silicate is supplied by terrestrial sources, through plankton uptake, death, and eventually deposits to the sea bottom, and cannot diffuse upward. This is a general silicon deficit process. Many global marine waters showed the same silicon transfer route: land→silicon biogeochemical process→sea bottom. River flow brings abundant silicate into marine waters, silicate concentration in the waters decreased in the distance away from the river estuaries. In discussion of silicon characteristics and its transfer route, it was considered that the main factor controlling the mechanism of diatom and non-diatom red tides occurrence is silicon, and the changes in silicon source. Human activities, such as sea-route cutting by building embankment and dam, and silicon supplement by the sea, such as sandstorm, rainstorm and storm tide, have largely impaired the earth ecosystem and hugely threatened the human existence. It is suggested in this paper that man should resume the original face of the Si input into the sea to keep natural ecosystem in sustainable pattern.

Continuous production of biodiesel from cottonseed oil and methanol using a column reactor packed with calcined sodium silicate base catalyst

Sodium silicate and that calcined at 400℃ for 2 h were used to catalyze the transesterification of cottonseed oil with methanol. Calcined sodium silicate （CSS） catalyst exhibited much higher catalytic activity and stability. A maximum biodiesel yield of 98.9~ was achieved at methanol/oil mole ratio of 12：1, reaction temperature 65℃, reaction time 3.0 h, and CSS/oil mass ratio of 2 Wffo. After 7 consecutive reactions without any treatment, biodiesel yield reduced to 82.5%. Considering technological and economic feasibility, CSS base catalyst supported on 0 rings was prepared for continuous transesterification. The maximum yield was 99.1% under optimum conditions （reaction temperature 55 ~C, methanol velocity 1 ml. rain- 1, oil velocity 3 ml- rain- 1, and 5 tower sec- tions）. These results indicate that this new continuous biodiesel production process and apparatus present a great potential for industrial application in biodiesel.

Formation kinetics and transition mechanism of CaO·SiO2 in low-calcium system during high-temperature sintering

The crystal structure,formation kinetics and micro-morphology of CaO·SiO2 during high-temperature sintering process were studied in low-calcium system by XRD,FT-IR,Raman and SEM-EDS methods.When the molar ratio of CaCO3 to SiO2 is 1.0,β-2CaO·SiO2 forms firstly during the heating process,and then CaO·SiO2 is generated by the transformation reaction of pre-formed 2CaO·SiO2 with SiO2.3CaO·SiO2 and 3CaO·2SiO2 do not form either in the heating or sintering process.Rising the sintering temperature and prolonging the holding time promote the phase transition of 2CaO·SiO2 to CaO·SiO2,resulting in the sintered products a small blue shift and broadening in Raman spectra.The content of CS can reach 97.4%when sintered at 1400℃ for 1 h.The formation kinetics of CaO·SiO2 follows the second-order chemical reaction model,and the corresponding apparent activation energy and pre-exponential factor are 505.82 kJ/mol and 2.16×10^14 s^−1 respectively.

BIOGEOCHEMICAL PROCESSES OF PHOSPHORUS AND SILICON IN SOUTHERN BOHAI SEA SURFACE SEDIMENTS

Based on the author’s previously obtained results on P and Si forms in southern Bohai Sea surface sediments,this study mainly foucusing on the controlling factors, existence forms, and biogeochemical processes of P and Si showed that the transferable forms of phosphorus in sediments were mainly controlled by the mineralization of organic matters and the reduction of high valence iron; whereas the transferable forms of silicon were possibly controlled by the dissolution and precipitation as well as biochemical processes of living organisms.

Laccase biosensor using magnetic multiwalled carbon nanotubes and chitosan/silica hybrid membrane modified magnetic carbon paste electrode

A simple and rapid strategy to construct laccase biosensor for determination of catechol was investigated. Magnetic multiwalled carbon nanotubes (MMCNT) which possess excellent capability of electron transfer were prepared by chemical coprecipitation method. Scanning electron microscope (SEM) and vibrating sample magnetometer (VSM) were used to identify its surfacetopography and magnetization, respectively. Laccase was immobilized on the MMCNT modified magnetic carbon paste electrode by the aid of chitosan/silica (CS) hybrid membrane. Using current-time detection method, the biosensor shows a linear response related to the concentration of catechol in the range from 10-7 to 0.165×10-3 mol/L. The corresponding detection limit is 3.34×10-8 mol/L based on signal-to-noise ratios (S/N) ≥3 under the optimized conditions. In addition, its response current retains 90% of the original after being stored for 45 d. The results indicate that this proposed strategy can be expected to develop other enzyme-based biosensors.

Effects of 4 Types of Remediation Agents on Reducing Cd Contents in Soil and Rice on Cd-contaminated Farmland

A field experiment was carried out in Cd-contaminated rice fields in a county of Hengyang to explore the effects of different types of remediation agents on the contents of soil available Cd and rice Cd,and rice yield by using one rice variety Longliangyouhuazhan,and 4 kinds of remediation agents:DG foliar control agent,SMA microbial inoculant,XFJ organic fertilizer and LXM calcium-and silicon-based passivator as test materials.The results showed that compared with CK,after applying DG foliar control agent,soil available Cd content increased rather than decreased,whereas rice Cd content decreased,not reaching a significant level.When applied with SMA microbial inoculant,soil pH value,soil available Cd and rice Cd contents showed a downward then upward trend with the increase of its application rates.Between 3 levels of SMA treatments,the content of soil available Cd in SMA2 was the lowest,decreased by 8.59%in comparison with CK,contrarily,two other SMA treatments were increasing instead of decreasing in the content of soil available Cd.The application of XFJ organic fertilizer and LXM calcium-and silicon-based passivator increased soil pH value,and reduced soil available Cd and rice Cd contents;the contents of soil available Cd and rice Cd decreased with their application rates increasing.Compared with CK,XFJ3 reduced soil available Cd content by 9.40%,and significantly reduced rice Cd content by 57.28%.In LXM3 treatment,soil available Cd content reduced by 14.57%,rice Cd content was 71.57%lower than CK,reaching the lowest level.In general,LXM calcium-and silicon-based passivator had the best Cd reduction effect,with the optimal application amount of 6000 kg/hm^(2).

Preparation and Characterization of Silica Modified with Calix[4]arene Derivatives

Three new silica gel modified with calix[4]arene derivatives （p-tert-butyl-calix[4]arene （PC4）, calix[4]arene （C4） and calix[4]arene sulfonate （C4S）） have been prepared via modification of activated silica gel with toluene 2,4-di-iso-cyanate （TDI） as linker in tow step. The modified silica were characterized by fourier transform infrared spectroscopy （FT1R）, thermal analysis （TGA） and elemental analysis. The FTIR spectra and TGA analysis verified that the calix[4]arene derivates are covalent attached to the silica. Scanning electron microscope SEM and Brunauer-Emmett-Teller BET analysis have been done to get information about the sample＇s surface shape and area. SEM and BET analysis reveal that the modified silica are in the range of microporous adsorbent.

Fabrication of a solid superacid with temperature-regulated silica-isolated biochar nanosheets

This paper reports a new strategy for the structural reconstruction of biomass carbon sulfonic acid(BCSA)to its solid superacid counterpart.In this approach,a cheap layered biomass carbon(BC)source is chemically exfoliated by cetyltrimethyl ammonium bromide and then converted to silica-isolated carbon nanosheets(CNSs)by a series of conversion steps.The state of the silica-isolated CNSs and the stacking density of their nanoparticles are regulated by the dehydration temperature.Only the highly isolated and non-crosslinked CNSs with loose particle stacking structures obtained upon dehydration at 250℃ can be turned into superacid sites(with stronger acidity than that of 100%H2 SO4)after sulfonation.This is accompanied by the creation of abundant hierarchical slit pores with high external surface area,mainly driven by the strong hydrogen bonding interactions between the introduced sulfonic acid groups.In typical acid-catalyzed esterification,etherification,and hydrolysis reactions,the newly formed superacid exhibits superior catalytic activity and stability compared to those of common BCSA and commercial Amberlyst-15 catalysts,owing to its good structural stability,highly exposed stable superacidic sites,and abundance of mesoporous/macroporous channels with excellent mass transfer rate.This groundbreaking work not only provides a novel strategy for fabricating bio-based solid superacids,but also overcomes the drawbacks of BCSA,i.e.,unsatisfactory structural stability,acidity,and porosity.

Biogenic characteristics of Mesozoic cherts in southern Tibet and its significance

The Xialu chert, which contains abundant biological information, were investigated by major element analysis, micro-Raman, SEM and EPMA. The results show that SiO2 content of chert is 84.12%-93.08%, averaging 89.84%. The close packed structures of low degree crystallinity of quartz indicate the hydrothermal origin. SiO2 of modern hot springs exhibit loose silica pellets and nodular, beaded structures. Under polarization microscope, the presence of biological skeleton structures indicate that biological activities are involved in the hydrothermal deposition, which correspond to the geochemical characteristics: w(SiO2)/ w(K2O+Na2O), w(SiO2)/w(Al2O3) and w(SiO2)/w(MgO), with average values of 295.29, 68.88 and 284.45, respectively. SiO2 is enriched in the organism(radiolarian) centers, the degree order of SiO2 within the biologic structures is much higher than that of outside. The impurity minerals albites are formed earlier than the original deposition. Kaolinites, feldspars and mixture of organic materials display lower degree of crystallinities and accumulate as vermicular aggregates.

Study on the thermodynamics and the growth kinetics of synthesis of the β-SiC whiskers

The thermodynamics and the growth kinetics of synthesis of the SiC whiskers (SiC w ) from rice hulls are studied in this paper. The results show that the intimate contact of SiO 2 with C in the rice hulls resulted in the formation of SiC particle (SiC p ) at lower temperature, and the external ash of the hulls (w (SiO 2 )>98%) is the main silicon source for SiCw growth. The metallic composite catalyst increases the selectivity for SiCw growth and the reaction rate. The growth mechanism of the SiCw can be characterized as the VLS (vapour liquid solid) with the presence of the whisker forming catalyst: from SiC nucleation through enlargement and growing with the <1 1 1> crystallographic orientation in a certain diameter, then the SiC w is a complete single crystal of β SiC. The generation reaction of SiO is the rate determing step for synthesis of SiC w .

Extraction and Structure Elucidation of Phenols from Dendrobium thyrsiflorum

[Objective] This study aimed to investigate the chemical constituents of Dendrobium thyrsiflorum and determine its bioactive compounds. [Method] The compounds were extracted by 95% alcohol and isolated by column chromatography on silica gel and Sephadex LH-20. Their structures were identified by spectroscopic analysis(1H NMR and13 C NMR). [Result] Seven compounds were obtained and identified as 4, 7-dihydroxy-2-methoxy-9, 10-dihydrophenan-threne(1), syringaldehyde(2),moscatin(3), gigantol(4), batatasin III(5), tristin(6) and stigmasterol(7). [Conclusion] Compounds 1 and 2 were isolated from this medicinal plant for the first time.

海绵硅蛋白研究进展

海绵是生物进化过程中最古老的多细胞动物,其中大部分能够利用二氧化硅在常温水环境下合成形状、大小和结构极为丰富的硅质骨骼。随着近年来人们发现其骨骼的基本组成单位骨针具有优异的光导性能和机械性能,海绵生物硅化过程及仿生纳米和微米硅质生物材料合成的研究成为生物技术和材料科学的热点。在海绵生物硅化过程中,一类被称为硅蛋白(Silicatein)的蛋白质表现出了特殊的催化活性,也因此得到了生物学家、化学家和材料学家的关注。以下将对硅蛋白的国际研究现状进行了评述,以期促进国内相关领域的研究。

Variability in the composition and export of silica in the Huanghe River Basin

Concentrations of suspended particle material(SPM), dissolved silicate(DSi), biogenic silica(BSi), phytoliths(plant produced siliceous microscopic structures), and other parameters were analyzed to examine the influence of both natural processes and human activities on silica delivery to the estuary of the Huanghe River(Yellow River). Our results indicate that the concentrations of DSi in the river decreased significantly since 1986. Approximately 34% of dissolved silica was trapped in the basin between 1986 and 2010 due to a reduction of soil erosion. Phytoliths comprised 67.2%–96.3% of BSi, with the smoothing bar type being the dominant form. Concentrations of BSi are significantly higher in the Huanghe River compared to other major rivers throughout the world due to its high sediment yield. We also found that the ratios of BSi/(BSi+DSi) and BSi/SPM were approximately 0.5 and 0.003 at Lijin near the river mouth, indicating that BSi carried in suspension by the Huanghe River was an important component of the rivers silica load. Significant amounts of BSi were also composed of phytoliths in Bohai Sea sediments near the Huanghe River estuary with the smoothing bar form again being the most abundant. The relatively high specific fluxes of BSi in the Huanghe River reflect its high turbidity and high erosion rates in the basin. The high sediment load originating on the Loess Plateau is likely responsible for the higher BSi flux, in agreement with a general trend of increasing BSi flux with increasing sediment flux in global river systems. This study demonstrates that BSi transported by rivers can be composed largely of phytoliths originating from the erosion of topsoils. The flux of phytoliths in river's suspended sediment load may therefore represent a significant contribution to the biogeochemical cycle of silica in coastal waters.

High hydrosilylation efficiency of porous silicon SiHx species produced by Pt-assisted chemical etching for biochip fabrication

Porous silicon （PSi） prepared from Pt metal-assisted chemical etching （MACE） was demonstrated to possess higher hydrosi- lylation efficiency （-57%） than anodized PSi （-11%） by surface reaction with co-undecenyl alcohol （UO）. Deconvolution of the SiHx （x = 1-3） stretching bands revealed the abundance of SiH2 species on MaCE PSi was 53%, -10% higher than on ano- dized samples, while both of Sill1 and Sill3 were -5% lower correspondently on MaCE PSi than on anodized samples. The surface SiHx abundances were suggested to account for the higher hydrosilylation efficiency on MaCE PSi. Optimization of Pt-assisted chemical etching parameters suggested a 7-15 nm thick Pt-coating and an etching time of 3-10 min for biochip ap- plications. Scanning electron microscopy images revealed that an isotropic top meso-porous layer was beneficial for hydrosi- lylation and long-term durability under ambient conditions. To end, an example of histidine-tagged protein immobilization and microarray was illustrated. Combining the materials＇ property, surface chemistry, and micro-fabrication technology together, we envision that silicon based biochip applications have a prosperous future.

Oligonucleotide delivery by chitosan-functionalized porous silicon nanoparticles

Porous silicon nanoparficles （pSiNPs） are a promising nanocarrier system for drug delivery owing to their biocompatibility, biodegradability, and non-inflammatory nature. Here, we investigate the fabrication and characterization of thermally hydrocarbonized pSiNPs （THCpSiNPs） and chitosan-coated THCpSiNPs for therapeutic oligonucleotide delivery. Chitosan coating after oligonucleotide loading significantly improves sustained oligonucleotide release and suppresses burst release effects. Moreover, cellular uptake, endocytosis, and cytotoxicity of oligonucleotide-loaded THCpSiNPs have been evaluated in vitro. Standard cell viability assays demonstrate that cells incubated with the NPs at a concentration of 0.1 mg/mL are 95% viable. In addition, chitosan coating significantly enhances the uptake of oligonucleotide-loaded THCpSiNPs across the cell membrane. Moreover, histopathological analysis of liver, kidney, spleen, and skin tissue collected from mice receiving NPs further demonstrates the biocompatible and non-inflammatory properties of the NPs as a gene delivery vehicle for intravenous and subcutaneous administration in vivo. Taken together, these results suggest that THCpSiNPs provide a versatile platform that could be used as efficient vehicles for the intracellular delivery of oligonucleotides for gene therapy.

High-yield preparation of robust gold nanoshells on silica nanorattles with good biocompatiblity

Although gold nanoshells are widely considered as one of the promising photothermal nanomaterials used for biomedicine, the high cost, low yield and poor stability severely limit their potential application in clinical trials.Herein, robust gold nanoshells on silica nanorattles(GSNs)were easily prepared in a high yield by an improved seedmediated method employing polyvinylpyrrolidone(PVP) as a stabilizing and capping agent. The present method is very simple, effective and reproducible and can well control the growth process of gold nanoshells. The as-prepared GSNs have a narrow size distribution(<10 % in standard deviation). Furthermore, the utilization rate of Au in the solution used for the growth of gold nanoshells increases by 70 %than that in previous method. The resultant GSNs have a good structural stability after placing over 6 months due to the protection of PVP. More importantly, in vivo and in vitro toxic studies indicate that the GSNs have good biocompatibility. We believe that our preparation method will remarkably promote the use of gold nanoshells for biomedicine.