Bioavailability of silicon from food and food supplements

The bioavailability of silicon from three different silicon sources was studied. A diet rich in silicon, a tablet containing a dry extract of horsetail and a solution of silicon in a choline-glycerol matrix were compared. Blood and urine of one healthy test person were sampled to monitor the silicon uptake. The silicon content of blood and serum samples was determined by graphite furnace atomic absorption spectrometry. Strongly diverging results were obtained for the three different silicon sources. Neither an increase in urinary silicon excretion nor in serum silicon content was observed when feeding the silicon rich diet. Urinary silicon excretion did significantly (P < 0.05) rise during supplementation with tablets containing dry extract of horsetail. Intake of a solution of silicon in a choline-glycerol matrix resulted in a significantly (P < 0.05) increased urinary silicon excretion and serum silicon content. From these results it can be concluded that speciation (chemical form, matrix) strongly influences the bioavailability of silicon. Received: 3 August 1998 / Revised: 25 September 1998 / Accepted: 30 September 1998     

超疏水多孔硅的制备及表面稳定性

在加热条件下采用氢化硅烷化反应对多孔硅表面进行改性,通过扫描电子显微镜、红外光谱及元素分析等手段表征了多孔硅改性前后的结构和组成,研究了不同反应时间对其性能的影响.结果表明,反应3 h后制得了超疏水表面的多孔硅,其在碱性及空气环境中具有良好的稳定性.     

Silicon-silica nanowires, nanotubes, and biaxial nanowires: inside, outside, and side-by-side growth of silicon versus silica on zeolite

It was demonstrated that zeolite can be used as a pseudo-template to grow very fine and uniform silicon nanostructures via disproportionation reaction of SiO by thermal evaporation. Three distinct types of composite nanowires and nanotubes of silicon and silica were grown on the surfaces of zeolite Y pellets. The first type is formed by an ultrafine crystalline silicon nanowire sheathed by an amorphous silica tube (a silicon nanowire inside a silica nanotube). The second type is formed by a crystalline silicon nanotube filled with amorphous silica (a silicon nanotube outside a silica nanowire). The third type is a biaxial silicon-silica nanowire structure with side-by-side growth of crystalline silicon and amorphous silica. These silicon nanostructures exhibit unusually intense photoluminescence (in comparison to ordinary silicon nanowires).     

介孔硅与大孔硅的结构、电学和气敏特性

采用双槽电化学腐蚀法在P型单晶硅表面制备两种多孔硅.根据它们的孔径将它们分为介孔硅和大孔硅.使用扫描电子显微镜(SEM)观察两种多孔硅表面和断面形貌,介孔硅和大孔硅的表面化学键用傅里叶变换红外(FTIR)光谱仪来研究,通过I-V特性测试表征两种多孔硅电学特性,随后在室温下测试其气敏特性.结果表明:介孔硅具有较高的气体灵敏度,大孔硅具有较好的气体响应恢复特性.介孔硅对NO2气体具有较好的选择性,大孔硅对NH3气体具有较好的选择性.     

Effects of Ultraviolet Illumination and Pre-treatments on Porous Silicon Formation

Although porous silicon is readily formed by anodizing silicon wafers in HF-based solutions, its application in silicon-based optoelectronic devices is greatly limited due to its poor stability and low luminescence yield. It is well recognized that the nature of silicon wafers and the fabrication condition parameters significantly influence uniformity, stability and optical properties of porous silicon. In this work, the ultraviolet illumination and pre-treatments were investigated for porous silicon formation. The surface morphologies and optical properties of the samples were also studied.     

Synthesis and properties of nanosilicon stabilized by butyl and perfluorobutyl ligands

Nanocrystalline silicon stabilized by butyl and perfluorobutyl ligands that form improper surface states of silicon nanocrystals were synthesized. The presence of perfluorobutyl ligands on the surface of silicon nanocrystals was proved by IR spectroscopy. Nanocrystals with perfluorobutyl ligands form aggregates, which decreases the efficiency of photoluminescence. The nanocrystals with butyl ligands have smaller size but their photoluminescence can be clearly recorded.     

Extremely superhydrophobic surfaces with micro- and nanostructures fabricated by copper catalytic etching

We demonstrate a simple method for the fabrication of rough silicon surfaces with micro- and nanostructures, which exhibited superhydrophobic behaviors. Hierarchically rough silicon surfaces were prepared by copper (Cu)-assisted chemical etching process where Cu nanoparticles having particle size of 10-30 nm were deposited on silicon surface, depending on the period of time of electroless Cu plating. Surface roughness was controlled by both the size of Cu nanoparticles and etching conditions. As-synthesized rough silicon surfaces showed water contact angles ranging from 93° to 149°. Moreover, the hierarchically rough silicon surfaces were chemically modified by spin-coating of a thin layer of Teflon precursor with low surface energy. And thus it exhibited nonsticky and enhanced hydrophobic properties with extremely high contact angle of nearly 180°.     

Formation of six-coordinated silicon in calcium phosphosilicate xerogels assisted by polyols at low temperature and pressure

Silicon is usually found to be four-coordinated when neighbored with oxygen. Six-coordinated silicon is only seen in samples at very specific composition or made at high temperature/pressure. In this study,we managed to synthesize calcium phosphosilicate xerogels containing six-coordinated silicon with the help of polyols by sol–gel method, without the need of treatment at high temperature or high pressure.Both phosphorus precursors and polyols were found to be essential for the formation of six-coordinated silicon species; in the absence of either species, only normal four-coordinated silicon was observed under otherwise identical conditions. Samples containing six-coordinated silicon sites were found to release silicon species faster than those without six-coordinated silicon sites upon dissolved in water,suggesting that six-coordinated silicon species have higher reactivity toward hydrolysis.     

Simultaneous direct determination of aluminum, calcium and iron in silicon carbide and silicon nitride powders by slurry-sampling graphite furnace AAS.

A fast and accurate analytical method was established for the simultaneous direct determination of aluminum, calcium and iron in silicon carbide and silicon nitride powders by graphite furnace atomic absorption spectrometry using a slurry sampling technique and a Hitachi Model Z-9000 atomic absorption spectrometer. The slurry samples were prepared by the ultrasonication of silicon carbide or silicon nitride powders with 0.1 M nitric acid. Calibration curves were prepared by using a mixed standard solution containing aluminum, calcium, iron and 0.1 M nitric acid. The analytical results of the proposed method for aluminum, calcium and iron in silicon carbide and silicon nitride reference materials were in good agreement with the reference values. The detection limits for aluminum, calcium and iron were 0.6 microg/g, 0.15 microg/g and 2.5 microg/g, respectively, in solid samples, when 200 mg of powdered samples were suspended in 20 ml of 0.1 M nitric acid and a 10 microl portion of the slurry sample was then measured. The relative standard deviation of the determination of aluminum, calcium and iron was 5 - 33%.     

多孔硅的制备与光伏特性研究

采用特制的电解池在不同条件下制备了一系列多孔硅样品。通过测定其ＳＰＳ发现，多孔硅的ＳＰＳ特征带同单晶硅相比有明显蓝移，并且随制备条件不同，蓝移效应也不同。电解质中ＨＦ浓度和电解时间对基ＳＰＳ响应有明显影响，这一现象的出现主要归因于最子线阵的生成。     

两步法制备多孔硅及其表征I:恒电流法(英文)

本工作通过采用电化学极 -化学氧化两步法在 1:1氢氟酸和乙醇溶液中制备出孔径约为 1～ 2 μm ,厚度大经为 6～ 10 μm的多孔硅样品 .首先将 0 .0 3A/cm2 的恒电流施加到p( 10 0 )硅片一段时间 ,然后将该硅片浸到 2 0 %的硝酸溶液中氧化一段时间 .通过此方法获得的多孔硅结构再进一步用扫描电子显微镜和拉曼光谱仪进行表面形貌和光学性质的考察 .所有制备出的多孔硅结构均有光致发光现象 .老化的多孔硅样品 (在干燥器放置一年 )的光致发光谱峰强度明显增强 ,但分别经过苯乙烯和十六碳烯 ( 1)两种有机溶剂处理 1h后的老化多孔硅样品的光致发光强度却没有显著改变 .     

单晶硅氩离子注入层的微观结构和微观摩擦磨损行为

利用离子注入技术对单晶硅表面进行了氩离子注入,用微摩擦磨损实验机研究了改性层的摩擦磨损行为,并用透射电子显微镜研究了改性层的微观结构.结果表明:经过一定剂量的氩离子注入后单晶硅的耐磨性能较注入前有了一定的提高,其中以注入剂量1×1016ions/cm2为最好,氩离子的注入使单晶硅表面形成了硅的微晶态与非晶态共存的混和态结构的改性层,使其具有良好的抗塑变和塑性剪切能力,从而改善了单晶硅的抗磨能力.     

四配位硅单体及其共聚物的制备和结构表征

研究了直接从无定形二氧化硅出发, 与乙二醇、氢氧化钾反应, 生成高反应活性的五配位硅钾化合物, 并以此为原料与含活泼氯的3-氯丙烯反应制备出含双键官能团的四配位硅单体. 讨论了合成单体的条件如温度、反应时间、反应物浓度、溶液pH值及溶剂等因素的影响. 然后以该四配位硅单体与甲基丙烯酸甲酯(MMA)在偶氮二异丁腈(AIBN)作引发剂下进行自由基聚合得到支链含硅共聚物. 并借助于红外光谱(IR)、核磁共振(¹³C和¹H, ²⁹Si)、能谱元素分析对合成的单体进行了结构表征; 用红外光谱(IR)、热失重谱(TG)、差示扫描量热谱(DSC)、凝胶渗透色谱法(GPC)等现代测试手段对支链含硅共聚物进行了结构表征及热性能分析. IR表明四配位硅单体在1646 cm^－1处是C＝C的伸缩振动吸收峰, 在共聚物中此峰消失; TG表明共聚物在249.6 ℃才开始失重, 552 ℃有机部分失重完毕; GPC分析表明共聚物的数均分子量为8.7万.     

Protein delivery based on uncoated and chitosan-coated mesoporous silicon microparticles

Mesoporous silicon is a biocompatible, biodegradable material that is receiving increased attention for pharmaceutical applications due to its extensive specific surface. This feature enables to load a variety of drugs in mesoporous silicon devices by simple adsorption-based procedures. In this work, we have addressed the fabrication and characterization of two new mesoporous silicon devices prepared by electrochemistry and intended for protein delivery, namely: (i) mesoporous silicon microparticles and (ii) chitosan-coated mesoporous silicon microparticles. Both carriers were investigated for their capacity to load a therapeutic protein (insulin) and a model antigen (bovine serum albumin) by adsorption. Our results show that mesoporous silicon microparticles prepared by electrochemical methods present moderate affinity for insulin and high affinity for albumin. However, mesoporous silicon presents an extensive capacity to load both proteins, leading to systems were protein could represent the major mass fraction of the formulation. The possibility to form a chitosan coating on the microparticles surface was confirmed both qualitatively by atomic force microscopy and quantitatively by a colorimetric method. Mesoporous silicon microparticles with mean pore size of 35 nm released the loaded insulin quickly, but not instantaneously. This profile could be slowed to a certain extent by the chitosan coating modification. With their high protein loading, their capacity to provide a controlled release of insulin over a period of 60-90 min, and the potential mucoadhesive effect of the chitosan coating, these composite devices comprise several features that render them interesting candidates as transmucosal protein delivery systems.     

Impact sensitivity of energy systems based on nanoporous silicon and oxidant: influence of the hydrogen content and specific surface

The impact sensitivity of the energy systems based on nanoporous silicon, obtained by electrochemical etching of monocrystalline silicon wafers in an HF-containing electrolyte, and calcium perchlorate was studied using a modified Weller—Ventselberg technique (estimation of the impact sensitivity of initiating explosives). The impact sensitivity of these systems is shown to be determined by both the presence of hydrogen, which is stored on the porous silicon surface during the preparation of the latter, and also the influence of other factors, including the specific surface of porous silicon. The composition, amount of the generated gas, and gas evolution rate during nonisothermal and isothermal calcination of porous silicon in a temperature range of 60—120 °С were determined using methods of thermal gravimetry (TG), measurement of the gas volume, and mass spectrometry. The generated gas almost completely consists of hydrogen, and its content in the studied samples of porous silicon achieved ~3.8 wt.%. The calculated activation energy of the hydrogen evolution process in vacuo was 103.7±3.3 kJ mol^–1. The dependences of the impact sensitivity of the energy composition based on porous silicon and heat of combustion of porous silicon on oxygen on the hydrogen content were established. The impact sensitivity of the energy system decreases with a decrease in the hydrogen content in porous silicon and its specific surface.     

The structure and properties of a new type of nanostructured composite Si/C electrodes for lithium ion accumulators

The results obtained in studies of the structure and electrochemical properties of film electrodes prepared by magnetron plasma sputtering of silicon and graphite and working under the conditions of lithium injection and extraction are generalized. Composite silicon-carbon electrodes synthesized by depositing silicon and carbon nanolayers with the use of a magnetron plasma were films 100–500 nm thick. Part of them exhibited highly uniform nanogranular structure based on a carbon matrix with inserted silicon clusters of size below 6 nm. The nanogranular structure of Si/C composites was observed for the first time; such a morphology was not characteristic of not structured silicon layers deposited under equal conditions. The factors that determined the electrochemical charging-discharging behavior of new composites were the degree of uniformity of the nanogranular structure, the ratio between the silicon and carbon components, and film thickness. For two thin films, the initial composite capacitance was higher than that corresponding to the Li_4.4Si stoichiometry for the silicon component and LiC₆ stoichiometry for the carbon component, which was related to the special nanostructured state of silicon and carbon. The effects (luminescence band and absorption bands in the visible range) characteristic of nanosized silicon particles were observed.     

混合酸制备四氟化硅气体用于硅同位素测量

1引言在自然界中,硅元素有3种稳定同位素28Si,29Si和30Si,丰度分别为92.23%,3.68%和3.09%。准确测量硅的摩尔质量,需准确测量硅的3种同位素的丰度值。目前,测量硅摩尔质量最佳的方法是采用SiF4气体测定硅同位素的丰度值,这     

Fabrication of nanostructured silicon by metal-assisted etching and its effects on matrix-free laser desorption/ionization mass spectrometry

A matrix-free, high sensitivity, nanostructured silicon surface assisted laser desorption/ionization mass spectrometry (LDI-MS) method fabricated by metal-assisted etching was investigated. Effects of key process parameters, such as etching time, substrate resistance and etchant composition, on the nanostructured silicon formation and its LDI-MS efficiency were studied. The results show that the nanostructured silicon pore depth and size increase with etching time, while MS ion intensity increases with etching time to 300 s then decreases until 600 s for both low resistance (0.001–0.02 Ω cm) and high resistance (1–100 Ω cm) silicon substrates. The nanostructured silicon surface morphologies were found to directly affect the LDI-MS signal ion intensity. By characterizing the nanostructured silicon surface roughness using atomic force microscopy (AFM) and sample absorption efficiency using fluorescence microscopy, it was further demonstrated that the nanostructured silicon surface roughness was highly correlated to the LDI-MS performance.     

硅(100)晶面上硅和二氧化硅的横向与纵向腐蚀速率

The method established previously for studying the etching rates of micro-scale silicon and silica was used to study the etching process of silicon and silica on the Si（100）surface. Photolithography was used to pattern a positive photoresist mask to confine the etching area,and the atomic force microscopy was used to probe the etched surface. The lateral etching rate of silicon or silica on the silicon surface was defined,and the lateral and longitudinal etching rates of silicon and silica on the Si（100）surface in 40% ammonium fluoride aqueous solution were measured. The effect of the dissolved oxygen on the etching rates was studied by bubbling the solution with high purity nitrogen. The lateral and longitudinal etching rates of silicon and silica on the（100）surface increase with temperatures except for the lateral etching rate of silica in a N2 -bubbled solution which probably reaches the limit of diffusion controlled reaction. The etching rates of silicon and thermal silica on the Si（100）surface show remarkable difference with that on the Si（111）surface in both air-saturated and N2 -bubbled solutions. The apparent activation energies for the silicon and silica etching processing in ammonium fluoride solution were obtained from the etching rates at different temperatures in the range 20. 6-34. 1℃. The similarity of the apparent activation energies for the etching processing of silicon and silica on the（100）surface to that on the（111）surface probably suggests that the rate-determined-step is the same in both cases. A lot of gas bubbles are seen to aggregate on the surface in silicon dissolution process at 38. 2℃,and it is found that the gas bubbles have great influence on the silicon etching rate. The formation of bubbles accelerates the silicon dissolution at the beginning but blocks the etching as the bubbles gradually aggregate on the surface.     

Effect of substrate surface on dewetting behavior and chain orientation of semicrystalline block copolymer thin films

Three symmetrical semicrystalline oxyethylene/oxybutylene block copolymers (EmBn) were spin-coated on different substrates including silicon, hydrophobically modified silicon, and mica. The effects of surface property on the dewetting behavior of EmBn thin films and the chain orientation of the crystalline block were investigated with atomic force microscopy and grazing incidence X-ray diffraction . The EmBn thin films on silicon exhibit an autophobic dewetting behavior, while ordinary dewetting occurs for the thin films on modified silicon. It was observed that the stems of the E crystals in the first half-polymer layer contacting the mica surface were parallel to the surface, in contrast to the perpendicular chain orientation of the other polymer layers and of the first half-polymer layer on silicon. This is attributed to the strong interaction between the E block and mica, verified by infrared spectra.