Selective adsorption and chiral amplification of amino acids in vermiculite clay-implications for the origin of biochirality

Smectite clays are hydrated layer silicates that, like micas, occur naturally in abundance. Importantly, they have readily modifiable interlayer spaces that provide excellent sites for nanochemistry. Vermiculite is one such smectite clay and in the presence of small chain-length alkyl-NH(3)Cl ions forms sensitive, 1-D ordered model clay systems with expandable nano-pore inter-layer regions. These inter-layers readily adsorb organic molecules. n-Propyl NH(3)Cl vermiculite clay gels were used to determine the adsorption of alanine, lysine and histidine by chiral HPLC. The results show that during reaction with fresh vermiculite interlayers, significant chiral enrichment of either L- and D-enantiomers occurs depending on the amino acid. Chiral enrichment of the supernatant solutions is up to about 1% per pass. In contrast, addition to clay interlayers already reacted with amino acid solutions resulted in little or no change in D/L ratio during the time of the experiment. Adsorption of small amounts of amphiphilic organic molecules in clay inter-layers is known to produce Layer-by-Layer or Langmuir-Blodgett films. Moreover atomistic simulations show that self-organization of organic species in clay interlayers is important. These non-centrosymmetric, chirally active nanofilms may cause clays to act subsequently as chiral amplifiers, concentrating organic material from dilute solution and having different adsorption energetics for D- and L-enantiomers. The additional role of clays in RNA oligomerization already postulated by Ferris and others, together with the need for the organization of amphiphilic molecules and lipids noted by Szostak and others, suggests that such chiral separation by clays in lagoonal environments at normal biological temperatures might also have played a significant role in the origin of biochirality.     

骨折长骨中超声导波传播特性的仿真研究

采用超声导波评价长骨骨折已成为近两年来的一个研究热点.本文采用混合边界元方法(HBEM)对超声导波在骨裂长骨中的传播情况以及各导波模式的反射系数和透射系数进行了数值分析.研究结果表明,入射导波模式经由裂纹处模式转换后依然保持为主要接收模式不变.对某一裂纹,各模式透射系数常在相近的频率点上达到局部峰值.对于不同深宽比(d/w)裂纹,某些模式透射系数曲线局部峰值所对应的频率存在着相互错开的现象,这些结果可用于选择最优入射导波模式和频率,以便更好地定量评价骨质以及骨裂状况.     

Hydrothermal Synthesis and Crystal Structure of a Novel Polyoxometalate K(C_4N_2H_(12))_4(C_4N_2H_(11))_(2-)[Mo_8~ⅤMo_4~ⅥCdP_8O_(54)(OH)_8]F·6H_2O

The title compound 1 has been synthesized by the reaction of H_2MoO_4, CdCl_2, H_3PO_4, KF, piperazine hexahydrate and water in aqueous solution under mild hydrothermal conditions. Single-crystal X-ray analysis reveals that the title compound crystallizes in the triclinic system, space group P(-1) with a = 14.049(3), b = 15.972(3), c = 20.043(4) (A), α = 85.82(3), β = 81.28(3),γ = 67.15(3)°, V= 4095.9(14) (A)~3, M_r = 3204.62, Z=2,D_c = 2.598 g/cm~3,μ = 2.360 mm~(-1), F(000) = 3124, the final R = 0.0314, wR = 0.0826 and S = 0.989 for 18592 observed reflections with I > 2σ(I). The crystal packing is stabilized by N-H…O and O-H…O intra- and intermolecular hydrogen bonds to form an infinite 3D network.     

A Simple and Rapid Label-free Fluorimetric “Turn Off-on” Sensor for Cadmium Detection Using Glutathione-capped CdS Quantum Dots

A convenient label-free fluorescence(FL) nanoprobe for rapid detection of cadmium(Cd) was established using glutathione-capped CdS quantum dots(QDs) and 1,10-phenanthroline(phen). The prepared CdS QDs exhibited a strong FL emission at 536 nm, which could be quenched by phen due to the photoinduced hole transfer(PHT) mechanism. The existence of Cd effectively recovered the FL intensity of CdS QDs, which was due to the easy detachment of phen from the surface of QDs to form[Cd(phen)₂(H₂O)₂]²⁺ in solution. Cd concentrations were linearly correlated with the FL intensity in the range of 0.0625-1.25 μmol/L under the optimized conditions and the detection limit was 0.01 μmol/L. Finally, the Cd concentration was accurately quantified in real water sample using the proposed sensor.     

基频估计算法研究平均骨小梁间距

超声背散射信号能提供松质骨微结构信息从而能有效的诊断骨质疏松,而平均骨小梁间距(MTBS)是表征松质骨微结构的重要参数之一。本文提出了一种基频估计的MTBS估计算法,对仿真信号和离体牛胫骨松质骨中的超声背散射信号分别进行分析处理,并和现有的两种算法(简易反向滤波跟踪(SIFT)算法和AR倒谱法)进行比较。实验结果表明基频估计算法对噪声和随机散射回波有更好的鲁棒性,在信噪比较低和随机散射回波幅度较大时估计值更加精确,且有很好的方差性能。充分说明了本文算法是一种有效的MTBS估计算法。     

时频方法分析长骨中的超声导波及皮质骨厚度

超声导波在长骨中传播时,接收信号中含有相互叠加的多个导波模式。本文提出将希尔伯特-黄变换(HHT)用于分析叠加的多模式导波信号,将其分解成许多单个独立的模式,然后对分解出的模式求得其对应频率下的群速度,并与短时傅里叶变换所得的结果进行比较。通过与理论计算结果比较,可得到长骨皮质骨的厚度。研究结果表明,实验得到的厚度与实际厚度一致。说明通过测量导波模式的速度可以评价皮质骨的厚度,也说明HHT方法是一种识别叠加多模式导波信号的有效方法。     

长骨裂纹宽度和角度对低阶超声导波的影响

超声导波检测长骨骨折和监测骨折愈合已成为一种极具前景的课题,但高频厚积下导波多模式混叠带来的模式识别和分离问题一直是一个难点。为避免上述问题,在低频下仅激励两个低阶兰姆波SO和AO模式,采用二维时域有限差分(2DFDTD)法定量分析裂纹宽度和骨折角度对SO和AO幅度的影响。结果表明,SO与AO模式的幅度均随裂纹宽度的增加而下降;AO的幅度随骨折角度增大而上升,SO幅度随骨折角度增大先下降后上升,转折点约为45°。SO与AO的幅度比值在不同骨折角度下均能较好地表征裂纹宽度的变化,可为横断型和斜切型长骨骨折状况的超声评价及骨折愈合监测提供依据。     

Barker码激励超声导波在长骨检测中的应用

单脉冲激励的超声导波在长骨中传播时,信号的衰减大,导致接收信号的幅度很小,且噪声严重。Barker码激励能有效增大接收信号幅度,提高信噪比(SNR)。将其应用到超声导波长骨检测中,进行仿真和长骨实验,得到的信号分别用加权匹配滤波器和有限冲激响应-最小均方误差(FIR-LS)逆滤波器进行压缩,并与单脉冲激励的结果进行了对比。结果表明,对于13位的Barker码,采用加权匹配滤波器进行解码时,压缩信号幅度是单脉冲激励接收信号的13倍;而FIR-LS逆滤波器则达到-63.59 dB的峰值旁瓣水平(PSL),更好地抑制噪声。说明可以将Barker码激励超声导波应用于长骨的检测中。     

超声导波的频散补偿与模式分离算法研究

超声导波已被广泛应用于无损检测与评价,针对超声导波应用中普遍存在的模式混叠与频散问题,本文在采用频谱相位与信号时延函数建模导波频散信号传递系统的基础上,提出了一种单一模式的频散补偿算法。进一步地,通过将选择性频散补偿技术与导波模式分离相结合,本文算法克服了传统补偿算法所不能解决的多模式导波频散问题。板中的Lamb波A0,A1和S0混合模式仿真分析表明,本算法不仅可用于单一导波模式信号合成与频散补偿,而且可在实现多模式混合导波信号选择性频散补偿基础上,解决多模式导波信号中单一模式提取与分离。本文研究有助于超声导波多模式频散信号的分析与处理.     

基于离散随机介质平均散射声功率的无损测温方法

生物组织中超声散射回波的平均功率与其温度有关.该理论包含:(1)生物组织近似为离散随机介质.(2)离散随机介质的平均散射功率与组织的衰减系数α和声速c有关。对于似水生物组织(如:猪肝),当温度升高时,衰减系数的减小使平均散射声功率增加,但其影响大小与时间窗△t有关,而声速的增大则使平均散射声功率减小。实验结果表明:生物组织的平均散射声功率随温度变化趋势明显,该结果提供一种肿瘤热疗无损伤检测温度的新方法。