Re‐Appearance of Cooperativity in Ultra‐Small Spin‐Crossover [Fe(pz){Ni(CN)4}] Nanoparticles

A reverse nanoemulsion technique was used for the elaboration of [Fe(pz){Ni(CN)₄}] nanoparticles. Low‐temperature micellar exchange made it possible to elaborate ultra‐small nanoparticles with sizes down to 2 nm. When decreasing the size of the particles from 110 to 12 nm the spin transition shifts to lower temperatures, becomes gradual, and the hysteresis shrinks. On the other hand, a re‐opening of the hysteresis was observed for smaller (2 nm) particles. A detailed ⁵⁷Fe Mössbauer spectroscopy analysis was used to correlate this unusual phenomenon to the modification of the stiffness of the nanoparticles thanks to the determination of their Debye temperature.     

Selective carboxylation of substituted phenols with engineered Escherichia coli whole-cells

Selective carboxylation of substituted phenols is realized in the presence of bicarbonate under ambient pressure by engineered Escherichia coli whole-cells expressing various hydroxybenzoate decarboxylases, leading to their corresponding ortho-hydroxybenzoates. This process may be further developed as an efficient route to upgrade lignin-derived phenolic compounds as valuable building blocks.     

Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP

Ring‐opening metathesis polymerization (ROMP) has become one of the most important living polymerizations. Cyclopropenes (CPEs) remain underexplored for ROMP. Described here is that the simple swap of 1‐methyl to 1‐phenyl on 1‐(benzoyloxymethyl)CPEs elicited strikingly different modes of reactivity, switching from living polymerization to either selective single‐addition or living alternating ROMP. The distinct reactivity stems from differences in steric repulsions at the Ru alkylidene after CPE ring opening. Possible olefin or oxygen chelation from ring‐opened CPE substituents was also observed to significantly affect the rate of propagation. These results demonstrate the versatility of CPEs as a new class of monomers for ROMP, provide mechanistic insights for designing new monomers with rare single‐addition reactivity, and generate a new functionalizable alternating copolymer scaffold with controlled molecular weight and low dispersity.     

以含碘氨基酸类激素为例刍议微量非金属元素在生物体内的作用机制

选取第五周期元素碘,结合多学科的研究方法论对含碘氨基酸类激素在生物体内的合成和分解代谢进行系统性分析。通过解析碘元素本身性质及其各个氧化态之间的转化,探讨碘元素在生物体内的作用机制,揭示自然界对物质代谢的精细调控。这一教学模式探索性地融入无机化学、元素有机化学、分子生物学、生物化学、生物物理学、化学生物学等一系列学科内容,旨在让学生在领悟生命科学内在规律,从而激发其科研及学习热情,并训练学生的类比思维和思辨能力。期对培养21世纪跨学科综合型人才的培养有所助益。     

多级孔芳香骨架材料的合成及固载硫脲催化剂的研究

合成了一种多级孔芳香骨架材料(PAF-70); 使用由氨基修饰过的单体, 应用该合成策略得到了同样具有窄分布介孔的含有氨基活性位点的PAF材料, 并通过硫脲单体与其氨基活性位点的反应, 将硫脲基团引入PAF-70材料中, 获得了含有硫脲催化位点的材料(PAF-70-thiourea). 氮气吸附-脱附测试结果显示, PAF-70存在孔径分布较窄的介孔, 介孔孔径为3.8 nm, 与模拟计算值(约3.7 nm)吻合. 热重分析结果表明, PAF-70具有很高的热稳定性. PAF-70在大多数溶剂中可以稳定存在, 具有良好的化学稳定性. 将PAF-70-thiourea作为催化剂, 应用在N-溴代琥珀酰亚胺(NBS)氧化醇类的反应中, 其表现出较高的催化活性、 较高的稳定性和广泛的底物适用性. 与含有相同硫脲催化位点的金属有机框架(MOF)材料(IRMOF-3-thiourea)作为催化剂对比, 进一步证实PAFs材料非常适合作为催化有机反应的固载平台.     

Identification and Characterization of a Novel Endo-β-1,4-Xylanase from Streptomyces sp. T7 and Its Application in Xylo-Oligosaccharide Production

A xylanase-producing strain, identified as Streptomyces sp. T7, was isolated from soil by our lab. The endo-β-1,4-xylanase (xynST7) gene was found in the genome sequence of strain T7, which was cloned and expressed in Escherichia coli. XynST7 belonged to the glycoside hydrolase family 10, with a molecular mass of approximately 47 kDa. The optimum pH and temperature of XynST7 were pH 6.0 and 60 °C, respectively, and it showed wide pH and temperature adaptability and stability, retaining more than half of its enzyme activity between pH 5.0 and 11.0 below 80 °C. XynST7 showed only endo-β-1,4-xylanase activity without cellulase- or β-xylosidase activity, and it showed maximal hydrolysis for corncob xylan in all the test substrates. Then, XynST7 was used for the production of xylo-oligosaccharides (XOSs) by hydrolyzing xylan extracted from raw corncobs. The maximum yield of the XOS was 8.61 ± 0.13 mg/mL using 15 U/mL of XynST7 and 1.5% corncob xylan after 10 h of incubation at 60 °C. The resulting hydrolysate products mainly consisted of xylobiose and xylotriose. These data indicated that XynST7 might by a promising tool for various industrial applications.     

Solvothermal Synthesis and Crystal Structure of a Layered Thioantimonate(Ⅲ) [C4H9NH3]2Sb4S7

An inorganic-organic hybrid thioantimonate(Ⅲ) [CH3(CH2)3NH3]2Sb4S7 1 with layered structure was synthesized by solvothermal method.1 crystallizes in the triclinic system, space group P with a = 7.0124(11), b = 11.919(2), c = 14.879(3) (A), α = 108.791(3), β = 102.441(3), γ = 92.846(2)o, V = 1140.1(3) (A)3, Mr = 859.71, Z = 2, Dc = 2.504 g/cm3, μ= 5.324 mm-1, F(000) = 804, S = 1.013, the final R = 0.0297 and wR = 0.0618 for 3534 observed reflections with I＞2σ(I). 1 consists of [C4H9NH3] cations and two-dimensional [Sb4S7]n2n-anion which is composed of three SbS3 trigonal pyramids and one SbS4 unit joined by sharing common corners. The anionic layers are stacked perpendicularly to the c axis of the unit cell forming two-dimensional channels between the layers. The [C4H9NH3] cations interdigitate in a bilayer and reside in the 2D channels leading to a sandwich-like arrangement of the anion and cations.     

基于表面增强拉曼光谱技术的心肌生物标志物检测

心血管疾病(CVD)是全球最主要的死亡原因,急性心肌梗死(AMI)是心血管疾病致死的主要病因,安全快速地诊断AMI对于降低患者的死亡率至关重要。因常用的检测方法如心电图(ECG)缺乏足够的敏感性,寻找并针对AMI生物标志物开展高灵敏检测已成为早期检测AMI重要手段。心肌肌钙蛋白I(cTnI)、肌酸激酶同工酶(CK-MB)和肌红蛋白(Myo)是目前公认的检测AMI的重要心肌生物标志物。在过去的几十年里,许多生物传感器被开发出来用于检测心肌生物标志物,其中基于表面增强拉曼光谱(SERS)的心肌生物标志物检测技术迅速发展,并表现出独特的技术优势和广阔的应用前景。本文首先介绍了多种心肌生物标志物及其与AMI的关联,在此基础上概述主要的心肌生物标志物检测方法的原理、优势及局限性,重点介绍近年来新兴的SERS技术及其在心肌生物标志物传感方面的最新研究进展,并对该技术在AMI诊断方面的应用前景以及有待突破的瓶颈进行了讨论和展望。     

超轻纳米纤维气凝胶的制备及其应用

超轻纳米纤维气凝胶是一种以一维纳米纤维为基本构筑单元的新型气凝胶材料,相比于传统气凝胶,其不仅具有更高的孔隙率和更低的密度,还拥有更优异的机械性能和理化性质,因此该材料的先进制备技术和在新兴领域的创新性应用是近年来超轻气凝胶领域的研究热点。本文结合国内外研究现状,按照材料体系分类系统综述了超轻纤维气凝胶的制备方法、结构特点以及在隔热、吸附、电化学、传感和生物医学等领域的重要应用,提出了现阶段该材料面临的一些挑战,并展望了其在未来的发展方向。