基于扩散强化的Pickering界面生物催化系统构建及CO2矿化过程研究

CO₂的有效利用有助于解决环境和生态问题.碳酸酐酶(CA)等酶分子可精准活化CO₂分子以降低反应能垒,为CO₂的高效和高选择性转化提供了一种有前景的途径.然而,酶离开生物体后易失活,且难以重复利用.目前,包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一,但载体的存在会造成反应物CO₂内扩散阻力增加,降低反应活性.此外,CO₂酶促转化是一个气-液-固三相反应过程,反应体系中CO₂的外扩散性能也需要加强.金属有机骨架(MOFs),特别是咪唑酯骨架(ZIFs),常被用作酶固定化的载体.ZIFs的拓扑结构可被设计成不同形貌,进而通过ZIFs的结构工程来加强分子向其中的内扩散.Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液.当固体颗粒具有催化活性时,催化剂颗粒会扩大液-液-固或气-液-固三相接触面积,从而有效协调反应物在不同相中的扩散时间.如果酶被用作这些颗粒的活性中心,所制备的Pickering乳液也可能具备类似的特性,可加强底物分子向酶的外扩散.本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8),原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液.ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构.ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构.与CA@ZIF-8颗粒相比,CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布,这有助于CO₂从CA@ZIF-L颗粒表面扩散至酶活性中心.利用酶活测试来研究内扩散是否通过结构工程得到了加强,发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%,推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO₂从颗粒表面扩散至酶活性中心的距离.同时,十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍),从而提升了反应物浓度并显示出更高的催化活性.本文还设计了吸附实验来进一步验证上述假设,发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒,说明与ZIF-8相比,酶包埋于ZIF-L具有更强的捕获小分子的能力,表明CO₂分子向CA@ZIF-L的扩散速度更快,即CA@ZIF-L的十字花状结构可强化系统的内扩散过程.进一步比较了PIBS和游离多酶体系的催化活性,将CO₂通入每个系统,在反应前20 min,PIBS的pH值下降速度比游离体系快得多,说明PIBS通过在气相和液相间构建更大的界面,缩短了CO₂向CA的扩散距离,从而提高了催化效率,促进了CO₂转化.上述假设也通过扩散动力学的计算得到了验证.为进一步研究PIBS的CO₂矿化能力,本文开展了CaCO₃矿化反应,发现PIBS的CaCO₃产量远高于游离多酶体系,表明构建的PIBS在强化内外扩散方面具有显著优势.最后,评估了PIBS在工业应用中的性能,由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性,在第8个循环后,PIBS仍可保持8.9 mg/5 min的CaCO₃产量.综上,PIBS可为CO₂的酶促转化和框架提供一个新方法和新平台.     

Synthesis and Chromatographic Evaluation of Perfluorooctyl Stationary Phase for Separation of Basic Compounds

Fluorinated stationary phases provide unique separation effect on basic compounds, due to the fluorine atoms, and pentafluorophenyl stationary phases (PFPs) are the most widely used. Considering that some fluoroalkyls have higher fluorine contents than PFPs do, it is speculated that fluoroalkyl stationary phases should have potential new applications. Herein, we synthesized a silica-based stationary phase bonding perfluoroctyl (FC8) proved by characterization through elemental analysis and solid-state ¹³C cross-polarization/magic-anglespinning nuclear magnetic resonance. The chromatographic behavior of the stationary phase was evaluated with test compounds. In addition, to further study the applicability of FC8 materials, Corydalis decumbens (Thunb.) Pers. fraction, considered as a challenging medicine on reversed-phase chromatography columns, was chosen as a test sample. Results demonstrated that the FC8 stationary phase had better and more satisfactory separation performance than the PFP stationary phase on basic compounds.

     

A New Lactam from Cannabis sativa

Chemistry of Natural Compounds - A new lactam, 5-hydroxy-1-[(4-hydroxyphenyl)methyl]-2-pyrrolidinone (1), was isolated from the ethyl acetate extract of Cannabis sativa L. The structure was...     

Energy Band Alignment and Redox-Active Sites in Metalloporphyrin-Spaced Metal-Catechol Frameworks for Enhanced CO2 Photoreduction

Two new chemically stable metalloporphyrin-bridged metal-catechol frameworks, InTCP-Co and FeTCP-Co, were constructed to achieve artificial photosynthesis without additional sacrificial agents and photosensitizers. The CO₂ photoreduction rate over FeTCP-Co considerably exceeds that obtained over InTCP-Co, and the incorporation of uncoordinated hydroxyl groups, associated with catechol, into the network further promotes the photocatalytic activity. The iron-oxo coordination chain assists energy band alignment and provides a redox-active site, and the uncoordinated hydroxyl group contributes to the visible-light absorptance, charge-carrier transfer, and CO₂-scaffold affinity. With a formic acid selectivity of 97.8 %, FeTCP-OH-Co affords CO₂ photoconversion with a reaction rate 4.3 and 15.7 times higher than those of FeTCP- Co and InTCP-Co, respectively. These findings are also consistent with the spectroscopic study and DFT calculation.     

Promotion Effect of Gold on Mo/ZSM-5 Catalyst for the Catalytic Cracking of Light Diesel Oil to Increase Propylene Production

Kinetics and Catalysis - Using a modified deposition-precipitation method, a series of Au–Mo/ZSM-5 catalysts with different Au loadings were prepared. The XRD, nitrogen adsorption-desorption,...     

基于磁响应光子晶体与量子点的多重变色防伪研究

结合Fe₃O₄@SiO₂ (M)超顺磁胶体粒子动态连续的磁致变色和碲化镉量子点(CdTe QDs)瞬时发射的光致发光特性, 采用聚二甲基硅氧烷(PDMS)弹性体封装含有M胶体粒子和CdTe QDs的乙二醇(EG)微液滴, 制得了具有多重变色功能的M/QDs/EG/PDMS复合薄膜. 利用光学显微镜、光纤光谱仪、荧光光谱仪、数码相机、拉力试验机对复合薄膜的内部结构、光学性质及力学性能进行表征. 结果表明, 在外界磁场的诱导下, 复合薄膜瞬时呈现明亮的结构色, 且随着磁场强度的降低, 复合薄膜的衍射波长发生连续红移, 移动范围可达145 nm. 此外, 在紫外光的激发下, 复合薄膜可呈现特定波长的荧光发射, 具备良好的光致发光特性. 同时, 复合薄膜断裂伸长率可达132%, 表现出良好的弹性, 这为其附着在不同材料表面实现防伪应用提供了基础. 进一步地, 通过图案化设计, 可制得响应变色迅速、图案隐现可逆、颜色变化多样的防伪薄膜, 这有利于其在信息加密和高级别防伪领域中的应用.     

Insight into the Excellent Tribological Performance of Highly Oriented Poly(phenylene sulfide)

Achieving low friction and wear of poly(phenylene sulfide)(PPS) without using fillers or blending is a challenging task, but one of considerable practical importance. Here we describe how neat PPS with high tribological performance is achieved by manipulating processing parameters(pressure, flow and temperature). The key to achieving high tribological performance is comparatively high molecular chain orientation, realized in neat PPS, at high shear rates and low pressure. The friction coefficient and wear rate are as low as ~0.3 and~10^-6 mm³·N^-1·m^-1, respectively, which break the record for neat PPS. These values are even better than those for PPS-based blends and comparable to PPS composites. Further studies show, for the first time, that wear rate decreases exponentially with increasing molecular chain orientation, prompting us to revise the classical Archard's law by including the effect of molecular chain orientation. These findings open the possibility of using neat PPS in highly demanding tribological applications.     

药物化学中的大分子效应※

药物种类按照分子量来划分可以分为小分子药物(自然提取或化学合成的)和大分子药物(生物制剂). 尽管目前小分子药物仍然是市场的主流, 但其研发增速趋缓, 而大分子药物在药物研发中的地位日渐突显, 并被预期在未来药物市场中占据越来越高的份额. 除了生物制剂大分子药物, 将小分子药物与天然或合成大分子结合制备得到的化学合成大分子药物, 近年来受到药物研究者们越来越多的关注. 由于大分子具有丰富的骨架结构及空间构架, 其所特有的骨架效应、多价效应, 以及通过分子组装而产生的聚集效应和靶向效应等, 能够为药物化学的设计带来更多新的可能. 有鉴于此, 本综述将简略介绍药物化学设计中的大分子效应, 重点讨论合成大分子的骨架效应、多价效应、聚集效应和靶向效应等为药物化学设计所带来的新性能. 通过对药物化学中大分子效应所带来的优势、问题和重要研究进展的探讨, 以期能够推动化学合成大分子药物的发展, 为药物化学设计提供新的思路.     

In2BP3O12:Cr3+宽带近红外荧光粉的发光性能及应用研究※

近红外光谱技术在安防监控、食品检测、生物成像、农业等领域具有重要应用价值, 而开发出紧凑高效的近红外光源是其大规模商业应用的前提. 荧光粉转换型近红外发光二极管(light emitting diodes, LED)光源具有结构紧凑、成本低、使用寿命长、发射光谱可调等优点, 因此近些年受到广泛关注, 其关键就在于开发出能被蓝光有效激发的高性能近红外荧光粉. 本工作利用高温固相法制备了一种新型宽带近红外荧光粉In₂BP₃O₁₂:Cr³⁺, 在480 nm激发下, 荧光粉发射峰值位于950 nm, 光谱覆盖了750~1350 nm范围, 半峰宽达到210 nm. 采用该荧光粉与商用蓝光InGaN LED芯片封装, 获得了具有宽带发射的近红外LED光源, 在60 mA的驱动电流下, 近红外光辐射功率为5 mW. 当采用该光源照射人的手掌, 用近红外电感耦合器(charge coupled device, CCD)相机能够对手掌中的血管进行清晰的成像. 上述结果表明该近红外荧光粉可用于制备基于蓝光芯片的宽带近红外LED光源, 并在生物医学等领域具有潜在应用前景.     

Controllable fabrication of ZnO nanorods@cellulose membrane with self-cleaning and passive radiative cooling properties for building energy-saving applications

Cellulose - The energy consumption for building cooling occupies non-ignorable part of global energy consumption, causing the increasing aggravation of energy crisis and environmental...