气凝胶-钒尾矿催化剂的表征及应用

以商洛本地丰富的钒尾矿与气凝胶结合,通过浸渍法制备气凝胶-钒尾矿催化剂,并对其进行扫描电镜和TG-DSC分析。考察催化剂对甲醇与乙醇一步合成异丁醛和仲丁醇氧化反应合成丁酮的催化活性,利用傅里叶变换红外光谱仪对反应产物进行检测。TG-DSC和扫描电镜结果表明,催化剂在(100~1 000)℃几乎不发生质量变化,耐热性良好,催化剂表面呈海绵多孔状,金属负载均匀,孔径从几十纳米到几百纳米。     

Lactoperoxidase-mediated degradation of single-walled carbon nanotubes in the presence of pulmonary surfactant

Carbon nanotubes (CNTs) may elicit inflammatory responses following pulmonary exposure. Conversely, enzymatic biodegradation of CNTs by inflammatory cells has also been reported. The aim of this study was to study the degradation of oxidized single-walled CNTs (ox-SWCNTs) by lactoperoxidase (LPO), a secreted peroxidase present in the airways, and whether pulmonary surfactant affects this biodegradation. To this end, ox-SWCNTs were incubated in vitro with recombinant bovine LPO + H₂O₂ + NaSCN in the presence and absence of porcine lung surfactant (Curosurf®) and biodegradation was monitored using UV–Vis–NIR spectroscopy, Raman spectroscopy, and scanning electron microscopy. The interaction of recombinant LPO with bundles of ox-SWCNTs was confirmed by atomic force microscopy. Cell-free biodegradation of ox-SWCNTs was also observed ex vivo in murine bronchoalveolar lavage fluid in the presence of H₂O₂ + NaSCN. Our study provides evidence for biodegradation of ox-SWCNTs with a lung surfactant ‘bio-corona’ and expands the repertoire of mammalian peroxidases capable of biodegradation of ox-SWCNTs. These findings are relevant to inhalation exposure to these materials, as LPO serves as an important component of the airway defense system.     

Nondestructive Estimation of Fat Constituents of Sesame (Sesamum indicum L.) Seeds by Near‐Infrared Reflectance Spectroscopy

A rapid and efficient method for oil constituent estimation in intact sesame seeds was developed through near‐infrared reflectance spectroscopy (NIRS) and was used to evaluate a sesame germplasm collection conserved in China. A total of 342 samples were scanned by reflectance NIR in a range of 950–1650 nm, and the reference values for oil content and fatty acid (FA) profiles were measured by Soxhlet and gas chromatograph methods. Useful chemometric models were developed using partial least squares regression with full cross‐validation. The equations had low standard errors of cross‐validation, and high coefficient of determination of cross‐validation (R_c²) values (>0.8) except for stearic acid (0.794). In external validation, r² values of oil and FA composition equations ranged from 0.815 (arachidonic acid) to 0.877 (linoleic acid). The relative predictive determinant (RPD_v) values for all equations were more than 2.0. The whole‐seed NIR spectroscopy equations for oil content and FA profiles can be used for sesame seed quality rapid evaluation. The background information of the 4399 germplasm resources and accessions with high linoleic acid content identified in this study should be useful for developing new sesame cultivars with desirable FA compositions in future breeding programs.     

Preparation and studies of transparent conductive monolayers of multiwall carbon nanotubes on quartz and flexible polymer with the use of modified Langmuir technique

An improved Langmuir method is described and applied to produce transparent, conductive and flexible single layer of multiwall carbon nanotubes. This paper presents properties of multiwall carbon nanotubes spread on water subphase and in a form of Langmuir–Schaefer layers on a quartz plate and on flexible polymeric foil. The results show very high homogeneity of the monolayers on a very large area obtained with the use of the proposed modified Langmuir method and indicate their relatively high radiation transmission and electrical conductivity. Laser scanning confocal and scanning electron microscopic images of the layers are presented. The microscopic visualization of the nanolayers is supported by spectroscopic studies (transmittance, photoacoustics) in the range from ultraviolet to mid-infrared. Moreover, electric measurements (current versus voltage characteristics) of the carbon material on the polymeric foil are presented.The obtained results of the investigated multiwall carbon nanotubes are discussed in a view of potential application in optoelectronics.     

铝酸钙玻璃中羟基对红外透过性能的影响

采用不同熔化方法制备了铝酸钙红外玻璃并考察了其红外透过性能。研究了结构中的羟基对玻璃红外透过性能的影响。通过红外光谱和固体核磁共振技术对玻璃中羟基的结构特征、氢键结合状态以及红外吸收情况进行了研究和探讨。结果表明:羟基会引起铝酸钙玻璃在近红外2.9μm左右的宽带吸收,这是由于玻璃中羟基结构形式的多样化所造成的;在玻璃结构中,羟基与氢键结合会造成振动频率下降,红外吸收峰向长波移动,羟基氢键结合强度越大,长波移动越严重,羟基与氢键结合形式越多,羟基的红外吸收范围越宽;在铝酸钙红外玻璃中主要存在3种羟基存在形式:孤立羟基基团、邻近的羟基对和带有氢键的单个羟基。不同制备方法获得的玻璃结构中羟基存在形式基本相同。     

Orthogonal Translation Meets Electron Transfer: In Vivo Labeling of Cytochrome c for Probing Local Electric Fields

Cytochrome c (cyt c), a redox protein involved in diverse fundamental biological processes, is among the most traditional model proteins for analyzing biological electron transfer and protein dynamics both in solution and at membranes. Studying the role of electric fields in energy transduction mediated by cyt c relies upon appropriate reporter groups. Up to now these had to be introduced into cyt c by in vitro chemical modification. Here, we have overcome this restriction by incorporating the noncanonical amino acid p‐cyanophenylalanine (pCNF) into cyt c in vivo. UV and CD spectroscopy indicate preservation of the overall protein fold, stability, and heme coordination, whereas a small shift of the redox potential was observed by cyclic voltammetry. The C≡N stretching mode of the incorporated pCNF detected in the IR spectra reveals a surprising difference, which is related to the oxidation state of the heme iron, thus indicating high sensitivity to changes in the electrostatics of cyt c.     

吡贝地尔的波谱学分析与结构确证

通过波谱学分析对吡贝地尔的化学结构进行确证。测定了吡贝地尔的高分辨质谱(HRMS)、核磁共振波谱(包括1 HNMR、13 CNMR、DEPT-135和HSQC)、质谱(MS)、紫外光谱(UV)、红外光谱(IR)等,并且对样品进行了差热分析(DSC)和热重分析(TGA)。对该化合物所有的1 HNMR和13 CNMR谱信号进行了归属,讨论了红外和紫外特征吸收峰所对应官能团的振动形式。对吡贝地尔的质量控制具有重要的参考价值。     

固体药物晶型定量分析方法

药物的不同晶型会影响药效及其生物利用度,药物晶型及其含量的确定是确保药物产品的最终质量并指导药物制剂开发和生产的主要问题。针对近年来固体药物多晶型定量分析领域的研究进展进行了综述,并结合实例对3类定量分析方法(X射线粉末衍射(XRPD)法、光谱法、热分析法)的特点、适用场合进行了分析评述。目前XRPD法仍是鉴别多晶型的最主要手段,但晶体的择优取向与试样制备过程均会影响定量分析的准确度。各种光谱法对于晶体结构差异的敏感性高,且快速、无损检测,试样处理简单,在晶型定量分析中的应用具有潜力。热分析法对试样具有不可逆损害,但由于其准确度相对较高且操作方便,将来仍会得到广泛应用。     

井下混合流体光谱在线分析技术研究

地层流体光谱实时分析技术通过光谱学原理对地层流体进行在线测量,可为地层流体取样提供重要参考依据。针对取样过程中出现的水基泥浆对地层原油污染的情况,提出一种基于近红外光谱分析技术的油水比在线测量方法。通过对3组不同的光谱预处理方式的建模效果进行分析和对比,证明了采用校正后连续光谱进行偏最小二乘法回归建模能够更准确地预测混合流体流经光学窗口时的含油比率。     

氧化热处理对VO2薄膜红外光学相变特性的影响

采用直流磁控溅射法在硅基底上制备VO2薄膜,并对薄膜氧化热处理。分别对热处理前后薄膜进行X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)透射率测试,分析了热处理对VO2薄膜晶相成分与红外透射率相变特性的影响。实验分析表明,经热处理的VO2发生非晶态向晶态转变,单斜金红石结构VO2(011)晶体具有明显择优取向,晶粒尺寸均匀度提高,且薄膜的红外透射率具有明显相变特性,相变温度为60.5℃,3~5μm、8~12μm波段的红外透射率对比值达到99%,适合应用于红外探测器的激光防护研究。