质谱分子成像技术与应用进展

该文总结了二次离子质谱、基质辅助激光解吸电离质谱和常压敞开式离子化质谱三大类型质谱分子成像（MSI）技术的概况、技术与方法及其应用新进展。MSI技术作为免标记、高覆盖、高灵敏、检测范围广的可视化分析手段,不局限于生物组织或细胞中某种特定分子的检测,可对已知和未知多种分子进行同时成像分析,获得不同分子的空间分布、相对含量及结构信息,实现其分子的定性、定量与定位分析;还可提供不同生理及病理过程中功能分子的动态时空变化信息等。因此,MSI技术成为质谱领域以及分析化学等领域的研究前沿与热点方向之一,并在化学、医学、生命科学、药学和环境科学等领域显示出重大应用前景。此外,MSI技术是单细胞可视化分析和空间分辨代谢组学的强有力分析手段,可从动物或器官组织的整体、微区、单细胞等不同空间尺度,获取具有空间分布特征、时空动态变化的功能分子全景轮廓信息等而备受关注。     

Paecilomyces variotii extract increases lifespan and protects against oxidative stress in Caenorhabditis elegans through SKN-1, but not DAF-16

A natural extract from Paecilomyces variotii (P. variotii extract, PVE), an endophytic fungus, has been used widely to improve agricultural crop performance and control multiple plant pathogens. Most recent studies focused on its application as a plant growth promoter, while relatively few studies have been reported on the antioxidant potential in vivo and the underlying mechanism. The present study was designed to determine the antioxidant activities of PVE and its mechanisms using Caenorhabditis elegans. Results showed that, compared to the solvent control, PVE at 1.0, 10 and 100 ng/mL significantly extended the lifespan of C. elegans by 36.60%, 59.80% and 53.30%, respectively. PVE at 10 ng/mL consistently promoted nematodes growth, but all treatments did not influence nematode fecundity, locomotion behavior, and pharyngeal pumping. Furthermore, PVE at the three tested concentrations significantly reduced accumulation of reactive oxygen species (ROS), lipofuscin, lipid and malondialdehyde (MDA) content, meanwhile significantly promoted activities of superoxide dismutase (SOD), catalase (CAT) and glutathione S-transferase (GST) in the nematodes. Compared with the solvent control, PVE up-regulated gene expression of skn-1, mev-1, sod-3, and daf-2, but significantly down-regulated the expression of nhr-49 and daf-16. Further evidence revealed that PVE at the three concentrations significantly promoted nuclear localization of SKN-1, but not affected that of DAF-16, indicating the complex roles of DAF-16 and SKN-1 in stress resistance and longevity regulation. Overall, our results demonstrated that SKN-1 played a critical role in increasing lifespan of C. elegans and protecting the nematodes from oxidative stress, independent of DAF-16.     

Organocatalytic asymmetric [3 + 3] annulation of isatin N,N'-cyclic azomethine imines with enals: Efficient approach to functionalized spiro N-heterocyclic oxindoles

An unprecedented chiral secondary amine-catalyzed [3 + 3] annulation of isatin N,N'-cyclic azomethine imines with α,β-unsaturated aldehydes was developed. This strategy allowed the construction of structurally novel spiro N-heterocyclic oxindole derivatives in good yields (up to 91%) and good to excellent enantioselectivities (up to >99% ee), albeit with modest diastereoselectivities (up to 3.1:1 dr).     

Synthesis of linseed oil based biodegradable homo and copolymers: role as multifunctional greener additives in lube oil

Abstract

Homopolymer of linseed oil and its four copolymers with styrene, 1-decene, isodecyl acrylate and octyl acrylate, respectively, have been synthesized in this present context. The prepared polymers are characterized by NMR and FTIR spectroscopy. The molecular weights have been measured by gel permeation chromatography. Their effectiveness as pour point depressant (PPD), viscosity index improver (VII) and their shear stability in terms of permanent shear stability index have been evaluated in lube oil. The copolymers acted as better PPDs than the homopolymer whereas the homopolymer of linseed oil excelled as VII. Further it was observed that all the prepared polymers were stable enough under severe mechanical shear.     

In Silico Analysis of P450s and Their Role in Secondary Metabolism in the Bacterial Class Gammaproteobacteria

The impact of lifestyle on shaping the genome content of an organism is a well-known phenomenon and cytochrome P450 enzymes (CYPs/P450s), heme-thiolate proteins that are ubiquitously present in organisms, are no exception. Recent studies focusing on a few bacterial species such as Streptomyces, Mycobacterium, Cyanobacteria and Firmicutes revealed that the impact of lifestyle affected the P450 repertoire in these species. However, this phenomenon needs to be understood in other bacterial species. We therefore performed genome data mining, annotation, phylogenetic analysis of P450s and their role in secondary metabolism in the bacterial class Gammaproteobacteria. Genome-wide data mining for P450s in 1261 Gammaproteobacterial species belonging to 161 genera revealed that only 169 species belonging to 41 genera have P450s. A total of 277 P450s found in 169 species grouped into 84 P450 families and 105 P450 subfamilies, where 38 new P450 families were found. Only 18% of P450s were found to be involved in secondary metabolism in Gammaproteobacterial species, as observed in Firmicutes as well. The pathogenic or commensal lifestyle of Gammaproteobacterial species influences them to such an extent that they have the lowest number of P450s compared to other bacterial species, indicating the impact of lifestyle on shaping the P450 repertoire. This study is the first report on comprehensive analysis of P450s in Gammaproteobacteria.     

注塑制品残余应力的研究进展

由于实际工艺条件往往与理想值存在一定偏差,制品在成形后通常会存在一些难以避免的缺陷,而残余应力正是最为常见的一种。注塑制品的残余应力是在注塑成形过程中,外界约束去除后,仍存在于塑件内部的应力,在后期使用过程中容易引起塑件的翘曲、变形、乃至断裂破损,多数情况下对制品不利。因此,在塑料制品设计时应充分考虑到残余应力的影响。本文较为全面地介绍了注塑制品残余应力的产生、检测、减小残余应力的措施及残余应力的计算机模拟等内容。     

Dynamic Docking and Undocking Processes Addressing Selectively the Outside and Inside of Polymersomes

Increasing complexity and diversity of polymersomes and their compartments is a key issue for mimicking cellular functions and protocells. Thus, new challenges arise in terms of achieving tunable membrane permeability and combining it with control over the membrane diffusion process, and thus enabling a localized and dynamic control of functionality and docking possibilities within or on the surface of polymeric compartments. This study reports the concept of polymersomes with pH‐tunable membrane permeability for controlling sequential docking and undocking processes of small molecules and nanometer‐sized protein mimics selectively on the inside and outside of the polymersome membrane as a further step toward the design of intelligent multifunctional compartments for use in synthetic biology and as protocells. Host–guest interactions between adamantane and β‐cyclodextrin as well as noncovalent interactions between poly(ethylene glycol) tails and β‐cyclodextrin are used to achieve selective and dynamic functionalization of the inner and outer spheres of the polymersome membrane.     

混合碱处理制备微介孔催化剂及其噻吩烷基化催化性能

以SiO_2/Al2O3物质的量比为50的H-ZSM-5分子筛为母体,分别采用Na_2CO_3溶液处理后加入TPAOH溶液进行二次晶化法以及Na_2CO_3/TPAOH混合溶液同时处理法,制备了微孔-介孔多级孔HZSM-5催化剂,对其噻吩烷基化反应催化性能进行了研究。结果表明,采用4 mol/L的Na_2CO_3溶液处理后的催化剂在TPAOH溶液中发生了二次晶化;当TPAOH溶液浓度为0.3 mol/L、晶化温度为170℃、晶化时间为24 h时,得到的HZ(CO_2-3-TPA+,0.3-24-170)催化剂具有适宜的孔径和酸性,其噻吩烷基化转化率最高(99.1%)。而Na_2CO_3/TPAOH同时处理HZSM-5分子筛所得的催化剂,由于生成大量SiO_2堵塞了孔道,覆盖了催化剂表面,降低了催化剂的平均孔径和酸性,不适合噻吩烷基化反应。     

高残炭硼酚醛树脂的制备

酚醛树脂(PF)因其具有良好的耐热性能和机械性能而被广泛应用。但其耐热性能已经满足不了现代航空航天技术的需求,研究发现,采用硼酸对酚醛树脂进行改性,可以制得具有优良耐高温性能的硼酚醛树脂(BPF)。采用硼酸酯法合成硼酚醛树脂,n(苯酚)∶n(甲醛)=1∶1.5时耐热性最佳。热分析结果表明,合成的BPF在1000℃条件下的残炭率为78%,其耐热性能明显优于传统的酚醛树脂。同时讨论了不同硼酸含量对BPF耐热性能的影响,当n(硼酸)∶n(苯酚)0.33∶1时,残炭率趋于稳定。此外,利用差示扫描量热仪(DSC)方法确定BPF预固化温度为160℃,后固化温度为220℃。     

SDEs with constraints driven by semimartingales and processes with bounded p-variation

We study the existence, uniqueness and stability of solutions of general stochastic differential equations with constraints driven by semimartingales and processes with bounded $p$-variation. Applications to SDEs with constraints driven by fractional Brownian motion and standard Brownian motion are given.