Ultrafast Photoconversion Dynamics of the Knotless Phytochrome SynCph2

The family of phytochrome photoreceptors contains proteins with different domain architectures and spectral properties. Knotless phytochromes are one of the three main subgroups classified by their distinct lack of the PAS domain in their photosensory core module, which is in contrast to the canonical PAS-GAF-PHY array. Despite intensive research on the ultrafast photodynamics of phytochromes, little is known about the primary kinetics in knotless phytochromes. Here, we present the ultrafast P_r ⇆ P_fr photodynamics of SynCph2, the best-known knotless phytochrome. Our results show that the excited state lifetime of P_r* (~200 ps) is similar to bacteriophytochromes, but much longer than in most canonical phytochromes. We assign the slow P_r* kinetics to relaxation processes of the chromophore-binding pocket that controls the bilin chromophore’s isomerization step. The P_fr photoconversion dynamics starts with a faster excited state relaxation than in canonical phytochromes, but, despite the differences in the respective domain architectures, proceeds via similar ground state intermediate steps up to Meta-F. Based on our observations, we propose that the kinetic features and overall dynamics of the ultrafast photoreaction are determined to a great extent by the geometrical context (i.e., available space and flexibility) within the binding pocket, while the general reaction steps following the photoexcitation are most likely conserved among the red/far-red phytochromes.     

光化学合成维生素D

本文报道了维生素D的发现以及它们的光化学合成与进展。中国科学院理化技术研究所开发了一条从胆固醇合成 7 DHC的新路线,提出了一条光化学合成维生素D3 的创新技术路线,并已经转让实施。同时还提出一条光化学合成维生素D2 的创新技术路线。     

Synthesis of 5,5′‐Diformyl‐2,2′‐difuran from 2‐Furfural by Photochemical Aryl Coupling

The synthesis of 5,5′‐diformyl‐2,2′‐difuran (IUPAC name: [2,2′‐bifuryl]‐5,5′‐dicarbaldehyde) in good yields by the intermolecular coupling of 2‐furfural and 5‐bromo‐2‐furfural has been achieved. Optimum yields were obtained when mixtures of the substrates in acetonitrile were treated with polyvinylpyridine powder (Reillex 402), and irradiated with UV light through a quartz filter. Low yields of coupling product were obtained in the absence of this base or if hydrocarbon solvents were used. A mechanistic pathway involving a transient exciplex intermediate has been proposed.     

后处理中锕系元素和贵金属元素光化学调价方法

PUREX流程是目前世界上唯一实现工业化应用的后处理流程,该流程的关键技术之一在于调控Pu、Np、Tc等元素的价态。传统上PUREX流程采用化学法调节元素价态,但化学调价有时会遇到困难,比如在硝酸体系下用化学试剂将Np调节至单一价态十分困难。和化学法相比,光化学调价具有方法简单、二次废物体积少、方便远程控制、对材料耐辐照要求不高等优点。将光化学调价和溶剂萃取结合很有潜力实现金属元素的高效分离,只依靠光化学方法将金属离子还原至单质状态也可以实现金属元素的分离和回收。此外,紫外光的照射还能在室温下显著促进UO_2在硝酸溶液中的溶解。     

荧光磁性微球Fe_3O_4@PHEMA-Eu的制备、表征及其载药性研究

在亲水性Fe3O4磁流体中,以甲基丙烯酸-2-羟基乙酯(HEMA)为单体,N,N’-亚甲基双丙烯酰胺(MBA)为交联剂,采用光化学方法在水溶液体系中首先合成磁性聚甲基丙烯酸-2-羟基乙酯(PHEMA)微球,进而在60℃下PHEMA与Eu离子反应合成具有荧光特性的磁性微球(FMPMs),同时用丝裂霉素C(MMC)考查了其载药性。运用VSM、PCS、FTIR、TGA、SEM、FS、HPLC等技术对微球的性能进行了表征。结果表明,荧光磁性高分子微球有超顺磁性,荧光性,呈很好的球形,载药率和包裹率较高。     

光电化学刻蚀方法去除SiC衬底外延石墨烯缓冲层及其表征

高温条件下裂解碳化硅（SiC）单晶,在直径5 cm的4H-SiC（0001）面制备出单层石墨烯。利用光电化学刻蚀方法,使KOH刻蚀液与SiC发生反应,降低石墨烯与衬底之间的相互作用力,去掉原位生长过程中SiC衬底与石墨烯之间存在的缓冲层,获得准自由的双层石墨烯。首先通过对比不同的电流密度和光照强度,总结出电流密度为6 mA·cm^-2、紫外灯与样品间距为3 cm时,石墨烯缓冲层的去除效率以及石墨烯质量皆为最佳。采用此优化后工艺处理的样品,拉曼光谱表明原位生长的缓冲层与衬底脱离,表现出准自由石墨烯的特性。X射线光电子能谱（XPS）C1s谱图中代表上层石墨烯与衬底Si悬键结合的S1、S2特征峰消失,即石墨烯缓冲层消失。通过分析刻蚀过程中的电化学曲线,提出了刻蚀过程的化学反应过程中的动态特性。     

Photochemical modulation of DNA conformation by organic dications

A group of azobenzene derivatives containing two quaternary ammonium groups with various intercharge distances between them was synthesised and used to control photochemically the conformation of genomic DNA by switching the distance between cationic ammonium groups in the dications. It was found that isomerisation of either dication from the trans form to cis resulted in an increase in the dication's efficiency for DNA compaction; this is associated with a decrease in intercharge distance between ammonium groups and leads to a better match of the binder's cationic groups to adjacent phosphate groups of DNA. Ammonium dications have several important advantages over the photosensitive surfactant type of diazobenzene reported earlier: they can be used at significantly lower (>100-fold) concentrations than photosensitive surfactants, and DNA conformation control can be performed over a broader concentration range of dications. The influence of intercharge distance in photosensitive dications on photo-induced DNA binding discrimination is discussed, and the molecular mechanism is proposed.     

UV radiation induces genome-mediated, site-specific cleavage in viral proteins

Much research has been dedicated to understanding the molecular basis of UV damage to biomolecules, yet many questions remain regarding the specific pathways involved. Here we describe a genome-mediated mechanism that causes site-specific virus protein cleavage upon UV irradiation. Bacteriophage MS2 was disinfected with 254 nm UV, and protein damage was characterized with ESI- and MALDI-based FT-ICR, Orbitrap, and TOF mass spectroscopy. Top-down mass spectrometry of the products identified the backbone cleavage site as Cys46-Ser47 in the virus capsid protein, a location of viral genome-protein interaction. The presence of viral RNA was essential to inducing backbone cleavage. The similar bacteriophage GA did not exhibit site-specific protein cleavage. Based on the major protein fragments identified by accurate mass analysis, a cleavage mechanism is proposed by radical formation. The mechanism involves initial oxidation of the Cys46 side chain followed by hydrogen atom abstraction from Ser47 C(α). Computational protein QM/MM studies confirmed the initial steps of the radical mechanism. Collectively, this study describes a rare incidence of genome-induced protein cleavage without the addition of sensitizers.