高功率固体激光器锥形空间滤波孔应用

锥形空间滤波孔是一种应用于高功率固体激光装置空间滤波的新型结构滤波小孔,其内部光滑的锥形结构可以有效滤除光束中的高频成分且避免等离子堵孔现象的发生。根据神光-Ⅲ主机装置结构特点,设计并加工了适用于主机装置的锥形空间滤波小孔,并开展了应用实验研究。通过与传统的平面结构滤波小孔对比可以看出,锥形小孔有效地避免了等离子体度堵孔现象,在与光束波前补偿技术配合使用条件下,保证光束顺利过孔,并成功实现了基频光7988 J的满能量输出。     

Molecular Hydrogels with Esterase-like Activity

The development of molecular hydrogels that can be applied for mimicking bioactive molecules attracts extensive interests of researchers in fields of self‐assembly. In this study, we reported on several molecular hydrogels based on naphthylacetic acid‐peptides containing L‐histidine formed by the heating‐cooling process. All hydrogels exhibited higher activity to hydrolyze 4‐nitrophenyl acetate (4‐NPA) than the free L‐histidine probably due the high density of L‐histidine residue at the surface of self‐assembled nanofibers. To calculate the 4‐NPA hydrolysis rates, the Michaelis‐Menten enzyme kinetics model was made. Among these gels, the gel of Nap‐GFFYGHY possesses the highest enzyme activity of making the ester bond cleavage, which is approximately 25 times higher than that of the control (free L‐histidine and Nap‐GFFYGYY). These results indicate that molecular hydrogels with self‐assembled nanofibers have great potential for the generation of self‐assembled multivalent materials.     

Syngas production from methane over CeO2-Fe2O3 mixed oxides using a chemical-looping method

A series of mixed oxides Ce_{1 ? x} Fe _x O₂ was prepared by a hydrothermal method. XRD and Raman spectra were measured to study the structure of the prepared materials. The temperature-programmed reduction was undertaken to estimate reducibility of the oxides. Syngas generation from methane using these materials as oxygen carriers/catalysts via a chemical-looping procedure was investigated in detail. This procedure includes catalytic oxidation and decomposition of methane to produce H₂-rich gas at the first step followed by the production of the CO-rich gas by oxidizing the carbon deposited on deactivated catalysts. The results showed that all iron ions were incorporated into the ceria lattice with the formation of oxygen vacancies in the Ce_0.9Fe_0.1O₂ sample, while isolated Fe₂O₃ particles were distributed on the surface of the Ce_0.8Fe_0.2O₂ sample. TPR measurements and the analysis of the two-step chemical-looping reactions indicated a strong interaction between the Ce and Fe species which accounts for an increased activity of the mixed oxides in the syngas generation compared to that of individual oxides. Among the several samples, the Ce_0.8Fe_0.2O₂ catalyst showed the highest activity for methane partial oxidation due to the synergetic effects caused by the interaction of surface iron entities and Ce-Fe solid solution. In addition, selective oxidation of carbon by oxygen to CO can also be found over this material since gaseous products are formed at the carbon oxidation step with the selectivity to CO reaching 91.2%. Evidence is presented that syngas can be feasibly produced from methane with high selectivity via the chemical-looping procedure over the CeO₂-Fe₂O₃ mixed oxides.     

Theory on the molecular characteristic contour (II)--Molecular intrinsic characteristic contours of several typical organic molecules

The molecular intrinsic characteristic contour (MICC) is defined based on the classical turning point of electron movement in a molecule. Three typical organic molecules, I.e. Methane, methanol and formic acid, were employed as examples for detailed introduction of our method. Investigations on the cross-sections of MICC provide important information about atomic size changing in the process of forming molecules. The electron density distributions on the MICCs of these molecules were calculated and shown for the first time. Results showed that the electron density distribution on the MICC correlates closely with molecular chemical properties, and it provides a new insight into molecular boundary.     

Macromolecular brushes synthesized by “grafting from” approach based on “click chemistry” and RAFT polymerization

Well‐defined macromolecular brushes with poly(N‐isopropyl acrylamide) (PNIPAM) side chains on random copolymer backbones were synthesized by “grafting from” approach based on click chemistry and reversible addition‐fragmentation chain transfer (RAFT) polymerization. To prepare macromolecular brushes, two linear random copolymers of 2‐(trimethylsilyloxy)ethyl methacrylate (HEMA‐TMS) and methyl methacrylate (MMA) (poly(MMA‐co‐HEMA‐TMS)) were synthesized by atom transfer radical polymerization and were subsequently derivated to azide‐containing polymers. Novel alkyne‐terminated RAFT chain transfer agent (CTA) was grafted to polymer backbones by copper‐catalyzed 1,3‐dipolar cycloaddition (azide‐alkyne click chemistry), and macro‐RAFT CTAs were obtained. PNIPAM side chains were prepared by RAFT polymerization. The macromolecular brushes have well‐defined structures, controlled molecular weights, and molecular weight distributions (M_w/M_n ≦ 1.23). The RAFT polymerization of NIPAM exhibited pseudo‐first‐order kinetics and a linear molecular weight dependence on monomer conversion, and no detectable termination was observed in the polymerization. The macromolecular brushes can self‐assemble into micelles in aqueous solution. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 443–453, 2010     

Selective effect of guest molecule length and hydrogen bonding on the supramolecular host structure

A host supramolecular structure consisting of bis-(2,2':6',2' '-terpyridine)-4'-oxyhexadecane (BT-O-C16) is shown to respond to guest molecules in dramatic ways, as observed by using scanning tunneling microscopy (STM) on a highly oriented pyrolytic graphite surface under ambient conditions. It is observed that small linear molecules can be encapsulated within the host supramolecular lattice. The characteristics of the host structure were nearly unaffected by the encapsulated guest molecules of terphthalic acid (TPA) dimers, whereas appreciable changes in cavity dimension can be observed with azobenzene-4,4'-dicarboxylic acid. The STM study and density functional theory (DFT) analysis reveal that intermolecular hydrogen bonding interaction plays an essential role in forming the assembling structures. The difference in guest molecule length is considered the important cause for the different guest-host complexes.     

Rational design of iridium–porphyrin conjugates for novel synergistic photodynamic and photothermal therapy anticancer agents

Near-infrared (NIR) emitters are important probes for biomedical applications. Nanoparticles (NPs) incorporating mono- and tetranuclear iridium(iii) complexes attached to a porphyrin core have been synthesized. They possess deep-red absorbance, long-wavelength excitation (635 nm) and NIR emission (720 nm). TD-DFT calculations demonstrate that the iridium–porphyrin conjugates herein combine the respective advantages of small organic molecules and transition metal complexes as photosensitizers (PSs): (i) the conjugates retain the long-wavelength excitation and NIR emission of porphyrin itself; (ii) the conjugates possess highly effective intersystem crossing (ISC) to obtain a considerably more long-lived triplet photoexcited state. These photoexcited states do not have the usual radiative behavior of phosphorescent Ir(iii) complexes, and they play a very important role in promoting the singlet oxygen (¹O₂) and heat generation required for photodynamic therapy (PDT) and photothermal therapy (PTT). The tetranuclear 4-Ir NPs exhibit high ¹O₂ generation ability, outstanding photothermal conversion efficiency (49.5%), good biocompatibility, low half-maximal inhibitory concentration (IC₅₀) (0.057 μM), excellent photothermal imaging and synergistic PDT and PTT under 635 nm laser irradiation. To our knowledge this is the first example of iridium–porphyrin conjugates as PSs for photothermal imaging-guided synergistic PDT and PTT treatment in vivo.

Iridium–porphyrin conjugates assembled in nanoparticles are photosensitizers that exhibit excellent photothermal imaging and synergistic PDT and PTT in vivo.     

光合释氧机理的ABEEM/MM/MD和BS-DFT理论研究

建立了S₂态光合释氧络合物（OEC）的原子-键电负性均衡模型（ABEEMσπ）的电荷参数,并使用ABEEM/MM/MD可极化力场的分子动力学模拟和对称性破损的DFT研究了光合作用制造氧气的微观机制.HF/STO-3G（采用此基组的原因请见引用文献）水平下的电荷拟合结果证明了ABEEMσπ模型计算电荷分布的合理性和高效性.MD模拟显示,S₂态Mn₄CaO₅的双向异构化过程伴随Ca上的水分子W3转移至Mn1（III）/Mn4（III）,它很可能作为底物水之一,与O5在S₄态结合产生O₂.基于此,考察了全自旋态下两种异构体形式中O－O键形成的自由基耦合机理.BS-DFT计算结果表明,开立方结构的释氧活性大大优于闭立方结构,金属锰和氧自由基的自旋耦合方式也是反应性的决定性因素,同时,OEC的结构灵活性对于S态循环和光合水分解至关重要.     

Novel tissue-engineered vascular patches based on decellularized canine aortas and their recellularization in vitro

Decellularized allo- or xenogeneic vascular grafts have been found to give more promising results than some biodegradable synthetic polymers. However, owing to absence of well-organized cells, especially confluent endothelial cells, their long-term patency is limited. Seeding vessel-originated cells on these grafts may overcome the deficiency. In this study, canine aortas were decellularized and cross-linked. 4′,6-Diamidino-2-phenylindole (DAPI) and Masson’ trichrome staining showed complete removal of cell debris, while structure integrity of extracellular matrix (ECM) was remained. Human umbilical vein endothelial cells (HUVECs) and human umbilical artery smooth muscle cells (HUASMCs) were seeded on these decellularized aorta patches in three manners, ECs alone (EC/O), SMCs alone (SMC/O) and ECs on SMCs layer (EC/SMC). In EC/O and SMC/O, scanning electron microscopy (SEM) examination indicated both cells could form confluent layers on the decellularized patches when seeded at high density, but their morphology and alignment changed with seeding density. In EC/SMC, ECs could grow well on SMCs layer, but their morphology, alignment, and confluence degree were deeply influenced by the density of SMCs beneath.     

飞秒激光在晶体中传输的级联非线性过程

系统地回顾了有关级联过程导致的各种非线性效应的工作,指出了级联效应可导致不同光谱成分间出现能量转移现象,且二阶级联过程中产生的白光还能够提供种子光进而得到基于参量放大过程的宽带锥形辐射。在此基础上,进一步研究了入射的基频波长对于超连续白光能量转移效果及产生倍频效率的影响以及二阶级联过程引起的偏振调制现象,指出当入射波长越靠近相位匹配波长时倍频效率越高,发现二阶级联效应还可以引起显著的基频光偏振调制。