基于SiPM和TCMPC的时间分辨拉曼散射测量技术研究

报道了一种基于硅光电信增管(SiPM)的时间相关多光子计数(TCMPC)技术并将其应用于时间分辨拉曼散射测量。相比于常规基于光电倍增管(PMT)或单光子雪崩二极管(SPAD)的时间相关单光子(TCSPC)技术,由于SiPM可以分辨信号脉冲的具体光子数,基于SiPM的TCMPC技术消除了信号脉冲包含的光子数必须小于等于1的限制,光子计数效率提高了10倍以上,大大节省了测量时间。此外,多光子测量比单光子测量能够得到更好的时间分辨率,时间分辨拉曼散射系统的仪器响应函数(IRF)从单光子81.4 ps缩短至双光子59.7 ps,因而可以用更窄的时间门限抑制荧光本底等噪声对拉曼散射测量的影响。使用TCMPC技术测量CCl₄在0.5和1.5 p.e.两个不同光子数阈值的拉曼峰的峰本比,后者较高的光子数阈值能进一步降低SiPM暗计数噪声的影响,增加了拉曼信号测量的信噪比,测量得到的CCl₄ 459 cm-1拉曼峰的峰本比是前者的6.4倍。将所述新的拉曼散射测量技术与基于PMT和锁相放大器(LIA)的传统拉曼散射测量技术进行了比较研究,前者由于可以使用仅有数十皮秒的测量门限,可以有效抑制荧光、环境杂散光和SiPM暗计数等噪声的影响,所得光谱具有更好的峰本比,测得CCl₄的459 cm-1拉曼峰和Si的一阶拉曼峰的峰本比分别是后者的3.9倍和5.5倍。     

Unnatural base pair systems toward the expansion of the genetic alphabet in the central dogma

Toward the expansion of the genetic alphabet of DNA, several artificial third base pairs (unnatural base pairs) have been created. Synthetic DNAs containing the unnatural base pairs can be amplified faithfully by PCR, along with the natural A-T and G-C pairs, and transcribed into RNA. The unnatural base pair systems now have high potential to open the door to next generation biotechnology. The creation of unnatural base pairs is a consequence of repeating "proof of concept" experiments. In the process, initially designed base pairs were modified to address their weak points. Some of them were artificially evolved to ones with higher efficiency and selectivity in polymerase reactions, while others were eliminated from the analysis. Here, we describe the process of unnatural base pair development, as well as the tests of their applications.(Communicated by Takao SEKIYA, M.J.A.).     

Dislocations hétéro-interfaciales vis perçant une plaquette mince

A specimen observed in high-resolution transmission electron microscopy is electron transparent and its thickness is often less than about 10 nm. When it contains a linear defect like a screw dislocation, the obtained image can exhibit more or less important perturbations due to elastic relaxation nearby both free surfaces. Therefore, the theoretical interpretation of an image should include this relaxation in the calculation model. In the present work, it is evaluated for screw misfit dislocations piercing normally an elastically heterogeneous bicristalline plate (thickness 2h) from the following assumptions: there is no applied force on the thin plate and any surface stress related to a possible nanometric structure along the two free surfaces is neglected. The solution is found from an appropriate combination of known elastic fields in an infinite medium, which enables total stresses applying on two planes distant of 2h to be cancelled. This solution generalizes for the first time that of Eshelby and Stroh (1951), who consider an isolated screw dislocation normal to a homogeneous plate.     

Base‐dependent selectivity of an SNAr reaction

A detailed kinetic analysis and computational study of an S_NAr reaction between 2,5,6‐trifluoronicotinonitrile, 2 , and the ambident 3‐isopropoxy‐1H‐pyrazol‐5‐amine, 3 , is presented. The selectivity with respect to the reaction at the primary amino group of 2 , to give the desired product, 2,5‐difluoro‐6‐[(3‐isopropoxy‐1H‐pyrazol‐5‐yl)amino]nicotinonitrile, 1 , is strongly dependent upon reaction conditions. Reaction is found to proceed via both uncatalysed and base catalysed routes, and selectivity towards 1 is strongly enhanced in the presence of the base diazabicyclo[2,2,2]octane (DABCO). Computational studies in tetrahydrofuran solution at the B3LYP/6‐31G* level of theory have provided valuable insight into alternative kinetically indistinguishable reaction pathways. The results suggest that for reaction at the primary amino group, proton removal by DABCO accompanying amine addition allows avoidance of a high‐energy, zwitterionic Meisenheimer intermediate. Reactions at the alternative pyrazole nitrogen atoms are less sensitive to the presence of base because of stabilisation of the Meisenheimer zwitterions by intramolecular hydrogen bonding. Copyright © 2010 John Wiley & Sons, Ltd.     

Deterministic joint remote preparation of arbitrary multi-qudit states

In this Letter, we put forward a new nontrivial three-step strategy for joint remote preparation of arbitrary two-qudit states (JRSP) in a deterministic manner from a spatially separated multi-sender to one receiver. The scheme is then extended to the arbitrary multi-qudit case. In our schemes, various partially entangled GHZ-like states with arbitrary complex parameters are used as the quantum channels. It overcomes state preparation failure leading to the loss of valuable quantum channel resource and ensures the prepared data available for the remote terminals under extreme conditions such as limited number of quantum channels and limited quantum information processing technologies.     

The SN3–SN2 spectrum. Rate constants and product selectivities for solvolyses of benzenesulfonyl chlorides in aqueous alcohols

Rate constants for a wide range of binary aqueous mixtures and product selectivities (S) in ethanol–water (EW) and methanol–water (MW) mixtures, are reported at 25 °C for solvolyses of benzenesulfonyl chloride and the 4‐chloro‐derivative. S is defined as follows using molar concentrations: S = ([ester product]/[acid product]) × ([water solvent]/[alcohol solvent]). Additional selectivity data are reported for solvolyses of 4‐Z‐substituted sulfonyl chlorides (Z = OMe, Me, H, Cl and NO₂) in 2,2,2‐trifluoroethanol–water. To explain these results and previously published data on kinetic solvent isotope effects (KSIEs) and on other solvolyses of 4‐nitro and 4‐methoxybenzenesulfonyl chloride, a mechanistic spectrum involving a change from third order to second order is proposed. The molecularity of these reactions is discussed, along with new term ‘S_N3–S_N2 spectrum’ and its connection with the better established term ‘S_N2–S_N1 spectrum’. Copyright © 2009 John Wiley & Sons, Ltd.     

Biodiesel production from non-edible Silybum marianum oil using heterogeneous solid base catalyst under ultrasonication

The aim of this study is to investigate modified TiO₂ doped with C₄H₄O₆HK as heterogeneous solid base catalyst for transesterification of non-edible, Silybum marianum oil to biodiesel using methanol under ultrasonication. Upon screening the catalytic performance of modified TiO₂ doped with different K-compounds, 0.7 C₄H₄O₆HK doped on TiO₂ was selected. The preparation of the catalyst was done using incipient wetness impregnation method. Having doped modified TiO₂ with C₄H₄O₆HK, followed by impregnation, drying and calcination at 600 °C for 6 h, the catalyst was characterized by XRD, FTIR, SEM, BET, TGA, UV and the Hammett indicators. The yield of the biodiesel was proportional to the catalyst basicity. The catalyst had granular and porous structures with high basicity and superior performance. Combined conditions of 16:1 molar ratio of methanol to oil, 5 wt.% catalyst amount, 60 °C reaction temperature and 30 min reaction time was enough for maximum yield of 90.1%. The catalyst maintained sustained activity after five cycles of use. The oxidative stability which was the main problem of the biodiesel was improved from 2.0 h to 3.2 h after 30 days using ascorbic acid as antioxidant. The other properties including the flash point, cetane number and the cold flow ones were however, comparable to international standards. The study indicated that Ti-0.7-600-6 is an efficient, economical and environmentally, friendly catalyst under ultrasonication for producing biodiesel from S. marianum oil with a substantial yield.     

时基反馈控制的Tesla变压器初级电源

LC谐振充电是Tesla变压器常用的初级电容充电技术,但存在对控制时序要求高、易受电磁干扰和不具备故障保护能力等缺陷。针对这个问题,提出了一种时基反馈控制的LC谐振充电电源。该电源与传统LC谐振电源的主要区别在于,采用特殊设计的时基反馈电路取代多路时基控制器,将能量回收开关反向阻断瞬间的电压突变调制为谐振晶闸管触发信号,从而在能量回收结束时刻启动谐振充电,实现各工作回路准确按照预定时序运行。时基反馈电路由高压元件构成,不易受电磁干扰,且在原理上具备负载短路保护能力。该技术已经应用于CKP1000,CKP5000等多台Tesla型超宽谱脉冲源。实验结果表明,在强脉冲辐射环境下,该电源能够1000 Hz重频稳定运行,且能够在Tesla变压器初级短路故障时进行快速自动保护。     

适于遥感图像实时压缩的小波基的选择

遥感图像相关性弱,纹理细节丰富,故对其采用基于小波变换的图像编码方法进行编码压缩,而在对图像进行小波变换时,小波基的选取是至关重要的,它直接影响到变换速度和编码效率。在详细分析小波基的基本性质及其与图像编码的关系的基础上,选出数种典型小波基进行实验比较。实验结果表明D5/3双正交小波基最适合于遥感图像实时压缩,最后经实验验证其选取是合理的。     

Efficient epoxidation over cyanocobalamine containing SBA-15 organic-inorganic nanohybrids

SBA-15 mesoporous silica is synthesized using triblock copolymer P123 surfactant and chemically modified by aminopropyl, thiol, ammonium and sulfonic acid functional groups. Functionalization is performed via post synthesize method using 3-aminopropyltriethoxysilane (APTES) or 3-mercatopropyl trimethoxysilane (MPTMS) precursor. The as synthesized mesoporous systems are applied for immobilization of cyanocobalamine. Functionalization effectively improves sorption properties of the supports, while different functional groups exert different effects. The organic-inorganic mesoporous materials are characterized via X-ray diffraction (XRD), nitrogen adsorption and desorption, transmission electron microscopy (TEM), FT-IR and inductively coupled plasma-optical emission (ICP). The newly synthesized systems exhibit high catalytic activity for heterogeneous epoxidation of cyclooctene in presence of hydrogen peroxide. Reaction conditions are optimized, effect of functional groups on performance of the catalysts is taken into consideration and reusability of the designed heterogeneous systems is studied. Systems with chemically modified supports are shown to be more efficient and stable catalysts however; chemical nature of functional groups plays a crucial role.