The effects of electron-hole pair coupling on the infrared laser-controlled vibrational excitation of NO on Au(111)

In this work, we present theoretical simulations of laser-driven vibrational control of NO adsorbed on a gold surface. Our goal is to tailor laser pulses to selectively excite specific modes and vibrational eigenstates, as well as to favor photodesorption of the adsorbed molecule. To this end, various control schemes and algorithms are applied. For adsorbates at metallic surfaces, the creation of electron-hole pairs in the substrate is known to play a dominant role in the transfer of energy from the system to the surroundings. These nonadiabatic couplings are included perturbatively in our reduced density matrix simulations using a generalization of the state-resolved position-dependent anharmonic rate model we recently introduced. An extension of the reduced density matrix is also proposed to provide a sound model for photodesorption in dissipative systems.     

估测作物冠层生物量的新植被指数的研究

冠层鲜生物量是指示作物长势状况的重要指标,可用于诊断作物氮素营养状况。但常规测定生物量的方法需要破坏性取样,不利于帮助精准施肥管理决策。遥感技术作为快速分析手段可用于估测作物多种生理、生化参数,特别是借助植被指数。研究表明归一化差值植被指数(normalized difference vegetationindex,NDVI)、最优土壤调节指数(optimization of soil-adjusted vegetation index,OSAVI)等现已构建植被指数可用于准确估测中低生物量信息,但在较高冠层生物量条件下,它们的估测能力显著下降。文章旨在提出更通用的新植被指数用于估测冠层生物量,以提高遥感技术在较高生物量条件下的预测准确度。试验在加拿大魁北克省的St-Jean-sur-Richelieu地区进行,5年(2004~2008)试验中采集了玉米及小麦不同生育期的地面高光谱数据及对应生物量信息,并在2005年获取航空机载高光谱影像一景(compact airborne spectro-graphic imager,CASI)。研究提出了红边三角植被指数(red-edge triangular vegetation index,RTVI),并将其与一些常见植被指数进行比较分析。结果表明RTVI是最好的估测冠层生物量的指数,在较高生物量条件下仍保持其对生物量变化的高敏感性,其与生物量间的决定系数为0.96。基于CASI影像,RTVI预测生物量值与实际测定值间的决定系数(R2)为0.58,预测标准误差为0.44 kg.m-2,取得了较好的结果。     

Intermolecular energy transfer from Tb3+ to Eu3+ in aqueous aggregates and on the surface of human cells

Efficient intermolecular energy transfer from carbostyril 124-sensitized Tb(3+) to Eu(3+) in aqueous aggregates is reported. This energy transfer was also recapitulated on the cell surface of a human kidney cell line (HEK-293T) and imaged by fluorescence microscopy as an example for the applicability of this energy transfer probe for imaging in biological systems.     

Formal enantioselective synthesis of (+)-compactin

[reaction: see text] The challenging structural features and important biological activity of (+)-compactin (1) explain the substantial synthetic interest that it has generated. We report a novel enantioselective approach to the advanced intermediate 2a, which constitutes a formal synthesis of (+)-1. The sequence utilizes MacMillan's organocatalytic Mukaiyama-Michael reaction, which stereoselectively adds the silyloxyfuran 6 to alpha,beta-unsaturated aldehyde 7. The chirality generated in this reaction guides the formation of the other three consecutive stereocenters found in 2a.     

Effect of substitution of Ce on superconducting properties of Bi1.7Pb0.3Sr2Ca2−x Ce x Cu3O10+δ system

We have investigated the superconducting properties of the Bi_1.7 Pb_0.3Sr₂Ca_2−xCe _x Cu₃O_10+δ system with x=0.00, 0.02, 0.04, 0.08 and 0.1 by X-ray diffraction and magnetic susceptibility. The substitution of Ce for Ca has been found to drastically change the superconducting properties of the system. X-ray diffraction studies on these compounds indicate decrease in the c-parameter with increased substitution of Ce at Ca site and volume fraction of high T _c (2 : 2 : 2 : 3) phase decreases and low T _c phase increases. The magnetic susceptibility of this compound shows that the diamagnetic on set superconducting transition temperature (onset) varies from 109 K to 51 K for x=0.00, 0.02, 0.04, 0.08 and 0.1. These results suggest the possible existence of Ce in a tetravalent state rather than a trivalent state in this system; that is, Ca²⁺ → Ce⁴⁺ replacement changes the hole carrier concentration. Hole filling is the cause of lowering T _c of the system.     

Hydrogen‐Bond and Supramolecular‐Contact Mediated Fluorescence Enhancement of Electrochromic Azomethines

An electronic push–pull fluorophore consisting of an intrinsically fluorescent central fluorene capped with two diaminophenyl groups was prepared. An aminothiophene was conjugated to the two flanking diphenylamines through a fluorescent quenching azomethine bond. X‐ray crystallographic analysis confirmed that the fluorophore formed multiple intermolecular supramolecular bonds. It formed two hydrogen bonds involving a terminal amine, resulting in an antiparallel supramolecular dimer. Hydrogen bonding was also confirmed by FTIR and NMR spectroscopic analyses, and further validated theoretically by DFT calculations. Intrinsic fluorescence quenching modes could be reduced by intermolecular supramolecular contacts. These contacts could be engaged at high concentrations and in thin films, resulting in fluorescence enhancement. The fluorescence of the fluorophore could also be restored to an intensity similar to its azomethine‐free counterpart with the addition of water in >50 % v/v in tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), and acetonitrile. The fluorophore also exhibited reversible oxidation and its color could be switched between yellow and blue when oxidized. Reversible electrochemically mediated fluorescence turn‐off on turn‐on was also possible.     

Detection of acute brain injury by Raman spectral signature

Brain injury can lead to irreversible tissue loss and functional deficit along with significant health care costs. Raman spectroscopy can be used as a non-invasive technique to provide detailed information on the molecular composition of diseased and damaged tissues. This technique was used to examine acute mouse brain injury, focusing on the motor cortex, a region directly involved in controlling execution of movement. The spectral profile obtained from the injured brain tissue revealed a markedly different signature, particularly in the amide I and amide III vibrational region when compared to that of healthy brain tissue. Most noticeably, there was a significant reduction of the amide I vibration at the acute injury site and the appearance of two distinct features at 1586 and 1618 cm(-1). Complementary immunohistochemical analysis of the injured brain tissue showed an abundant expression of Caspase 3 (a cysteine protease marker used for apoptosis), suggesting that the injury-induced specific Raman shifts may be correlated with cell death. Taken together, this study demonstrates that Raman spectroscopy can play an important role in detecting the changes that occur in the injured brain and provide a possible technology for monitoring the recovery process.