Combined DFT and wave function theory approach to excited states of lanthanide luminescent materials: A case study of LaF3:Ce3+

Lanthanide luminescent materials play key roles in modern society, but their first-principles treatment remains a great challenge due to complex manifold of electronic excited states and the difficulty in performing excited state structural relaxations that is necessary to model luminescent properties. Herein, we propose a practical approach that combines embedded cluster model (ECM) based multi-configurational wave function theory (WFT) and occupancy constrained density-functional theory plus the Hubbard U correction (OC-DFT + U) to treat lanthanide doped luminescent materials, using LaF₃:Ce³⁺, a typical scintillator with low symmetry, as a case study. We show that the combined approach yields accurate absorption energies with an error on the order of 200 cm⁻¹, but the emission energies are significantly underestimated, the origin of which is further clarified by vibrationally resolved absorption and emission spectra calculation. This work demonstrates the possibility of combining ECM-based wave function theory and periodic DFT into a comprehensive computational scheme for lanthanide luminescent materials and highlights the limitations of the current implementation of OC-DFT + U for excited state structural optimization.     

Electronic and optical properties of quaternary selenides for optoelectronic applications: Insights from DFT+U-computations

The optical properties, electronic charge density, electronic structure of the new layered selenides materials, BaGdCuSe₃, CsUCuSe₃, CsZrCuSe₃, and CsGdZnSe₃ compounds have been calculated by using the full potential and linear augmented plane wave (FP-LAPW) methods as applied in the WIEN2k package, which is based on the density functional theory. The ALnMSe3 compound's structure of these was (A = Cs, Ba; Ln = Zr, Gd, U; M = Cu, Zn) is composed of (n = 1, 2) layers, which might be separated by A atoms. It is to be observed that there is strong hybridization between the s, p, and d states of Zr, Gd, and Cu atoms. Around the gadolinium atom, the charge density contours are completely circular, but the Gadolinium “Gd” atom shows an ionic nature. To calculate the refractive index, we used Kramer's Kronig correlations with the imaginary part dielectric function. The decrease in the refractive index is due to the lack of probability for direct excitation of the electrons, resulting in a loss of energy. The value of the static refractive index for all reference compounds is about 1.75–2.25, which is indication that the material used in optoelectronic devices.     

活性导向的化学探针在氨基酸反应活性表征中的应用进展

原创药物的研制得益于蛋白质新靶标的发现,而新靶标的发现依赖于高可信度、高通量的药物-蛋白质相互作用分析方法。蛋白质作为生命功能的执行者,其表达量、空间定位与结构差异直接影响药效的发挥。目前,超过85%的蛋白质尚被认为是无法成药的,主要原因是缺少药物分子靶向的空腔以及相应的反应活性位点。因此,基于蛋白质组学层次实现对氨基酸反应活性位点的表征成为原创共价靶向药物设计的关键,也是克服难以成药靶标蛋白问题的关键。近年来,质谱技术的飞速发展极大地推动了基于蛋白质组学技术的药物-靶蛋白相互作用研究。其中基于活性的蛋白质组分析(ABPP)策略是利用活性位点导向的化学探针分子在复杂样品中实现功能状态酶和药物靶标等蛋白质的检测。基于化学探针的开发和质谱定量技术的发展,ABPP技术在氨基酸反应活性表征研究中展现出重要的应用潜力,将助力于药物新靶标的发现和药物先导化合物的开发。ABPP策略主要基于蛋白质的活性特征进行富集,活性探针作为ABPP策略的核心,近年来取得了飞速进展。该文回顾了ABPP策略的发展历程,重点介绍基于广谱活性探针的ABPP技术在多种氨基酸反应活性筛选领域的研究进展,并对其在药物靶点发现中...     

Separating Vibrational Coherences in Ground/Excited Electronic States of Solvent/Solute Following Non-Resonant/Resonant Impulsive Excitation

In a quest to track down the origin of coherent vibrational motions observed in femtosecond pump-probe transients, whether they arise from ground/excited electronic state of solute or are contributed by the solvent, we demonstrate a method for extricating vibrations under resonant and non-resonant impulsive excitations using a diatomic solute in condensed phase (iodine in carbon tetrachloride) with aid of spectral dispersion of the chirped broadband probe. Most importantly, we show how a sum over intensities for a select region of detection wavelengths and Fourier transform of data over select temporal window untwine contributions from vibrational modes of different origins. Thus, in a single pump-probe experiment, vibrational features specific to solute as well as solvent are disentangled that are otherwise spectrally overlapping and are non-separable in conventional (spontaneous/stimulated) Raman spectroscopy employing narrowband excitation. We envision wide-ranging applications of this method to unveil vibrational features in complex molecular systems.     

Light-induced Photoswitching of 4-(Phenylazo)benzoic Acid on Au(111)

Photochromic molecules can undergo a reversible conversion between two isomeric forms upon exposure to external stimuli such as electromagnetic radiation. A significant physical transformation accompanying the photoisomerization process defines them as photoswitches, with potential applications in various molecular electronic devices. As such, a detailed understanding of the photoisomerization process on surfaces and the influence of the local chemical environment on switching efficiency is essential. Herein, we use scanning tunneling microscopy to observe the photoisomerization of 4-(phenylazo)benzoic acid (PABA) assembled on Au(111) in kinetically constrained metastable states guided by pulse deposition. Photoswitching is observed at low molecular density and is absent in tight-packed islands. Furthermore, switching events were noted in PABA molecules coadsorbed in a host octanethiol monolayer, suggesting an influence of the surrounding chemical environment on photoswitching efficiency.     

Development of an Organic Dye-Conjugated β-Diketonate-Europium Complex Luminescence Probe for Discrimination and Detection of Intracellular Biothiols

Small molecular biothiols, cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), play important roles in organisms, and their concentration levels are indicative of some human diseases. Herein we report an organic dye-conjugated β-diketonate-Eu³⁺ complex, [Eu(NBD-keto)₃(DPBT)] (NBD-keto: 7-nitro-2,1,3-benzoxadiazole (NBD)-conjugated to 1,1,1,2,2-pentafluoro-5-phenyl-3,5-pentanedionate through a “O” ether bond; DPBT: 2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine), which acts as a unique luminescent probe for detecting and discriminating biothiols. [Eu(NBD-keto)₃(DPBT)] itself is not luminescent due to intramolecular interactions between NBD and β-diketonate-Eu³⁺ moieties. Upon reaction with biothiols, the β-diketonate-Eu³⁺ complex [Eu(keto)₃(DPBT)] is generated, which emits long-lived red emission at 610 nm. Meanwhile, three biothiol-substituted NBD derivatives that exhibit different luminescence behaviors, green emissive (short-lived) NBD-NR (R=Cys or Hcy) at 540 nm and non-luminescent NBD-SR (R=GSH), are also generated. These luminescence response behaviors allow time-gated and steady-state luminescence modes to be combined for detecting total biothiols and discriminating GSH and Cys/Hcy. Using this probe, the quantitative detection and discrimination of GSH and Cys/Hcy in lysis solutions of HeLa cells were realized, which revealed the potential of the probe for biomedical applications.     

超级微波消解-电感耦合等离子体发射光谱（ICP-OES）法测定土壤中18种元素

为提高土壤多元素同时检测的效率,采用超级微波消解-电感耦合等离子体发射光谱法测定土壤中钾、钠、钙、镁、铜、铁、锰、锌、磷、硫、硼、砷、镉、铬、铅、钴、镓、锂等18种元素含量。比较了超级微波消解、常规微波消解和电热板消解的处理效果,采用超级微波消解法对样品进行前处理,并优化了消解条件。在最优条件下,各元素的检出限在0.05~20 mg/kg,加标回收率在86.2%~107.5%,RSD在0.1%~3.0%,方法准确度及精密度可以满足多元素同时测定的需求,且该方法具有简单、快速、成本低、用酸量少、重现性好等特点。     

Fe2BiTaO7纳米催化剂的组织结构及光催化性能

用固相反应合成法合成了光催化剂Fe2BiTaO7,通过XRD、SEM、TEM、紫外-可见漫反射等表征方法对其组织结构及光催化性能进行了研究。结果表明Fe2BiTaO7为立方晶系烧绿石结构,空间群为Fd3m,禁带宽度为1.72 e V。通过比较Fe2BiTaO7、P25TiO2、掺氮Ti O2和Bi2In Ta O7的可见光光催化降解罗丹明B,发现Fe2BiTaO7降解效果及催化活性均高于其它催化剂,并且Fe2BiTaO7降解罗丹明B效率是掺氮二氧化钛的1.5倍。Fe2BiTaO7降解罗丹明B的曲线符合一级动力学,一级动力学常数为0.022 93 min-1。研究了罗丹明B可能的降解路径和Fe2BiTaO7在可见光下降解苯酚的效果。Fe2BiTaO7(可见光)光催化剂系统适用于纺织工业废水处理。     

钴( Ⅱ)与1,3-间苯咪唑及间苯二甲酸根构筑的两个配位聚合物的合成、晶体结构及性质

以间苯咪唑(1,3-bib)和间苯二甲酸(H2MPA)为配体,在温和的水热条件下,合成了Co( Ⅱ)的2个配位聚合物{[Co(1,3-bib)(MPA)(H2O)2]·H2O}n(1)和{[Co2(1,3-bib)2(MPA)2]·5H2O}n(2),分别用X-射线单晶衍射、元素分析、IR和热重等手段对它们进行了表征,结果表明,配位聚合物1为1D层状结构,属于正交晶系,Pnma空间群;配位聚合物2为双核2D结构,属于三斜晶系,P1空间群。在室温下研究了它们的光学性质。     

一种应用于活细胞中检测Hg(Ⅱ)的苯并噻唑类荧光探针

合成和表征了一种苯并噻唑类的荧光探针(YH1),并用光谱法研究了它对不同金属离子的响应。结果表明:YH1对Hg2+显示出好的选择性和灵敏度,与Hg2+作用后,在紫外光的激发下它的溶液颜色由蓝色变为无色。在1.4~8.8μmol·L-1浓度的范围内,YH1的荧光强度与Hg2+浓度有线性关系,其对Hg2+的检出限为0.56μmol·L-1。此外,YH1可跨过细胞膜,细胞毒性低,还可应用于He La活细胞中对Hg2+进行荧光成像。