An investigation on the defect structures and spin Hamiltonian parameters for the two orthorhombic Ti3+ centers in ZnWO4

By employing the perturbation formulae of the spin Hamiltonian parameters (SHPs) (g factors g_xx, g_yy, g_zz, hyperfine structure constants A_xx, A_yy, A_zz and superhyperfine parameters A_xx׳, A_yy׳, A_zz׳) for a 3d¹ ion in orthorhombically elongated octahedra and tetrahedra, the defect structures and the experimental EPR spectra are theoretically and systematically investigated for the two orthorhombic Ti³⁺ centers C₁ and C₂ in ZnWO₄. Center C₁ is ascribed to the impurity Ti³⁺ at host W⁶⁺ site associated with two nearest neighbor oxygen vacancies due to charge compensation. The resultant tetrahedral [TiO₄]^5– cluster is determined to undergo the local orthorhombic elongation distortion, characterized by the axial distortion angle Δθ (=θ–θ₀≈–6.84°) of the local impurity-ligand bond angle θ related to θ₀ (≈54.74°) and the perpendicular distortion angle Δε (=ε–ε₀≈2.5°) related to ε₀ (≈45°) of an ideal tetrahedron because of the Jahn–Teller effect. Center C₂ is attributed to Ti³⁺ on Zn²⁺ site, and this octahedral [TiO₆]^9– cluster may experience the local axial elongation ΔZ (≈0.001 Ǻ) and the planar bond angle variation Δφ (≈9.1°) due to the Jahn–Teller effect, resulting in a more regular oxygen octahedron. All the calculated SHPs (i.e., g factors for both centers, the hyperfine structure constants for center C₂ and superhyperfine parameters of next nearest neighbor ligand W for center C₁) show good agreement with the observed values. However, the theoretical results based on the previous assignment of center C₁ as Ti³⁺ on W⁶⁺ site with only one nearest planar oxygen vacancy (i.e., five-fold coordinated octahedral [TiO₅]^7– cluster) show much worse agreement with the experimental data. The defect structures and the SHPs (especially the g anisotropies) are discussed for both centers. The present studies on the superhyperfine parameters of ligand W⁶⁺ for center C₁ would be helpful to further investigations on the superhyperfine interactions of cation ligands which were rather scarcely treated before.     

A simple,rapid and sensitive method based on modified multiwalled carbon nanotube for preconcentration and determination of lead ions in aqueous media in natural pHs

In this study, multiwalled carbon nanotube (MWCNT) was modified by the pyridine group using a silane agent and characterized by infrared spectroscopy (IR), thermal analysis (TG/DTA), and elemental analysis (CHN) and scanning electron microscopy (SEM). The application of this sorbent was investigated in determination of lead ions in aqueous samples, using flame atomic absorption spectrometry (FAAS). Through this study, different parameters such as pH and sample flow rate on adsorption process and eluent concentration, volume and flow rate were optimized. The limit of detection (LOD), the relative standard deviation and the recovery of the method were 2 ng mL^?1, 1.3% and 99.7%, respectively. Two standard reference materials (NIST 1571 and NIST 1572) were used to verify accuracy of this method. Finally, the sorbent was successfully applied for extraction and determination of low levels of Pb(II) ions in aqueous samples.     

Near-Ultraviolet Circular Dichroism and Two-Dimensional Spectroscopy of Polypeptides

A fully quantitative theory of the relationship between protein conformation and optical spectroscopy would facilitate deeper insights into biophysical and simulation studies of protein dynamics and folding. In contrast to intense bands in the far-ultraviolet, near-UV bands are much weaker and have been challenging to compute theoretically. We report some advances in the accuracy of calculations in the near-UV, which were realised through the consideration of the vibrational structure of the electronic transitions of aromatic side chains.     

Dynamic Interactions in Synthetic Receptors: A Guest Exchange Saturation Transfer Study

The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF₄⁻ are mediated by the side chains on the receptor (100 s⁻¹<k_ex<5000 s⁻¹), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method.     

Reactions of quinones with some amino alcohols,thiols and a UV-Vis study

Abstract

In the present study, the reactions of 2,3-dichloro-1,4-naphthoquinone (DCNQ) with amino-1,2-propanediol and some thiols were investigated. Novel N-, N,S-, and S,O- substituted derivatives were obtained and the structures of all compounds were characterized by spectroscopic methods (FT-IR, ¹H NMR, ¹³ Baker, R. A.; Tatum, J. H.; Nemec, S. Antimicrobial Activity of Naphthoquinones from Fusaria. Mycopathologia 1990, 111, 9–15. DOI: 10.1007/BF02277294.[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]C NMR, Mass spectroscopy) and microanalysis. The absorption behaviors of novel compounds were also investigated with UV-Vis spectroscopy in different solvents, such as ethanol, tetrahydrofuran and chloroform.     

Fluorescence properties of riboflavin-functionalized mesoporous silica SBA-15 and riboflavin solutions in presence of different metal and organic cations

Riboflavin was covalently linked to mesoporous SBA-15 silica surface via grafting technique. Then fluorescence properties of the system obtained were analyzed in the presence of several metal and organic cations. Both quenching and strengthening of fluorescence as well as significant changes in the maximum fluorescence wavelength were observed. The results were compared with absorption and fluorescence data obtained for riboflavin water solutions.     

Thermally induced solid-state transformation of cimetidine. A multi-spectroscopic/chemometrics determination of the kinetics of the process and structural elucidation of one of the products as a stable N3-enamino tautomer

Exposure of cimetidine (CIM) to dry heat (160–180 °C) afforded, upon cooling, a glassy solid containing new and hitherto unknown products. The kinetics of this process was studied by a second order chemometrics-assisted multi-spectroscopic approach. Proton and carbon-13 nuclear magnetic resonance (NMR), as well as ultraviolet and infrared spectroscopic data were jointly used, whereas multivariate curve resolution with alternating least squares (MCR-ALS) was employed as the chemometrics method to extract process information. It was established that drug degradation follows a first order kinetics.     

Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

QEPAS系统中石英音叉模态仿真计算与研究

对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算，获得石英音叉前6阶振型与模态频率，认知了第4阶对称摆动振型为有效振动，利用单因素法分析了石英音叉的音臂长度l₁、音臂宽度w₁、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响，敏感度依次为： l₁> w₁>d>θ>t>h，考虑实际设计情形，筛选出了l₁，w₁，d与h四个石英音叉设计变量，采用Box-Behnken实验设计方案与RSM(response surface methodology)方法，以Fre为函数目标，建立l₁，w₁，d与h的二次回归响应面模型，得到了参数之间的交互作用，利用Design-Expert软件对响应面模型进行设计参数反求，结果表明，在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小，基本满足QEPAS系统的计算需求，所提出的研究与设计方法具有一定通用性，可为QEPAS系统中石英音叉结构参数设计提供参考。     

Comparative absorption kinetics of seven active ingredients of Eucommia ulmoides extracts by intestinal in situ circulatory perfusion in normal and spontaneous hypertensive rats

Eucommia ulmoides Oliv. (E. ulmoides) is a valuable and nourishing medicinal herb in China that has been used in the treatment of hypertension. Given the fact that most traditional Chinese medicine is mainly used to treat disease, investigating the pharmacokinetics of traditional Chinese medicines in the pathological state is more useful than that in the normal state. However, the differences in the absorption kinetics of active ingredients of E. ulmoides extract between pathological and physiological conditions have not been reported. Therefore, in this study, the rat intestinal in situ circulatory perfusion model was used to investigate the differences in absorption kinetics of seven active ingredients of E. ulmoides extract in normal and spontaneously hypertensive rats, namely, genipinic acid, protocatechuic acid, neochlorogenic acid, chlorogenic acid, cryptochlorogenic acid, (+)-pinoresinol di-O-β-D -glucopyranoside and (+)-pinoresinol 4′-O-β-D -glucopyranoside. Our results indicate that the pathological state of spontaneous hypertension may change the absorption of active components of E. ulmoides extracts, and these findings may provide a reference for improving the rational use of E. ulmoides in the clinic.