Syntheses,crystal structures and properties of Cd(II) and Ag(I) complexes based on 2-p-methylphenyl-5-(2-pyridyl)-1,3,4-thiadiazole

Abstract

Complexes of [CdL₂(NO₃)₂]·1.5H₂O and [Ag₂(μ-L)₂(NO₃)₂] were synthesized by the reactions of 2-p-methylphenyl-5-(2-pyridyl)-1,3,4-thiadiazole (L) with Cd(NO₃)₂·4H₂O and AgNO₃, respectively. Their structures were determined by single crystal X-ray diffraction. The photophysical property and thermal stability were characterized by FT???IR, UV???Vis absorption, fluorescence, and thermogravimetric analysis (TGA). Both complexes belong to the triclinic system with space group p???1. The central metal of [CdL₂(NO₃)₂]·1.5H₂O has a distorted octahedral geometry [CdN₄O₂], while two central Ag(I) atoms of [Ag₂(μ-L)₂(NO₃)₂] exhibit distorted tetrahedral geometries [AgN₃O].     

Theoretical study of (e,2e) triple differential cross sections of pyrimidine and tetrahydrofurfuryl alcohol molecules using multi-center distorted-wave method

We report theoretical studies of electron impact triple differential cross sections of two bio-molecules,pyrimidine and tetrahydrofurfuryl alcohol,in the coplanar asymmetric kinematic conditions with the impact energy of 250 eV and ejected electron energy of 20 eV at three scattering angles of-5°,-10°,and-15°.Present multi-center distorted-wave method well describes the experimental data,which was obtained by performing(e,2e)experiment.The calculations show that the secondary electron produced by the primary impact electron is strongly influenced by the molecular ionic multi-center potential,which must be considered when the low energy electron interacts with DNA analogues.     

Sentinel-2卫星的多光谱轻量级船舶目标检测算法

近年来深度卷积神经网络在可见光船舶检测方面取得了显著的进展，然而，大多数相关研究是通过改进大型的网络结构来提高检测性能，因此加大了对更高计算机性能的需求。此外，可见光图像难以在云、雾、海杂波、黑夜等复杂场景检测到船舶。针对以上问题，提出了一种融合红（red, R）、绿（green, G）、蓝（blue, B）和近红外（NIR）4个波段光谱信息的由粗到精细的轻量型船舶检测算法。与现有的方法中根据光谱特性利用水体检测算法提取水体区域不同之处是该算法是利用改进的水体检测算法来提取船舶候选区域。为获取更准确的候选区域，对船舶、厚云、薄云、平静海面、杂波海面5种场景中4个波段的像素值进行了统计分析，选取近红外大于阈值作为辅助判断，并以其中心点获取候选区域32×32大小的切片，并对切片进行非极大值抑制，由此获得了船舶粗检测结果。随后构建了轻量级LSGFNet网络对船舶候选区域切片进行精细识别。构建的网络融合了1×1卷积提取的波谱特征与3×3的提取几何特征，为防止光谱特征与几何特征的信息在融合时“信息不流通”，在LSGFNet网络中引入了ShuffleNet中的通道打乱机制，并减小了模型结构，与典型的轻量级网络相比具有更好的效果且模型较小。最后，利用Sentinel-2卫星多光谱10 m分辨率数据构建了512×512大小的1 120组数据进行粗检测，以及32×32大小的6 014组数据进行精细网络训练，其中候选区域粗提取的查全率为98.99%，精细识别网络精确度为96.04%，不同场景下的平均精确度为92.98%。实验表明该算法在抑制云层、海浪杂波等干扰的复杂背景下具有较高的检测效率，且训练时间短、计算机性能需求低。     

The 1H and 13C NMR chemical shifts of Strychnos alkaloids revisited at the DFT level

The density functional theory calculation of ¹H and ¹³C NMR chemical shifts in a series of ten 10 classically known Strychnos alkaloids with a strychnine skeleton was performed at the PBE0/pcSseg-2//pcseg-2 level. It was found that calculated ¹H and ¹³C NMR chemical shifts provided a markedly good correlation with experiment characterized by a mean absolute error of 0.08 ppm in the range of 7 ppm for protons and 1.67 ppm in the range of 150 ppm for carbons, so that a mean absolute percentage error was as small as ~1% in both cases.     

Identifying aspirin polymorphs from combined DFT-based crystal structure prediction and solid-state NMR

A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated ¹H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs.     

Computational and dynamic NMR investigation of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane

The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by ¹H- and ¹³C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C₂ symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a C_s transition state with a calculated relative free energy of 11.0 kcal mol⁻¹. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol⁻¹ at 298 K.     

Nano-sized Cu(II) and Zn(II) complexes and their use as a precursor for synthesis of CuO and ZnO nanoparticles: A study on their sonochemical synthesis,characterization, and DNA-binding/cleavage,anticancer, and antimicrobial activities

Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)₂] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.     

Identification of metabolic markers in patients with type 2 Diabetes by Ultrafast gas chromatography coupled to electronic nose. A pilot study

Metabolomics is a potential tool for the discovery of new biomarkers in the early diagnosis of diseases. An ultra-fast gas chromatography system equipped to an electronic nose detector (FGC eNose) was used to identify the metabolomic profile of Volatile Organic Compounds (VOCs) in type 2 diabetes (T2D) urine from Mexican population. A cross-sectional, comparative, and clinical study with translational approach was performed. We recruited twenty T2D patients and twenty-one healthy subjects. Urine samples were taken and analyzed by FGC eNose. Eighty-eight compounds were identified through Kovats's indexes. A natural variation of 30% between the metabolites, expressed by study groups, was observed in Principal Component 1 and 2 with a significant difference (p < 0.001). The model, performed through a Canonical Analysis of Principal coordinated (CAP), allowed a correct classification of 84.6% between healthy and T2D patients, with a 15.4% error. The metabolites 2-propenal, 2-propanol, butane- 2,3-dione and 2-methylpropanal, were increased in patients with T2D, and they were strongly correlated with discrimination between clinically healthy people and T2D patients. This study identified metabolites in urine through FGC eNose that can be used as biomarkers in the identification of T2D patients. However, more studies are needed for its implementation in clinical practice.