Mg,N掺杂β-Ga2O3光电性质的第一性原理计算

通过基于密度泛函理论的第一性原理计算,研究了Mg单掺杂、N单掺杂和不同浓度的Mg-N共掺杂β-Ga₂O₃的结构性质、电子性质和光学性质,以期获得性能比较优异的p型β-Ga₂O₃材料。建立了五种模型:Mg单掺杂、N单掺杂、1个Mg-N共掺杂、2个Mg-N共掺杂和3个Mg-N共掺杂β-Ga₂O₃。经过计算,3个Mg-N共掺杂β-Ga₂O₃体系的结构最稳定。此外,在5种模型中,3个Mg-N共掺杂β-Ga₂O₃体系的禁带宽度是最小的,并且N 2p和Mg 3s贡献的占据态抑制了氧空位的形成,从而增加了空穴浓度。因此,3个Mg-N共掺杂β-Ga₂O₃体系表现出优异的p型性质。3个Mg-N共掺杂体系的吸收峰出现明显红移,在太阳盲区的光吸收系数较大,这归因于导带Ga 4s、Ga 4p、Mg 3s向价带O 2p、N 2p的带间电子跃迁。本工作将为p型β-Ga₂O₃日盲光电材料的研究和应用提供理论指导。     

Circularly Polarized Luminescence and Circular Dichroism of Bichromophoric Difluoroboron-β-diketonates: Inversion and Enhanced Chirality Based on Spatial Arrangements and Self-Assembly

We synthesized two bichromophoric difluoroboron-β-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge ( para and meta (R/S)-CyDFB ). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher g_abs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the g_lum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the g_lum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores.     

饮用水中三氯甲烷与其他氯消毒副产物在活性炭上的吸附竞争研究

通过等温吸附实验，探究了三氯甲烷（CHCl₃）与二氯一溴甲烷（CHBrCl₂）、二氯乙酸（Cl₂CHCOOH）在活性炭上的竞争吸附关系，同时探究了在低浓度条件下CHBrCl₂和Cl₂CHCOOH浓度变化对活性炭吸附CHCl₃的影响。实验结果表明，活性炭吸附CHCl₃和CHBrCl₂符合Freundlich模型，对Cl₂CHCOOH的吸附符合Langmuir模型；活性炭对3种消毒副产物均为优先吸附，吸附能力由大到小依次为CHBrCl₂、CHCl₃、Cl₂CHCOOH；低浓度条件下，活性炭对消毒副产物的吸附效果随体系中物质种类的增加而降低；低浓度条件下，Cl₂CHCOOH的浓度变化对CHCl₃的吸附效果影响不大，但吸附效果随水体中CHBrCl₂浓度的升高而降低。     

高效液相色谱手性固定相法拆分BETTI碱及其衍生物对映体

在纤维素三（3,5-二甲基苯基氨基甲酸酯）（Chiralcel OD-H）和Pirkle型(R, R)-Whelk-O1手性柱上对手性氨基酚1-(α-氨基苄基)-2-萘酚（Betti 碱）及其衍生物1-(α-苄氨基苄基)-2-萘酚和1-(α-哌啶基苄基)-2-萘酚对映体分离进行了研究，分别考察了在正己烷流动相中，碱性添加剂、醇类添加剂的种类和浓度对手性拆分的影响。结果表明：溶质在Chiralcel OD-H柱上的分离效果好，而在(R, R)-Whelk-O1手性柱上只有1-(α-苄氨基苄基)-2-萘酚部分分离。研究了空间立体结构因素对手性分离的影响，初步探讨和比较了溶质在这2种手性柱上的手性识别机理。发现对(R, R)-Whelk-O1柱，溶质与固定相之间的吸引作用很小，而对于Chiralcel OD-H柱，溶质在手性空腔中的空间适应性很可能是手性识别的关键。     

Preparation and characterization of nano-Co-[4-chlorophenyl-salicylaldimine-methyl pyranopyrazole]Cl2 as a new Schiff base complex and catalyst for the solvent-free synthesis of 1-amidoalkyl-2-naphthols

By the reaction of 4-chlorobenzaldehyde with ethyl acetoacetate, malononitrile, and hydrazine hydrate, 6-amino-4-(4-chlorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile was prepared and then reacted with salicylaldehyde and CoCl₂·6H₂O to produce nano-Co-[4-cholorophenyl-salicylaldimine-methylpyranopyrazole]Cl₂ (nano-[Co-4CSMP]Cl₂). The prepared nano-Schiff base complex was reported for the first time and fully characterized by Fourier transform-infrared spectroscopy, thermal gravimetric analysis, differential thermal gravimetric analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and Brunner–Emmett–Teller analyses and applied as an efficient catalyst for the synthesis of some 1-amidoalkyl-2-naphthol derivatives.     

碱金属盐催化1,2,4-三唑与α,β-不饱和酮及二酰亚胺的氮杂Michael反应

发展了一种高效的碱金属盐催化1,2,4-三唑与α,β-不饱和酮及α,β-不饱和二酰亚胺的氮杂Michael加成反应的新方法,以中等到优异的产率得到目标产物.该方法原料易得,底物普适性好,反应条件温和,易实现克级规模的制备.产物容易转化为相应的γ-氨基醇.     

Role of anti-inflammatory interventions in high-fat-diet-induced obesity

Lipotoxicity is defined as deposition of excess fat associated with an inflammatory response. Metabolomic analysis of fatty acids (FAs) can be a marker of silent inflammation. ω3-Enriched diet, celecoxib, and safranal may have a protective anti-inflammatory role. In this work, total FAs extracted from red blood cells and arachidonic acid-to-eicosapentaenoic acid (AA-to-EPA) ratios were assessed using GC–MS assay in single-ion monitoring mode. The study was conducted on 64 male rats divided into eight groups: I, controls; II, rats received high-fat diet (HFD), III, rats received ω-6-enriched HFD; IV, rats received ω-3-enriched HFD; V, rats received celecoxib with HFD; VI, rats received safranal with HFD; VII and VIII, rats received celecoxib and safranal with ω-3 HFD, respectively. GC–MS Gas chromatography Mass spectrometry was performed for analysis of fatty acid methyl ester. Enzyme-linked immunosorbent assay was used to analyze serum interleukin-6 (IL-6) and transforming growth factor-beta 1 (TGF-β1) concentrations. A statistically significant decrease of AA-to-EPA ratio was observed in group VII when compared with the groups receiving HFDs. This group also showed the lowest serum IL-6 level and highest TGF-β1 level. In conclusion, ω3-enriched diet along with drugs (e.g. celecoxib) and herbal medications (e.g. safranal) may have an anti-inflammatory effect in lipotoxicity. GC–MS with single-ion monitoring is valid for the analysis of FAs.     

Late-Stage Functionalization by Chan–Lam Amination: Rapid Access to Potent and Selective Integrin Inhibitors

A late-stage functionalization of the aromatic ring in amino acid derivatives is described. The key step is a copper-catalysed diversification of a boronate ester by amination (Chan–Lam reaction) that can be carried out on a complex β-aryl-β-amino acid scaffold. This not only considerably extends the substrate scope of amination partners, but also delivers an array of potent and selective integrin inhibitors as potential treatment agents of idiopathic pulmonary fibrosis (IPF). This versatile chemical strategy, which is amenable to high-throughput-array protocols, allows the installation of pharmaceutically valuable heteroaromatic fragments at a late stage by direct coupling to NH heterocycles, leading to compounds with drug-like attributes. It thus constitutes a useful addition to the medicinal chemist's repertoire.     

One-Pot Synthesis of Enantioenriched β-Amino Secondary Amides via an Enantioselective [4+2] Cycloaddition Reaction of Vinyl Azides with N-Acyl Imines Catalyzed by a Chiral Brønsted Acid

A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides.     

Conceptualization and Synthesis of the First Inosito-Inositol (Decahydroxydecalin,DHD): In silico Binding to β-Amyloid Protein

Previously unknown entities in the form of 1,2,3,4,5,6,7,8,9,10-decahydroxydecalins (DHDs) have been conceptualized and the first member of this class, an inosito-inositol, has been synthesized from aromatic hydrocarbon naphthalene following a flexible strategy that is amenable to diversity creation. The DHD accessed here has been subjected to preliminary in silico evaluation with Aβ and may hold some promise in Alzheimer's disease therapeutics.