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91.
Nonlinear optical (NLO) crystals assembled with conventional non-π-conjugated tetrahedral functional building units (FBUs), generally referring to [PO4] and [BO4], usually exhibit weak nonlinearity and poor birefringence. It is currently proposed that partially substituting oxygen atoms with fluoride atoms in these FBUs could enhance these crucial properties. Hence, we investigated for the first time the NLO-related properties of NH4BAsO4F (ABAF), which was constructed from tetrahedral [BO3F] and [AsO4] FBUs, and enhancements of these properties were observed in this material, that is large second-harmonic generation (SHG) response (2 × KDP) and improved birefringence (0.03 at 1064 nm). Notably, both SHG coefficient and birefringence of ABAF exceeded those of a great majority of phosphates, sulfates, or boron phosphates and achieved a preferable balance. It is interesting that ABAF shows vast structural similarities to the typical NLO crystals Sr2Be2B2O7 (SBBO) and KBe2BO3F2 (KBBF), which might be the partial reason why it showed improvement in these vital properties. This work may afford some inspiration for enhancing the key performances of NLO crystals assembled with non-π-conjugated tetrahedra.We report a new nonlinear optical crystal assembled exclusively with tetrahedral functional building units in which enhanced birefringence (Δn) and second-harmonic generation (deff) were observed. 相似文献
92.
Kwang-Woo Jung Moon-Soo Chung Hyoung-Woo Bai Byung-Yeoup Chung Sungbeom Lee 《Molecules (Basel, Switzerland)》2021,26(11)
Due to lifespan extension and changes in global climate, the increase in mycoses caused by primary and opportunistic fungal pathogens is now a global concern. Despite increasing attention, limited options are available for the treatment of systematic and invasive mycoses, owing to the evolutionary similarity between humans and fungi. Although plants produce a diversity of chemicals to protect themselves from pathogens, the molecular targets and modes of action of these plant-derived chemicals have not been well characterized. Using a reverse genetics approach, the present study revealed that thymol, a monoterpene alcohol from Thymus vulgaris L., (Lamiaceae), exhibits antifungal activity against Cryptococcus neoformans by regulating multiple signaling pathways including calcineurin, unfolded protein response, and HOG (high-osmolarity glycerol) MAPK (mitogen-activated protein kinase) pathways. Thymol treatment reduced the intracellular concentration of Ca2+ by controlling the expression levels of calcium transporter genes in a calcineurin-dependent manner. We demonstrated that thymol decreased N-glycosylation by regulating the expression levels of genes involved in glycan-mediated post-translational modifications. Furthermore, thymol treatment reduced endogenous ergosterol content by decreasing the expression of ergosterol biosynthesis genes in a HOG MAPK pathway-dependent manner. Collectively, this study sheds light on the antifungal mechanisms of thymol against C. neoformans. 相似文献
93.
The molecular structures, electron affinities, and dissociation energies of the Si(n)H/Si(n)H- (n = 4-10) species have been examined via five hybrid and pure density functional theory (DFT) methods. The basis set used in this work is of double-zeta plus polarization quality with additional diffuse s- and p-type functions, denoted DZP++. The geometries are fully optimized with each DFT method independently. The three different types of neutral-anion energy separations presented in this work are the adiabatic electron affinity (EA(ad)), the vertical electron affinity (EA(vert)), and the vertical detachment energy (VDE). The first Si-H dissociation energies, D(e)(Si(n)H --> Si(n) + H) for neutral Si(n)H and D(e)(Si(n)H- --> Si(n)- + H) for anionic Si(n)H- species, have also been reported. The structures of the ground states of these clusters are traditional H-Si single-bond forms. The ground-state geometries of Si5H, Si6H, Si8H, and Si9H predicted by the DFT methods are different from previous calculations, such as those obtained by Car-Parrinello molecular dynamics and nonorthogonal tight-binding molecular dynamics schemes. The most reliable EA(ad) values obtained at the B3LYP level of theory are 2.59 (Si4H), 2.84 (Si5H), 2.86 (Si6H), 3.19 (Si7H), 3.14 (Si8H), 3.36 (Si9H), and 3.56 (Si10H) eV. The first dissociation energies (Si(n)H --> Si(n) + H) predicted by all of these methods are 2.20-2.29 (Si4H), 2.30-2.83 (Si5H), 2.12-2.41 (Si6H), 1.75-2.03 (Si7H), 2.41-2.72 (Si8H), 1.86-2.11 (Si9H), and 1.92-2.27 (Si10H) eV. For the negatively charged ion clusters (Si(n)H- --> Si(n)- + H), the dissociation energies predicted are 2.56-2.69 (Si4H-), 2.80-3.01 (Si5H-), 2.86-3.06 (Si6H-), 2.80-3.03 (Si7H-), 2.69-2.92 (Si8H-), 2.92-3.18 (Si9H-), and 2.89-3.25 (Si10H-) eV. 相似文献
94.
The refolding of the reduced-denatured insulin from bovine pancreas was investigated with the size exclusion chromatography (SEC). It was shown that the reduced-denatured insulin originally denatured with 7.0 mol L?1 guanidine hydrochloride (GuHCI) or 8.0 mol L?1 urea could not be refolded with a non-oxidized mobile phase. Although the oxidized and reduced glutathione (GSSG and GSH) were employed in the oxidized mobile phase, the reduced-denatured insulin still could not be renatured. However, in the presence of 2.0 mol Lt-1 urea in the oxidized mobile phase employed, the reduced-denatured insulin can be refolded with SEC, and the aggregation of denatured insulin can be diminished by urea. In addition, the disulfide exchange of reduced-denatured insulin also can be accelerated with GSSG/GSH in the oxidized mobile phase. The three disulfide bridges of insulin were formed correctly and the reduced-unfolded insulin can be renatured completely. The results were further tested with reversed-phase liquid chromatography (RPLC) and hydrophobic interaction chromatography (HIC). 相似文献
95.
Bai Y Song N Gao JP Sun X Wang X Yu G Wang ZY 《Journal of the American Chemical Society》2005,127(7):2060-2061
A new, practical approach to a variety of highly electrooptically active polymers for device development is described. It involves the use of a new thermally cross-linkable, hyperbranched oligomer containing nonlinear optical (NLO) chromophores as a macromolecular dopant in a common host polymer. A series of NLO polymeric blends were readily formulated and showed large and stable electrooptic (EO) coefficients (up to 65 pm/V). In comparison with previously studied linear NLO polyimides and guest-host polymers doped with molecular chromophores and even linear NLO analogous oligomers, this new approach offers clear advantages for device development in terms of improved poling efficiency, larger EO coefficients, good temporal stability, and versatile material formulation. 相似文献
96.
Fangli Fan Jing Bai Fuyou Fan Xiaojie Yin Yang Wang Wei Tian Xiaolei Wu Zhi Qin 《Journal of Radioanalytical and Nuclear Chemistry》2014,300(3):1039-1043
Solvent extraction of uranium with α-benzoinoxime from aqueous solutions has been systematically investigated. The extraction equilibration was very fast and achieved at 60 s for uranium. The extraction of uranium was pH-dependent using α-benzoinoxime as extractant. The effect concentration of uranium and α-benzoinoxime was studied. The uranium loaded in the organic phase can be stripped efficiently with 93 % yield using 0.1 M HCl as the stripping agent in a single stripping step. A good selectivity for uranium was observed through α-benzoinoxime as extractant from aqueous solution with other interfering cation ions. Present study suggested that α-benzoinoxime can be used as a potential extractant for separation of uranium from aqueous solution using centrifugal extractor in industrial application. 相似文献
97.
Shuhua Liu Lu Wang Yuxin Gao Baoying Yu Yun Bai 《Journal of Thermal Analysis and Calorimetry》2014,118(3):1483-1492
The hydration properties of slag sulfate cement (SSC), slag Portland cement (PSC), and ordinary Portland cement (POC) were compared in this study by determining the compressive strength of pastes, the hydration heat of binders within 72 h, the pore structure, the hydration products, and the hydration degree. The results indicated that main hydration products of PSC paste and POC paste are calcium hydroxide and C–S–H gel, while those of SSC paste are ettringite and C–S–H gel from the analyses of XRD, TG–DTA, and SEM. At the early curing age, the compressive strength depends on the clinker content in the cementitious system, while at the late curing age, which is related to the potential reactivity of slag. From hydration heat analysis, the cumulative hydration heat of PSC is lower than that of POC, but higher than that of SSC. Slag can limit chemical reaction and the delayed coagulation of gypsum, which also plays a role in the early hydration. So SSC shows the lowest heat release and slag can’t be simulated without a suitable alkaline solution. Based on MIP analysis, the porosity of POC paste is the smallest while the average pore size is the biggest. At the age of 90 days, the compressive strength of SSC can get higher development because of its relative smaller pore size than that of PSC and POC paste. 相似文献
98.
报道了一种以KF/Al_2O_3催化合成4-甲基-4-氮杂-21E-苯亚甲基-5-孕烯-3,20-二酮类化合物的方法。以黄体酮为原料,经NaIO_4/KMnO_4氧化裂解、胺解关环得到重要中间体4-甲基-4-氮杂-5-孕烯-3,20-二酮,后者在KF/Al_2O_3催化下经克莱森缩合得到目标产物。考察了不同的催化剂、反应温度、催化剂用量对目标产物的影响。条件优化的结果为:n(3)∶n(KF/Al_2O_3)=1∶1,回流状态下反应4 h,产率为56%~68%。此方法适用性好,为4-氮杂甾体苯亚甲基衍生物的合成提供了一种方便而有效的方法。 相似文献
99.
Peripheral Templation‐Modulated Interconversion between an A4L6 Tetrahedral Anion Cage and A2L3 Triple Helicate with Guest Capture/Release 下载免费PDF全文
Xuemin Bai Prof. Chuandong Jia Prof. Yanxia Zhao Dr. Dong Yang Shi‐Cheng Wang Prof. Anyang Li Prof. Yi‐Tsu Chan Prof. Yao‐Yu Wang Prof. Xiao‐Juan Yang Prof. Biao Wu 《Angewandte Chemie (International ed. in English)》2018,57(7):1851-1855
An anion‐coordination‐based A4L6 (“A” denotes anion and “L” is ligand) tetrahedral cage was constructed by a C2‐symmetric bis‐bis(urea) ligand and phosphate anion, which showed reversible interconversion with the A2L3 triple helicate as a response to the template, concentration, or solvent. Notably, an unusual “peripheral” templation was found to be critical to stabilize the tetrahedral structure. This peripheral effect was utilized to assemble an “empty” A4L6 cage that allows the multi‐stimuli‐controlled capture/release of biologically important species such as choline and acetylcholine. 相似文献
100.
Modular One‐Step Three‐Component Synthesis of Tetrahydroisoquinolines Using a Catellani Strategy 下载免费PDF全文
Guangyin Qian Miao Bai Shijun Gao Han Chen Siwei Zhou Dr. Hong‐Gang Cheng Wei Yan Prof. Dr. Qianghui Zhou 《Angewandte Chemie (International ed. in English)》2018,57(34):10980-10984
Reported is a modular one‐step three‐component synthesis of tetrahydroisoquinolines using a Catellani strategy. This process exploits aziridines as the alkylating reagents, through palladium/norbornene cooperative catalysis, to enable a Catellani/Heck/aza‐Michael addition cascade. This mild, chemoselective, and scalable protocol has broad substrate scope (43 examples, up to 90 % yield). The most striking feature of this protocol is the excellent regioselectivity and diastereoselectivity observed for 2‐alkyl‐ and 2‐aryl‐substituted aziridines to access 1,3‐cis‐substituted and 1,4‐cis‐substituted tetrahydroisoquinolines, respectively. Moreover, this is a versatile process with high step and atom economy. 相似文献