基于罗丹明B的激活型α-酮戊二酸荧光探针

α-酮戊二酸(α-KA)是人体三羧酸循环的一个重要代谢中间体,异柠檬酸脱氢酶-1(IDH1)及异柠檬酸脱氢酶-2(IDH2)的突变将导致α-KA转化为2-羟基戊二酸(2HG),该过程与急性骨髓性白血病(AML)密切相关,因此检测人体内α-KA的含量变化具有重要意义。本文以罗丹明B作为荧光基团,通过将罗丹明B与水合肼反应得到能够检测α-KA的荧光增强型探针RBN,并优化了检测温度、pH及响应时间等条件。研究表明,RBN对α-KA表现出很好的选择性,不受人体内常见氨基酸、化学结构类似的羰基化合物及活性氧化物(ROS)的影响,具有潜在的应用价值。     

Photoluminescence properties and application of yellow Ca0.65Si10Al2O0.7N15.3:xEu2+ phosphors for white LEDs

A series of yellow-emitting oxynitride Ca_0.65Si₁₀Al₂O_0.7N_15.3:xEu²⁺ phosphors with α-sialon structure were synthesized. The phase composition and crystal structure were identified by X-ray diffraction and the Rietveld refinement. The excitation and emission spectra, reflectance spectra and thermal stability were investigated in detail, respectively. Results show that Ca_0.65Si₁₀Al₂O_0.7N_15.3:0.12Eu²⁺ phosphors can be efficiently excited by UV-Vis light in the broad range of 290–450 nm and exhibit broad emission spectra peaking at 550–575 nm. The concentration quenching mechanism are discussed in detail and determined to be the dipole-dipole interaction. When the temperature increased to 150 °C, the emission intensity of Ca_0.65Si₁₀Al₂O_0.7N_15.3:0.12Eu²⁺ phosphor is 88.46% of the initial value at room temperature. White LED was fabricated with N-UV LED chip combined with blue Ca₃Si₂O₄N₂:Ce³⁺ and yellow Ca_0.65Si₁₀Al₂O_0.7N_15.3:Eu²⁺ phosphors. The color rendering index and correlated color temperature of this white LED were measured to 78.94 and 6728.12 K, respectively. All above results demonstrate that the as-prepared Ca_0.65Si₁₀Al₂O_0.7N_15.3:xEu²⁺ may serve as a potential yellow phosphor for N-UV w-LEDs.     

α-混合序列部分和乘积精确渐近性的一般形式

利用前人获得的α-混合序列部分和乘积的渐近分布的结果,对一般的边界函数和拟权函数得到了α-混合序列部分和乘积的精确渐近性的一般形式.     

Bloch Constant on α-Bloch Mappings of the Unit Ball

This note is denoted to establishing sharp distortion theorems for subclasses of α-Bloch mappings defined in the unit ball of Cn with critical points.Furthermore,the estimates of Bloch constant with respect to these subclasses are given.     

Highly Sensitive Electrochemical Immunosensor Based on Mesoporous PdPt Nanoparticles Anchored on a Three-dimensional PANI@CNTs Network as Nanozyme Labels

In this study, a novel strategy to amplify electrochemical signals by mesoporous PdPt nanoparticles with core-shell structures anchored on a three-dimensional PANI@CNTs network as nanozyme labels (PdPt/PANI@CNTs) was proposed for the sensitive monitoring of α-fetoprotein (AFP, Ag). First, the mesoporous PdPt nanoparticles prepared by a facile chemical reduction method had excellent biocompatibility with biomolecules, which could capture a large amount of AFP-Ab₂ (Ab₂) and exhibit plentiful pores to entrap more thionine (Thi) into mesoporous PdPt nanoparticles with enhanced loading and abundant active sites. Furthermore, the resulting mesoporous PdPt nanoparticles were abundantly dotted on the surface of a three-dimensional PANI@CNTs network with excellent conductivity and a high specific surface area through the bonding of the amino group to form PdPt/PANI@CNTs nanozyme labels. Most importantly, the as-prepared PdPt/PANI@CNTs nanozyme labels exhibited unexpected enzyme-like activity towards the reduction of hydrogen peroxide owing to the highly indexed facets, enhancing the current response to realize signal amplification. In view of the advantages of nanozyme labels and the involvement of gold nanoparticles (AuNPs, which behave as electrode materials) for the sensitive determination of AFP, the as-developed immunosensor could obtain a dynamic working range of 0.001 ng mL^−1–100.0 ng mL⁻¹ at a detection limit of 0.33 pg mL⁻¹ via DPV (at 3σ). Furthermore, the nanozyme-based electrochemical immunosensor exhibited remarkable analytical performance, which brought about feasible ideas for disease diagnosis in the future.     

Giant Tunability of Charge Transport in 2D Inorganic Molecular Crystals by Pressure Engineering

The unique intermolecular van der Waals force in emerging two-dimensional inorganic molecular crystals (2DIMCs) endows them with highly tunable structures and properties upon applying external stimuli. Using high pressure to modulate the intermolecular bonding, here we reveal the highly tunable charge transport behavior in 2DIMCs for the first time, from an insulator to a semiconductor. As pressure increases, 2D α-Sb₂O₃ molecular crystal undergoes three isostructural transitions, and the intermolecular bonding enhances gradually, which results in a considerably decreased band gap by 25 % and a greatly enhanced charge transport. Impressively, the in situ resistivity measurement of the α-Sb₂O₃ flake shows a sharp drop by 5 orders of magnitude in 0–3.2 GPa. This work sheds new light on the manipulation of charge transport in 2DIMCs and is of great significance for promoting the fundamental understanding and potential applications of 2DIMCs in advanced modern technologies.     

Sustainable Synthesis of α-Hydroxycarboxylic Acids by Manganese Catalyzed Acceptorless Dehydrogenative Coupling of Ethylene Glycol and Primary Alcohols**

Herein, we report a straightforward synthesis of valuable α-hydroxycarboxylic acid molecules via an acceptorless dehydrogenative coupling of ethylene glycol and primary alcohols. A bench-stable manganese complex catalyzed the reaction, which is scalable, with the product being isolated with high yields and selectivities under mild conditions. The protocol is environmentally benign, producing water and hydrogen gas as the only byproducts. Methanol can also be used as a C1 source for producing the platform molecule lactic acid, with a high turnover of >10⁴. The methodology was also used to functionalize alcohols derived from natural products and fatty acids. Furthermore, it was applied for synthesizing α-amino acid, α-thiocarboxylic acid, and several drugs and bioactive molecules, including endogenous metabolites, Danshensu, Enalapril, Lisinopril, and Rosmarinic acid. Preliminary mechanistic studies were performed to shed light on the mechanism involved in the reaction.     

Enantioselective De Novo Synthesis of α,α-Diaryl Ketones from Alkynes

Chiral α,α-diaryl ketones are structural motifs commonly present in bioactive molecules, and they are also valuable building blocks in synthetic organic chemistry. However, catalytic asymmetric synthesis of α,α-diaryl ketones bearing a tertiary stereogenic center remains largely unsolved. Herein, we report a catalytic de novo enantioselective synthesis of α,α-diaryl ketones from simple alkynes via chiral phosphoric acid (CPA) catalysis. A broad range of enolizable α,α-diaryl ketones are prepared in good yields and with excellent enantioselectivities. The described protocol also serves as an efficient deuteration method for the preparation of enantiomerically enriched deuterated α,α-diaryl ketones. Using the methodology reported, bioactive molecules, including one of the best-selling anti-breast cancer drugs, tamoxifen, are readily synthesized.     

Palladium-Catalyzed Asymmetric Trifluoromethylated Allylic Alkylation of N-Substituted Glycine Ethyl Esters with α-(Trifluoromethyl)alkenyl Acetates

An efficient strategy for asymmetric trifluoromethylated allylic alkylation of easily available N-substituted glycine ethyl esters with α-(trifluoromethyl)alkenyl acetates has been developed. Catalyzed by a [Pd(C₃H₅)Cl]₂/(R)-BINAP, various trifluoromethyl-containing N-substituted glycine ethyl ester derivatives are afforded with good yields and excellent enantioselectivities. The product can be readily converted into diverse fluoro-substituted species, which shows the practicability of this method.