Salt Metathesis: Tetrafluoroborate Anion Rapidly Fluoridates Organoboronic Acids to give Organotrifluoroborates

Tetrafluoroborate (BF₄⁻) has long been used as a spectator counter anion. Herein, we report an unprecedented salt metathesis between a variety of BF₄⁻ salts and a series of organoboronic acids yielding the corresponding organotrifluoroborates. We identified conditions for fast and efficient fluoridation (<1 h) with minimal workup. Fundamentally, this work discloses the proclivity of BF₄⁻ to exchange fluoride atoms with organoboronates, highlighting the lability of BF₄⁻.     

酰氨基硫脲类新型分子钳受体的合成及其对氟离子的识别性能研究

本文设计并高产率合成了三种新型阴离子识别受体化合物,它们对F-的识别选择性较卤素其他阴离子的高。其对F-的识别性能通过紫外—可见光谱和核磁共振氢谱进行了检测,光谱数据表明,在DMSO溶液中受体与F-通过氢键相互作用形成1:1配合物。与以前我们报道的受体化合物相比,由于此类分子钳受体化合物具有更多的阴离子识别位点,因此具有更好地阴离子识别性能。     

A Nonenzymatic Glucose Sensor Using Nanoporous Platinum Electrodes Prepared by Electrochemical Alloying/Dealloying in a Water‐Insensitive Zinc Chloride‐1‐Ethyl‐3‐Methylimidazolium Chloride Ionic Liquid

We report here a nonenzymatic sensor by using a nanoporous platinum electrode to detect glucose directly. The electrode was fabricated by electrochemical deposition and dissolution of PtZn alloy in zinc chloride‐1‐ethyl‐3‐methylimidazolium chloride (ZnCl₂‐EMIC) ionic liquid. Both SEM and electrochemical studies showed the evidences for the nanoporous characteristics of the as‐prepared Pt electrodes. Amperometric measurements allow observation of the electrochemical oxidation of glucose at 0.4 V (vs. Ag/AgCl) in pH 7.4 phosphate buffer solution. The sensor also demonstrates significant reproducibility in glucose detection; the higher the roughness factor of the Pt electrode, the lower the detection limit of glucose. The interfering species such as ascorbic acid and p‐acetamidophenol can be avoided by using a Pt electrode with a high roughness factor of 151. Overall, the nanoporous Pt electrode is promising for enzymeless detection of glucose at physiological condition.     

Nonexistence of Ground States of -△u = u^p - u^q

The authors use the method of moving spheres to prove the nonexistence of ground states of -△u = u^p - u^q for n≥3,-∞〈p〈（n＋2）/（n-2） and q〉max （1,p）,
In fact this conclusion is a special case of -△u =f（u） for n≥2.     

Optically active supramolecular complex formed by ionic self-assembly of cationic perylenediimide derivative and adenosine triphosphate

Ionically self-assembled complex between a water-soluble perylenediimide (PDI) derivative, N,N'-bis(propylenetrimethylammonium)-3,4,9,10-perylenediimide (BPTA-PDI), and adenosine triphosphate (ATP) has been prepared. Absorption, emission, and circular dichroism (CD) spectroscopic techniques were used to monitor the complex formation. It was found that, upon the addition of ATP into the solution of an intrinsically achiral BPTA-PDI, the complex exhibits a unique split-type induced CD (ICD) in the pi-pi* transition region of the PDI chromophore, indicating that the molecular chirality of nucleotides is expressed in the perylene moiety through the multiple electrostatic interactions. The influences of BPTA-PDI concentration, temperature, and adenosine nucleotides bearing different numbers of phosphate groups on the chirality induction to BPTA-PDI were also investigated. On the basis of extensive investigations performed with absorption, emission, and CD spectroscopy, a possible mechanism for the formation of chiral superstructures is proposed.     

Most efficient cocaine hydrolase designed by virtual screening of transition states

Cocaine is recognized as the most reinforcing of all drugs of abuse. There is no anticocaine medication available. The disastrous medical and social consequences of cocaine addiction have made the development of an anticocaine medication a high priority. It has been recognized that an ideal anticocaine medication is one that accelerates cocaine metabolism producing biologically inactive metabolites via a route similar to the primary cocaine-metabolizing pathway, i.e., cocaine hydrolysis catalyzed by plasma enzyme butyrylcholinesterase (BChE). However, wild-type BChE has a low catalytic efficiency against the abused cocaine. Design of a high-activity enzyme mutant is extremely challenging, particularly when the chemical reaction process is rate-determining for the enzymatic reaction. Here we report the design and discovery of a high-activity mutant of human BChE by using a novel, systematic computational design approach based on transition-state simulations and activation energy calculations. The novel computational design approach has led to discovery of the most efficient cocaine hydrolase, i.e., a human BChE mutant with an approximately 2000-fold improved catalytic efficiency, promising for therapeutic treatment of cocaine overdose and addiction as an exogenous enzyme in human. The encouraging discovery resulted from the computational design not only provides a promising anticocaine medication but also demonstrates that the novel, generally applicable computational design approach is promising for rational enzyme redesign and drug discovery.     

Photoactivation mechanism of orthovanadate-like (V=O)O3 species

The photoluminescence spectrum and action spectrum for the photooxidation of orthovanadate-like (V=O)O₃ species exhibiting photoluminescence at 520 nm indicate that the triplet excited state T₁ of the orthovanadate-like species, which is formed from the singlet excited states S₁ and S₂ by intersystem crossing, is directly involved in the photooxidation of cyclohexane into cyclohexanone in the presence of molecular oxygen.     

Cross‐Platform DNA Encoding for Single‐Cell Imaging of Gene Expression

Integration of imaging data across different molecular target types can provide in‐depth insight into cell physiology and pathology, but remains challenging owing to poor compatibility between target‐type‐specific labeling methods. We show that cross‐platform imaging analysis can be readily achieved through DNA encoding of molecular targets, which translates the molecular identity of various target types into a uniform in situ array of ssDNA tags for subsequent labeling with complementary imaging probes. The concept was demonstrated through multiplexed imaging of mRNAs and their corresponding proteins with multicolor quantum dots. The results reveal heterogeneity of cell transfection with siRNA and outline disparity in RNA interference (RNAi) kinetics at the level of both the mRNA and the encoded protein.     

Triticonazole enantiomers: Separation by supercritical fluid chromatography and the effect of the chromatographic conditions

Enantiomeric pairs of triticonazole have been successfully separated by supercritical fluid chromatography coupled with a tris(3,5‐dimethylphenylcarbamoyl) cellulose‐coated chiral stationary phase in this work. The effects of co‐solvent, dissolution solvent, flow rate, backpressure, and column temperature have been studied in detail with respect to retention, selectivity, and resolution of triticonazole. As indicated, the co‐solvents mostly affected the retention factors and resolution, due to the different molecular structure and polarity. In addition, the dissolution solvents, namely, chloromethanes and alcohols, have been also important for enantioseparation because of the different interaction with stationary phase. Higher flow rate and backpressure led to faster elution of the triticonazole molecules, and the change of column temperature showed slight effect on the resolution of triticonazole racemate. Moreover, a comparative separation experiment between supercritical fluid chromatography and high performance liquid chromatography revealed that chiral supercritical fluid chromatography gave the 3.5 times value of R_s/t_R2 than high performance liquid chromatography, which demonstrated that supercritical fluid chromatography had much higher separation efficiency.     

Facile and scalable fabrication engineering of fullerenol nanoparticles by improved alkaline-oxidation approach and its antioxidant potential in maize

A feasible in operation, labor-saving and low-cost one-step technology to fabricate fullerenol nanoparticles (FNPs) up to 10 g in laboratory was developed by improved alkaline-oxidation approach using moderately concentrated sodium hydroxide solution as the hydroxylation agent and o-dichlorobenzene as the solvent. This strategy paves the avenue for industrial-scale bulk production of FNPs. The resulted product, [C₆₀(OH)₂₂·8H₂O]_n, were characterized by various measurements including matrix-assisted laser desorption ionization time-of-flight mass spectrometry, high-resolution ¹H nuclear magnetic resonance spectrometry, Fourier transform infrared spectroscopy, UV-Visible spectrophotometer, thermogravimetric analysis, differential scanning calorimetry, dynamic light scattering analysis, scanning electron microscopy, and electron spin resonance spectrometer. Radical scavenging assay in vitro confirmed the high efficiency of water-soluble [C₆₀(OH)₂₂·8H₂O]_n as a novel radical scavenger. Furthermore, [C₆₀(OH)₂₂·8H₂O]_n as an excellent candidate has the potential to serve as the plant defense stimulation agent in maize.

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