Ru/CeO2催化剂催化苯乙烯氢甲氧基羰基化反应高选择性制备直链酯类化合物

酯类化合物在工业上具有广泛应用,例如可用于合成香水、调味剂(味精)、洗涤剂和表面活性剂等.其中,烯烃的氢烷氧基羰基化反应是一种合成酯类化合物的重要方法,其低消耗、100%的原子经济性和原料的易获得等优势使其在制备酯类化合物中成为一个有效且实际可行的方法.对于该反应,文献多采用Pd或Rh的络合均相催化剂,其中控制反应过程中直链酯类化合物(L)和支链酯类化合物(B)的选择性是一项颇具挑战性的课题.虽然目前可通过配体的设计和修饰来调节,但多集中在均相催化体系,因此在选择性调变方面的研究仍很欠缺.相对于均相催化,多相催化由于产物易分离和提纯、催化剂可循环使用等优势而逐渐引起了研究者的广泛关注.在多相催化体系中, Pd负载在强酸性树脂作为催化剂已被应用于苯乙烯氢甲氧基羰基化反应,但在该反应中支链酯类化合物为主要产物.因此,寻找一个可有效改善多相反应体系中选择性问题的方法是非常有意义的.在本研究工作中,我们分别以CeO2纳米颗粒(NP)、CeO2纳米棒(Rod)和CeO2纳米立方体为载体,利用浸渍法制备了Ru/CeO2、Ru/CeO2-rod和Ru/CeO2-cube三种催化剂,并进一步用于苯乙烯氢甲氧基羰基化反应.探究了CO压力、反应温度和反应时间对三种催化剂催化苯乙烯氢甲氧基羰基化反应的影响.结果表明, Ru/CeO2作为多相催化剂催化苯乙烯氢甲氧基羰基化反应时,苯乙烯选择性高于99%,直链酯选择性为83%,支链酯选择性为12%.机理研究表明,该反应为自由基机理.动力学分析表明,该反应的反应活化能为48.50 k Jmol^–1.结合三种催化剂的反应活性以及HRTEM结构表征结果可知,该反应中L/B比值与Ru的尺寸有较大关系.进一步的拉曼表征和NH3-TPD表征结果证明, Ru的尺寸与金属-载体之间的相互作用以及催化剂表面的氧空位浓度有直接关系.     

Late-Stage Modification of Aminoglycoside Antibiotics Overcomes Bacterial Resistance Mediated by APH(3’) Kinases

The continuous emergence of antimicrobial resistance is causing a threat to patients infected by multidrug-resistant pathogens. In particular, the clinical use of aminoglycoside antibiotics, broad-spectrum antibacterials of last resort, is limited due to rising bacterial resistance. One of the major resistance mechanisms in Gram-positive and Gram-negative bacteria is phosphorylation of these amino sugars at the 3’-position by O-phosphotransferases [APH(3’)s]. Structural alteration of these antibiotics at the 3’-position would be an obvious strategy to tackle this resistance mechanism. However, the access to such derivatives requires cumbersome multi-step synthesis, which is not appealing for pharma industry in this low-return-on-investment market. To overcome this obstacle and combat bacterial resistance mediated by APH(3’)s, we introduce a novel regioselective modification of aminoglycosides in the 3’-position via palladium-catalyzed oxidation. To underline the effectiveness of our method for structural modification of aminoglycosides, we have developed two novel antibiotic candidates overcoming APH(3’)s-mediated resistance employing only four synthetic steps.     

Binding,Release and Functionalization of Intact Pnictogen Tetrahedra Coordinated to Dicopper Complexes

The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu₂(μ,η¹ : η¹-MeCN)][X]₂ (X=weakly coordinating anion, NTf₂ ( 1 a ), FAl[OC₆F₁₀(C₆F₅)]₃ ( 1 b ), Al[OC(CF₃)₃]₄ ( 1 c )) was replaced by white phosphorus (P₄) or yellow arsenic (As₄) to yield [(DPFN)Cu₂(μ,η² : η²-E₄)][X]₂ (E=P ( 2 a – c ), As ( 3 a – c )). The molecular structures in the solid state reveal novel coordination modes for E₄ tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E₄ tetrahedra. Reactions with N-heterocyclic carbenes (NHCs) led to replacement of the E₄ tetrahedra with release of P₄ or As₄ and formation of [(DPFN)Cu₂(μ,η¹ : η¹-^MeNHC)][X]₂ ( 4 a,b ) or to an opening of one E−E bond leading to an unusual E₄ butterfly structural motif in [(DPFN)Cu₂(μ,η¹ : η¹-E₄^DippNHC)][X]₂ (E=P ( 5 a,b ), E=As ( 6 )). With a cyclic alkyl amino carbene (^EtCAAC), cleavage of two As−As bonds was observed to give two isomers of [(DPFN)Cu₂(μ,η² : η²-As₄^EtCAAC)][X]₂ ( 7 a,b ) with an unusual As₄-triangle+1 unit.     

Raman Optical Activity of N-Acetyl-L-Cysteine in Water and in Methanol: The “Clusters-in-a-Liquid” Model and ab Initio Molecular Dynamics Simulations

Raman and Raman Optical Activity (ROA) spectra of N-acetyl-L-cysteine (NALC), a flexible chiral molecule, were measured in water and in methanol to evaluate the solvent effects. Two different solvation approaches, that is, the DFT based “clusters-in-a-liquid” solvent model and the ab initio molecular dynamics (AIMD) simulations, were applied to simulate the Raman and ROA spectra. Systematic conformational searches were carried out using a recently developed conformational searching tool, CREST, with the inclusion of polarizable continuum model of water and of methanol. The CREST candidates of NALC and the NALC-solvent complexes were re-optimized and their Raman and ROA simulations were done at the B3LYP−D3BJ/def2-TZVP and the B3LYP-aug-cc-pVDZ//cc-pVTZ levels. Also, AIMD simulations, which includes some anharmonic effects and all intermolecular interactions in solution, were performed. By empirically weighting the computed Raman and ROA spectra of each conformer, good agreements with the experimental data were achieved with both approaches, while AIMD offered some improvements in the carbonyl and in the low wavenumber regions over the static DFT approach. The pros and cons of these two different approaches for accounting the solvent effects on Raman and ROA of this flexible chiral system will also be discussed.     

Zwitterionic Cellulose Carbamate with Regioselective Substitution Pattern: A Coating Material Possessing Antimicrobial Activity

A polyzwitterion is synthesized by regioselective functionalization of cellulose possessing a uniform charge distribution. The positively charged ammonium group is present at position 6, while the negative charge of carboxylate is located at positions 2 and 3 of the repeating unit. The molecular structure of the biopolymer derivative is proved by NMR spectroscopy. This cellulose‐based zwitterion is applied to several support materials by spin‐coating and characterized by means of atomic force microscope, contact angle measurements, ellipsometry, and X‐ray photoelectron spectroscopy. The coatings possess antimicrobial activity depending on the support materials (glass, titanium, tissue culture poly(styrene)) as revealed by confocal laser scanning microscopy and live/dead staining.

     

Microchip capillary electrophoresis/electrochemistry

Microfabricated fluidic devices have generated considerable interest over the past ten years due to the fact that sample preparation, injection, separation, derivatization, and detection can be integrated into one miniaturized device. This review reports progress in the development of microfabricated analytical systems based on microchip capillary electrophoresis (CE) with electrochemical (EC) detection. Electrochemical detection has several advantages for use with microchip electrophoresis systems, for example, ease of miniaturization, sensitivity, and selectivity. In this review, the basic components necessary for microchip CEEC are described, including several examples of different detector configurations. Lastly, details of the application of this technique to the determination of catechols and phenols, amino acids, peptides, carbohydrates, nitroaromatics, polymerase chain reaction (PCR) products, organophosphates, and hydrazines are described.     

Mechanism of enhanced conversion of 1,2,3-trichloropropane by mutant haloalkane dehalogenase revealed by molecular modeling

1,2,3-Trichloropropane (TCP) is a highly toxic, recalcitrant byproduct of epichlorohydrin manufacture. Haloalkane dehalogenase (DhaA) from Rhodococcus sp. hydrolyses the carbon–halogen bond in various halogenated compounds including TCP, but with low efficiency (k _cat/K _m = 36 s^-1 M^-1). A Cys176Tyr-DhaA mutant with a threefold higher catalytic efficiency for TCP dehalogenation has been previously obtained by error-prone PCR. We have used molecular simulations and quantum mechanical calculations to elucidate the molecular mechanisms involved in the improved catalysis of the mutant, and enantioselectivity of DhaA toward TCP. The Cys176Tyr mutation modifies the protein access and export routes. Substitution of the Cys residue by the bulkier Tyr narrows the upper tunnel, making the second tunnel “slot” the preferred route. TCP can adopt two major orientations in the DhaA enzyme, in one of which the halide-stabilizing residue Asn41 forms a hydrogen bond with the terminal halogen atom of the TCP molecule, while in the other it bonds with the central halogen atom. The differences in these binding patterns explain the preferential formation of the (R)- over the (S)-enantiomer of 2,3-dichloropropane-1-ol in the reaction catalyzed by the enzyme.     

Synthesis, photophysical and electrochemical properties and theoretical studies on three novel indolo[3,2-b]carbazole derivatives containing benzothiazole units

Three novel indolo[3,2-b]carbazoles derivatives were successfully synthesized by condensation reaction and structurally characterized by elemental analysis, mass spectrometry and proton nuclear magnetic resonance spectroscopy methods, which belong to donor-π-acceptor systems comprising an indolo[3,2-b]carbazole group as an electron donor and two benzothiazole rings as electron acceptors. The thermal, electrochemical and photophysical properties of the compounds were characterized by thermogravimetric analysis combined with electrochemistry, UV-vis absorption spectroscopy and fluorescence spectroscopy. On the other hand, the geometries, molecular orbitals, charge-injection and transport properties were determined by quantum chemical calculations. The results show that the compounds synthesized exhibit good thermal stability and high fluorescence quantum yields, indicating the potential application as optoelectronic materials.