Dimeric Manganese-Catalyzed Hydroarylation and Hydroalkenylation of Unsaturated Amides

An unprecedented Mn(I)-catalyzed selective hydroarylation and hydroalkenylation of unsaturated amides with commercially available organic boronic acids is reported. Alkenyl boronic acids have been successfully employed for the first time in Mn(I)-catalyzed carbon–carbon bond formation. A wide array of β-alkenylated amide products can be obtained in moderate to good yields, which offers practical access to five- and six-membered lactams. This protocol has predictable regio- and chemoselectivity, excellent functional group compatibility and ease of operation in air, representing a significant step-forward towards manganese-catalyzed C−C coupling.     

Ultrafast dynamics of resonance energy transfer in cryptochrome

In this communication, we report the ultrafast dynamics of resonance energy transfer in a blue-light photoreceptor, Vibrio cholerae cryptochrome. The transfer was observed to occur in 60 ps. We also studied the local rigidity and solvation around the binding site of the photoantenna molecule. The results for the first time show energy transfer in cryptochrome suggesting some mechanistic similarities between photolyase that repairs damaged DNA and cryptochrome that mediates blue-light signaling.     

Preparation and study on the novel solid inclusion complex of ciprofloxacin with HP-beta-cyclodextrin

The interaction of ciprofloxacin with HP-beta-cyclodextrin (HP-beta-CD) has been studied by several analytical techniques, including 1H nuclear magnetic resonance (NMR), 13C NMR, fluorescence spectra, infrared spectroscopy, thermal analyzer and scanning electron microscope. In this paper, solid inclusion complex of ciprofloxacin with HP-beta-CD was synthesized by the coprecipitation method. In addition, the characterization of the inclusion complex has been proved by fluorimetry, infrared, differential scanning calorimetry and one-dimensional (1D), 2D NMR. The experimental results confirmed the existence of 1:1 inclusion complex of ciprofloxacin with HP-beta-CD. The formation constant of complex was determined by fluorescence method and 1H NMR. Spacial configuration of complex has been proposed on two-dimensional NMR technique.     

Influence of the built-in pyridinium salt on asymmetric epoxidation of substituted chromenes catalysed by chiral (pyrrolidine salen)Mn(III) complexes

Chiral (pyrrolidine salen)Mn(III) complexes 1 with an N-benzoyl group and 2 with an N-isonicotinoyl group as well as the corresponding N-methyl (3) and N-benzyl (4) pyridinium salts of 2 were synthesized. The catalytic properties of 1–4 and 2 with excess CH₃I were explored to figure out the influence of the internal pyridinium salt in the catalyst on asymmetric epoxidation of substituted chromenes with NaClO/PPNO as an oxidant system in the aqueous/organic biphasic medium. The (pyrrolidine salen)Mn(III) complexes with an internal pyridinium salt, either formed in situ or isolated, displayed higher activities than analogous complexes 1, 2 and Jacobsen's catalyst in the aforementioned reaction, with comparable high yields and ee values. The acceleration of the reaction rate is attributed to the phase transfer capability of the built-in pyridinium salt of the (salen)Mn(III) catalyst. The effect of the internal pyridinium salt on the epoxidation of substituted chromenes is similar to that of the external pyridinium salts and ammonium halides.     

Synthesis and Chromatographic Evaluation of Perfluorooctyl Stationary Phase for Separation of Basic Compounds

Fluorinated stationary phases provide unique separation effect on basic compounds, due to the fluorine atoms, and pentafluorophenyl stationary phases (PFPs) are the most widely used. Considering that some fluoroalkyls have higher fluorine contents than PFPs do, it is speculated that fluoroalkyl stationary phases should have potential new applications. Herein, we synthesized a silica-based stationary phase bonding perfluoroctyl (FC8) proved by characterization through elemental analysis and solid-state ¹³C cross-polarization/magic-anglespinning nuclear magnetic resonance. The chromatographic behavior of the stationary phase was evaluated with test compounds. In addition, to further study the applicability of FC8 materials, Corydalis decumbens (Thunb.) Pers. fraction, considered as a challenging medicine on reversed-phase chromatography columns, was chosen as a test sample. Results demonstrated that the FC8 stationary phase had better and more satisfactory separation performance than the PFP stationary phase on basic compounds.

     

High-performance liquid chromatography quantitative analysis of ephedrine alkaloids in Ephedrae Herba on a perfluorooctyl stationary phase

Ephedrae Herba is one of the most commonly used herbal medicines, and it has been shown that most of the clinical efficacy for cold and asthma is exerted by its alkaloidal components. A simple and sensitive high-performance liquid chromatography method was developed using a perfluorooctyl column for the simultaneous determination of five alkaloids (norephedrine, norpseudoephedrine, ephedrine, pseudoephedrine, and methylephedrine) in Ephedrae Herba. The mobile phase comprising acetonitrile and 15 mM ammonium trifluoroacetate was used to elute the targets in isocratic elution mode. The method was validated for linearity (R² > 0.999), repeatability, intraday and interday precision, recoveries with trueness (93.87–110.99%), limits of detection (5.35–5.76 µg/mL), and limits of quantification (20 µg/mL). The quantitative results revealed that the developed method was precise and accurate. Then it was successfully applied to determine the difference in the contents of three batches of Ephedrae Herba from three pharmaceutical companies.     

Ultrafast solvation dynamics at internal sites of staphylococcal nuclease investigated by site-directed mutagenesis

Internal solvation of protein was studied by site-directed mutagenesis,with which an intrinsically fluorescent probe,tryptophan,is inserted into the desired position inside a protein molecule for ultrafast spectroscopic study.Here we review this unique method for protein dynamics research.We first introduce the frontiers of protein solvation,site-directed mutagenesis,protein stability and characteristics,and the spectroscopic methods.Then we present time-resolved spectroscopic dynamics of solvation dynamics inside cavities of active sites.The studies are carried out on a globular protein,staphylococcal nuclease.The solvation at sites inside the protein molecule’s cavities clearly reveals characteristics of the local environment.These solvation behaviors are directly correlated to enzyme activity.     

Rhodium‐Catalyzed Cyclization of Diynes with Nitrones: A Formal [2+2+5] Approach to Bridged Eight‐Membered Heterocycles

N‐aryl‐substituted nitrones were employed as five‐atom coupling partners in the rhodium‐catalyzed cyclization with diynes. In this reaction, the nitrone moiety served as a directing group for the catalytic C? H activation of the N‐aryl ring. This formal [2+2+5] approach allows rapid access to bridged eight‐membered heterocycles with broad substrate scope. The results of this study may provide new insight into the chemistry of nitrones and find applications in the synthesis of other heterocycles.