Sulfono‐γ‐AApeptides as a New Class of Nonnatural Helical Foldamer

Foldamers offer an attractive opportunity for the design of novel molecules that mimic the structures and functions of proteins and enzymes including biocatalysis and biomolecular recognition. Herein we report a new class of nonnatural helical sulfono‐γ‐AApeptide foldamers of varying lengths. The crystal structure of the sulfono‐γ‐AApeptide monomer S6 illustrates the intrinsic folding propensity of sulfono‐γ‐AApeptides, which likely originates from the bulkiness of tertiary sulfonamide moiety. The two‐dimensional solution NMR spectroscopy data for the longest sequence S1 demonstrates a 10/16 right‐handed helical structure. Optical analysis using circular dichroism further supports well‐ defined helical conformation of sulfono‐γ‐AApeptides in solution containing as few as five building blocks. Future development of sulfono‐γ‐AApeptides may lead to new foldamers with discrete functions, enabling expanded application in chemical biology and biomedical sciences.     

Lanthanum trilactate: Vibrational spectroscopic study − infrared/Raman spectroscopy

In this study lanthanum trilactate was prepared by neutralization reaction of lactic acid and lanthanum oxide, purified and identified by X-ray powder diffraction. Infrared spectra (Mid-IR region 4000–650 cm⁻¹) and Raman spectra (Stokes region 4000–100 cm⁻¹) of the high quality crystalline samples have been recorded and presented for the first time. For comparison DFT calculations were performed using Gaussian 09 D.01 and agreement between predicted and measured spectral data has been achieved. Acquired information can be utilized for substance identification for example in various industrial applications or in biological systems.     

A One‐Pot Synthesis of N‐Aryl‐2‐Oxazolidinones and Cyclic Urethanes by the Lewis Base Catalyzed Fixation of Carbon Dioxide into Anilines and Bromoalkanes

The multicomponent assembly of pharmaceutically relevant N‐aryl‐oxazolidinones through the direct insertion of carbon dioxide into readily available anilines and dibromoalkanes is described. The addition of catalytic amounts of an organosuperbase such as Barton's base enables this transformation to proceed with high yields and exquisite substrate functional‐group tolerance under ambient CO₂ pressure and mild temperature. This report also provides the first proof‐of‐principle for the single‐operation synthesis of elusive seven‐membered ring cyclic urethanes.     

水热法制备二氧化钛微球的形貌控制及机理研究

以钛粉、Na OH和H2O2为原料,采用水热法成功制备出二氧化钛微球。利用X-射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)和场发射扫描电镜(FESEM)对产物的结构、形貌和尺度进行了表征。结果表明,产物为金红石型Ti O2,微球的直径约为1~2μm,微球由许多纳米管组成。根据实验结果,讨论了二氧化钛纳米管的生长机理,初步研究了双氧水用量,水热温度以及煅烧温度等对产物形貌形成的影响。     

A green protocol for efficient discovery of novel natural compounds: Characterization of new ginsenosides from the stems and leaves of Panax ginseng as a case study

Exploration of new natural compounds is of vital significance for drug discovery and development. The conventional approaches by systematic phytochemical isolation are low-efficiency and consume masses of organic solvent. This study presents an integrated strategy that combines offline comprehensive two-dimensional liquid chromatography, hybrid linear ion-trap/Orbitrap mass spectrometry, and NMR analysis (2D LC/LTQ-Orbitrap-MS/NMR), aimed to establish a green protocol for the efficient discovery of new natural molecules. A comprehensive chemical analysis of the total ginsenosides of stems and leaves of Panax ginseng (SLP), a cardiovascular disease medicine, was performed following this strategy. An offline 2D LC system was constructed with an orthogonality of 0.79 and a practical peak capacity of 11,000. The much greener UHPLC separation and LTQ-Orbitrap-MS detection by data-dependent high-energy C-trap dissociation (HCD)/dynamic exclusion were employed for separation and characterization of ginsenosides from thirteen fractionated SLP samples. Consequently, a total of 646 ginsenosides were characterized, and 427 have not been isolated from the genus of Panax L. The ginsenosides identified from SLP exhibited distinct sapogenin diversity and molecular isomerism. NMR analysis was finally employed to verify and offer complementary structural information to MS-oriented characterization. The established 2D LC/LTQ-Orbitrap-MS/NMR approach outperforms the conventional approaches in respect of significantly improved efficiency, much less use of drug materials and organic solvent. The integrated strategy enables a deep investigation on the therapeutic basis of an herbal medicine, and facilitates new compounds discovery in an efficient and environmentally friendly manner as well.     

Metal-free phthalocyanine single crystal: Solvothermal synthesis and near-infrared electroluminescence

A metal-free purple H₂Pc single crystal was synthesized by a facile solvothermal method, and its solubility and near-infrared (NIR) optical properties were also investigated due to its potential applications as a light-emitting layer for OLEDs. The H₂Pc single crystal is insoluble in 1-chlorine naphthalene and other organic solvents. It gives a wide absorption in the range from 620 nm to 679 nm and a wide emission in near 922 nm. As an active light-emitting layer, H₂Pc was employed to fabricate electroluminescent (EL) devices with a structure of ITO/NPB (30 nm)/Alq₃:H₂Pc (30 nm)/BCP (20 nm)/Alq₃ (20 nm)/Al. The emission center is at 936 nm when the H₂Pc doping concentration is 20 wt%. The doping concentration strongly governs the emission intensity. When doping concentration decreases from 10 wt% to 1 wt%, the emission intensity remarkably fades, and simultaneously the emission center undergoes a blue shift.     

Palladium‐Catalyzed Direct Cross‐Coupling of Carboranyllithium with (Hetero)Aryl Halides

A palladium‐catalyzed direct C‐arylation reaction of readily available cage carboranyllithium reagents with aryl halides has been developed for the first time. This method is applicable to a wide range of aryl halide substrates including aryl iodides, aryl bromides, and heteroaromatic halides.     

Ni–Al composite hydroxides fabricated by cation–anion double hydrolysis method for high-performance supercapacitor

Chemical doping of nickel hydroxide with other cations(e.g. Al~(3+)) is an efficient way to enhance its electrochemical capacitive performances. Herein, a simple cation–anion(Ni~(2+)and AlO_2) double hydrolysis method was developed toward the synthesis of nickel–aluminum(Ni–Al) composite hydroxides. The obtained composite hydroxides possesses a porous structure, large surface area(121 m~2/g) and homogeneous element distribution. The electrochemical test shows that the obtained composite hydroxides exhibits a superior supercapacitive performances(specific capacitance of 1670F/g and rate capability of 87% from 0.5 A/g to 20 A/g) to doping-free nickel hydroxide(specific capacitance of 1227 F/g and rate capability of 47% from 0.5 A/g to 20 A/g). Moreover, the galvanostatic charge/discharge test displays that after 2000 cycles at large current density of 10 A/g, the composite hydroxides achieves a high capacitance retention of 98%, indicative of an excellent electrochemical cycleability.