α-Carbonyl Radicals for Total Synthesis of Natural Products

Intramolecular cyclization of α-carbonyl radicals to the trimethylsilylacetylenic side chain gives bicyclic vinylsilane ketones and enones. Application of this cyclization to total synthesis of (±)-modhephene is described.     

Quality assessment of Flos Chrysanthemi Indici from different growing areas in China by solid-phase microextraction-gas chromatography-mass spectrometry

Flos Chrysanthemi Indici is a common traditional Chinese medicine (TCM). In this paper, headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS) was developed for quality assessment of Flos Chrysanthemi Indici from different growing areas in China. SPME parameters such as extraction fibers, extraction temperature, extraction time and sample mass were investigated to achieve identical results to those obtained by the steam distillation (SD). The selected SPME conditions were as follows: SPME fiber coated with 65-microm PDMS/DVB, extraction temperature of 60 degrees C, extraction time of 30 min and sample mass of 1.0 g. Furthermore, four active compounds (eucalyptol, camphor, borneol and bornyl acetate) presented in the TCM were applied to evaluating the quality of Flos Chrysanthemi Indici from 20 various areas. The quality assessment was successfully performed to compare the similarity value (S) between different sample vector of Flos Chrysanthemi Indici and the standard profile vector (SPV). The results showed that the proposed HS-SPME-GC-MS was an alternative technique for quality assessment of Flos Chrysanthemi Indici samples.     

Intermolecular radical addition reactions of alpha-iodo cycloalkenones and a synthetic study of the formal synthesis of enantiopure fawcettimine

The generation of alpha-carbonyl vinyl radicals from alpha-iodo cycloalkenones, the scope of their participation in intermolecular addition reactions with electron-withdrawing olefins are studied and a synthetic study of the formal synthesis of enantiopure fawcettimine using this reaction is described.     

Facile synthesis of oleanolic acid monoglycosides and diglycosides

Oleanolic acid and its glycosides are important natural products, possessing various attractive biological activities such as antitumor, antivirus and anti-inflammatory properties. In the present work, fifteen oleanolic acid saponins bearing various saccharide moieties, including 3-monoglycoside, 28-monoglycoside and 3,28-diglycoside, were easily synthesized in high yields. Benzyl was chosen as the protective group for the COOH(28) group, instead of commonly used methyl and allyl, to avoid difficulties in the final deprotection. Alkali-promoted condensation of the carboxylic acid with bromo-glycosides was found to be more efficient in the synthesis of 28-glycosides. Two approaches were investigated and proved practicable in the preparation of 3,28- diglycosides. This method is suitable for preparing oleanolic acid glycosides with structural diversity for extensive biological evaluation and structure-activity relationship study, and it also apply new idea for the corresponding synthetic methods to the glycoside derivatives of other triterpenoid.     

Emission of ballistic photoelectrons from <Emphasis Type="Italic">p</Emphasis>-GaN(Cs,O) with the effective negative electron affinity

This paper reports on a study of the emission of ballistic photoelectrons from p-GaN(Cs,O) with an effective negative electron affinity. At photon energies less than the GaN band gap width, where emission of electrons originates from photoexcitation of surface and near-surface states, an increment in the energy of ballistic electrons is equal to that of exciting photons, which is substantiated by the dispersionless character of the initial states. At photon energies exceeding the band gap width, the excess energy of light is partitioned among the kinetic energies of ballistic photoelectrons and holes in accordance with their effective masses. This relation was used to determine the effective hole mass along the c axis of the GaN lattice of the wurtzite structure, which turned out to be m* _h‖ = (0.60 ± 0.15)m ₀.     

三氯化六氨合钴(Ⅲ)合成条件的改进

在无机化学实验"三氯化六氨合钴(Ⅲ)的制备及组分测定"中,产物合成产率较低,影响后续实验开展和教学效果。本文基于基本化学原理优化实验合成条件,考查了活性炭催化剂用量、粒度和盐酸用量对三氯化六氨合钴(Ⅲ)产率的影响。实验结果表明:当活性炭催化剂用量为0.2 g、粒度为120目、盐酸溶液为(25 mL热水+1 mL盐酸)、浓盐酸用量为3 mL时,三氯化六氨合钴(Ⅲ)产率可达到42.5%,产品颜色(橙色)、纯度和结晶度明显提高,达到了实验预期结果。并且对不同粒度的催化剂,确定了可靠活性炭用量。通过该实验提高了学生化学基本原理的应用能力和解决问题能力。     

Asymmetrical polar modification of a bivanadium-capped Keggin POM by multiple Cu-N coordination polymeric chains

An unprecedented asymmetrically modified bivanadium-capped Keggin polyoxometalate (POM), {AsMo12O40(VO)[VO(H2O)]}.[Cu(4,4'-bipy)]5.H2O (1) (bipy = bipyridine), has been hydrothermally synthesized and structurally characterized by a routine technique. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a unique (3,4,6)-connected 3D framework with a (6(2).8(1))2(8(3))2(6(4).8(2))2(6(1).8(14)) topology, constructed from {AsMo12O40(VO)[VO(H2O)]}5- polyoxoanions modified by six {Cu(bipy)}n coordination polymeric chains. The asymmetrical polar coordination mode has never been found in the POM chemistry hitherto. It is also the first example of the bivanadium-capped POM as an anionic template to construct a 3D framework with the highest connection number of bicapped POMs. Additionally, by just changing the length of the organic ligand, a new compound {[AsMo12O40(VO)2][Cu(bpe)]2}.[Cu(bpe)].[H2bpe].H2O (2) (bpe = bis(4-pyridyl)ethylene), has been obtained, in which the {AsMo12O40(VO)2} sections are modified by double monotrack {Cu(bpe)}n coordination polymeric chains to form a "rail-like" 1D structure.     

Ordering layers of [bmim][PF6] ionic liquid on graphite surfaces: molecular dynamics simulation

Microscopic structures of room temperature ionic liquid (IL) [bmim][PF6] on hydrophobic graphite surfaces have been studied in detail by molecular dynamics simulation. It is clearly shown that both the mass and electron densities of the surface adsorbed ionic liquid are oscillatory, and the first peak adjacent to the graphite surface is considerably higher than others, corresponding to a solidlike IL bottom layer of 6 angstroms thick. Three IL layers are indicated between the graphite surface and the inner bulk IL liquid. The individually simulated properties of single-, double-, and triple-IL layers on the graphite surface are very similar to those of the layers between the graphite surface and the bulk liquid, indicating an insignificant effect of vapor-IL interface on the ordered IL layers. The simulation also indicates that the imidazolium ring and butyl tail of the cation (bmim+) of the IL bottom layer lie flat on the graphite surface.     

Asymmetric petasis reactions catalyzed by chiral biphenols

Chiral biphenols catalyze the enantioselective Petasis reaction of alkenyl boronates, secondary amines, and ethyl glyoxylate. The reaction requires the use of 15 mol % of (S)-VAPOL as the catalyst, alkenyl boronates as nucleophiles, ethyl glyoxylate as the aldehyde component, and 3 A molecular sieves as an additive. The chiral alpha-amino ester products are obtained in good yields (71-92%) and high enantiomeric ratios (89:11-98:2). Mechanistic investigations indicate single ligand exchange of acyclic boronate with VAPOL and tetracoordinate boronate intermediates.     

Pd Loaded NiCo Hydroxides for Biomass Electrooxidation: Understanding the Synergistic Effect of Proton Deintercalation and Adsorption Kinetics

The key issue in the 5-hydroxymethylfurfural oxidation reaction (HMFOR) is to understand the synergistic mechanism involving the protons deintercalation of catalyst and the adsorption of the substrate. In this study, a Pd/NiCo catalyst was fabricated by modifying Pd clusters onto a Co-doped Ni(OH)₂ support, in which the introduction of Co induced lattice distortion and optimized the energy band structure of Ni sites, while the Pd clusters with an average size of 1.96 nm exhibited electronic interactions with NiCo support, resulting in electron transfer from Pd to Ni sites. The resulting Pd/NiCo exhibited low onset potential of 1.32 V and achieved a current density of 50 mA/cm² at only 1.38 V. Compared to unmodified Ni(OH)₂, the Pd/NiCo achieved an 8.3-fold increase in peak current density. DFT calculations and in situ XAFS revealed that the Co sites affected the conformation and band structure of neighboring Ni sites through CoO₆ octahedral distortion, reducing the proton deintercalation potential of Pd/NiCo and promoting the production of Ni³⁺−O active species accordingly. The involvement of Pd decreased the electronic transfer impedance, and thereby accelerated Ni³⁺−O formation. Moreover, the Pd clusters enhanced the adsorption of HMF through orbital hybridization, kinetically promoting the contact and reaction of HMF with Ni³⁺−O.