N-{4-{N-甲基-N-[2-羟基-3-(2,4-二氧代-1,2,3,4-四氢嘧啶-5-基)氨基]丙基}氨基-3-溴}苯甲酰基-L-谷氨酸二乙酯及其衍生物的合成

报道了N-{4-{N-甲基-N-[2-羟基-3-(2,4-二氧代-1,2,3,4-四氢嘧啶-5-基)氨基]丙基}氨基-3-溴}苯甲酰基-L-谷氨酸二乙酯及其衍生物的简便合成方法. 分别以4-氨基苯甲酸乙酯和4-氨基苯甲酰基-L-谷氨酸二乙酯为起始物, 经甲基化、烯丙基化、溴羟基化、环氧化、开环、脱保护等反应首次合成了6个新型5-取代氨基嘧啶类化合物, 并通过¹H NMR, ¹³C NMR 和MS对其化学结构进行了表征. 初步生物活性结果表明, 苯环侧链的L-谷氨酸酯部分是此类化合物抑制人重组二氢叶酸还原酶的必需结构.     

High speed injection molding of high density polyethylene �� Effects of injection speed on structure and properties

Thin wall samples of high density polyethylene (HDPE) were prepared via injection molding with different injection speeds ranging from 100 mm/s to 1200 mm/s. A significant decrease in the tensile strength and Young??s modulus was observed with increasing injection speed. In order to investigate the mechanism behind this decrease, the orientation, molecular weight, molecular weight distribution, melt flow rate, crystallinity and crystal morphology of HDPE were characterized using two-dimensional wide-angle X-ray diffraction (2D-WAXD), gel permeation chromatography (GPC), capillary rheometry and differential scanning calorimetry (DSC), respectively. It is demonstrated that the orientation, molecular weight, molecular weight distribution, melt flow rate and crystallinity have no obvious change with increasing injection speed. Nevertheless, the content of extended chain crystals or large folded chain crystals was found to decrease with increasing injection speed. Therefore, it is concluded that the decrease in tensile properties is mainly contributed by the reduced content of extended chain crystals or large folded chain crystals. This study provides industry with valuable information for the application of high speed injection molding.     

A new phosphine oxide host based on ortho-disubstituted dibenzofuran for efficient electrophosphorescence: towards high triplet state excited levels and excellent thermal, morphological and efficiency stability

An efficient host for blue and green electrophosphorescence, 4,6‐bis(diphenylphosphoryl)dibenzofuran ( o‐ DBFDPO ), with the structure of a short‐axis‐substituted dibenzofuran was designed and synthesised. It appears that the greater density of the diphenylphosphine oxide (DPPO) moieties in the short‐axis substitution configuration effectively restrains the intermolecular interactions, because only very weak π–π stacking interactions could be observed, with a centroid‐to‐centroid distance of 3.960 Å. The improved thermal stability of o‐ DBFDPO was corroborated by its very high glass transition temperature (T_g) of 191 °C, which is the result of the symmetric disubstitution structure. Photophysical investigation showed o‐ DBFDPO to be superior to the monosubstituted derivative, with a longer lifetime (1.95 ns) and a higher photoluminescent quantum efficiency (61 %). The lower first singlet state excited level (3.63 eV) of o‐ DBFDPO demonstrates the stronger polarisation effect attributable to the greater number of DPPO moieties. Simultaneously, an extremely high first triplet state excited level (T₁) of 3.16 eV is observed, demonstrating the tiny influence of short‐axis substitution on T₁. The improved carrier injection ability, which contributed to low driving voltages of blue‐ and green‐emitting phosphorescent organic light‐emitting diodes (PHOLEDs), was further confirmed by Gaussian calculation. Furthermore, the better thermal and morphological properties of o ‐DBFDPO and the matched frontier molecular orbital (FMO) levels in the devices significantly reduced efficiency roll‐offs. Efficient blue and green electrophosphorescence based on the o ‐DBFDPO host was demonstrated.     

Hybrid gold-nanoparticle-cored conjugated thiophene dendrimers: synthesis, characterization, and energy-transfer studies

A series of hybrid Au-nanoparticle-dendrimer materials: nanoparticle-cored thiophene dendrimers (NCTDs) were synthesized, characterized, and investigated for their energy-transfer properties. These hybrid nanoparticles were obtained by the simultaneous and in situ reduction of gold(III) chloride and self-assembly of the thiol-containing thiophene dendritic ligands. The dendron ligands were radially attached to the gold nanoparticles and were analyzed by TEM, UV/Vis, (1)H NMR, and FTIR spectroscopies. The solution fluorescence of the attached thiophene dendrons are quenched progressively. Both alkyl-chain length and dendron size have significant influence on the energy-transfer efficiency, as well as on core sizes and size distribution of the Au nanoparticles. In spite of the phenomenon's dependence on nanoparticle size, the energy transfer generally follows the 1/d(2) distance dependence. Single NCTD nanoparticles were also adsorbed on highly ordered pyrolytic graphite (HOPG) and uniform aggregates were observed on mica flat substrates.     

Organic ligand-free alkylation of amines, carboxamides, sulfonamides, and ketones by using alcohols catalyzed by heterogeneous Ag/Mo oxides

Complicated and expensive organic ligands are normally essential in fine chemical synthesis at preparative or industrial levels. The synthesis of fine chemicals by using heterogeneous catalyst systems without additive organic ligand is highly desirable but severely limited due to their poor generality and rigorous reaction conditions. Here, we show the results of carbon–nitrogen or carbon–carbon bond formation catalyzed by an Ag/Mo hybrid material with specific Ag₆Mo₁₀O₃₃ crystal structure. 48 nitrogen‐ or oxygen‐containing compounds, that is, amines, carboxamides, sulfonamides, and ketones, were successfully synthesized through a borrowing‐hydrogen mechanism. Up to 99 % isolated yields were obtained under relatively mild conditions without additive organic ligand. The catalytic process shows promise for the efficient and economic synthesis of amine, carboxamide, sulfonamide, and ketone derivatives because of the simplicity of the system and ease of operation.     

Facile synthesis of silver chalcogenide (Ag2E; E=Se, S, Te) semiconductor nanocrystals

A general, one-pot, single-step method for producing colloidal silver chalcogenide (Ag(2)E; E = Se, S, Te) nanocrystals is presented, with an emphasis on Ag(2)Se. The method avoids exotic chemicals, high temperatures, and high pressures and requires only a few minutes of reaction time. While Ag(2)S and Ag(2)Te are formed in their low-temperature monoclinic phases, Ag(2)Se is obtained in a metastable tetragonal phase not observed in the bulk.     

High-quality manganese-doped zinc sulfide quantum rods with tunable dual-color and multiphoton emissions

We report a simple, fast and green phosphine-free colloidal chemistry to synthesize high-quality wurtzite-type Mn-doped ZnS quantum rods (QRs) with tunable diameters (1.6-5.6 nm), high aspect ratios (up to 50), variable Mn doping levels (0.18-1.60%), and high quantum yields (up to 45%). The electron paramagnetic resonance spectra with modeling reveal the successful doping of paramagnetic Mn(2+) ions in the host ZnS QRs. The Mn-doped ZnS QRs demonstrate tunable dual-color (orange and blue) emissions by tuning the doping levels and UV excitation wavelengths. The orange emission with long decay lifetime (3.3 ms) originates from the doped Mn(2+) states, while the blue emission with fast decay lifetime (0.31 ns) is attributed to the QR surface states. The bright two- and three-photon excitation upconversion luminescence from the Mn-doped ZnS QRs have been observed using tunable near-infrared femtosecond laser. Our strategy provides a versatile route to programmably control the optical properties of anisotropic semiconductor nanomaterials, which may create new opportunities for photonic devices and bioimaging applications.