Efficient conversion of fructose to 5-hydroxymethylfurfural over sulfated porous carbon catalyst

Sulfated porous carbon (PC-SO3H) catalyst was successfully synthesized from one-pot treatment of porous polydivinylbenzene in H2SO4 at 250 C, which exhibited very good catalytic performances in the production of 5-hydroxymethylfurfural from fructose.     

Crystal structure and thermal stability of A μ1,1-(OMe)-bridged dimeric Schiff base iron(III) complex

A new μ_1,1-OMe-bridged dimeric iron(III) complex, [Fe₂L₂(μ_1,1-OMe)₂(NCS)₂], where L is the deprotonated form of 2-[(2-ethylaminoethylimino)methyl]-5-methoxyphenol, has been prepared and structural characterized by elemental analysis, IR spectrum, and single crystal X-ray crystallography. The complex crystallizes in the monoclinic space group P2₁/c, with unit cell dimensions a = 10.156(1) Å, b = 11.972(1) Å, c = 14.256(2) Å, β = 102.643(3)°, V = 1691.3(3) ų, Z = 2, R ₁ = 0.0394, and wR ₂ = 0.0922. Each Fe atom in the complex is in an octahedral coordination. The Fe...Fe distance is 3.102(1) Å. The thermal stability of the complex was studied.     

Topical application of zein-silk sericin nanoparticles loaded with curcumin for improved therapy of dermatitis

Atopic dermatitis is characterized by leukocyte migration into the skin dermis and typically driven by excessive chemokine production at the site of inflammation. Conventional topical formulations such as gels, creams, and ointments are insufficient for this treatment because of low penetration of drug molecules into the targeted skin tissues. Herein, using a simple, green, sustainable strategy, we have developed novel primary zein nanoparticles embedded in curcumin (Cur) and coated with silk sericin (ZHSCs) for the topical delivery of Cur to penetrate into the dermis and exercise anti-dermatitis effects on the lesion with minimal side-effects. Transdermal delivery experiments and porcine skin fluorescence imaging indicated that ZHSCs facilitate the penetration of Cur across the epidermis layer of skin to reach deep-seated sites. Notably, ZHSCs = 1:0.25 (zein-to-silk sericin mass ratios of 1:0.25) markedly elevated the skin permeability and cumulative turnover of Cur transferred, which were provided a greater than a 3.8-fold increase relative to free Cur. The special nanoparticles of ZHS = 1:0.25 possessed the deepest localization depth and experience a transition of the particle structure and core-shell separation after penetrating into the dermis of skin. In a cell model of dermatitis induced by tumor necrosis factor α/interferon γ co-stimulation, compared with free Cur, Cur-loaded ZHS nanoparticles down-regulated the generation of inflammatory cytokines and chemokines in keratinocytes through suppression of the nuclear translocation of NF-κBp65 and hence exerted an anti-dermatitis effect. This strategy may provide new avenues and direction for the demanding issues of valid topical delivery systems.     

Controllably Growing Topologies in One-shot RAFT Polymerization via Macro-latent Monomer Strategy

The controlled and efficient synthesis of polymers with tailored topologies is challenging but important for exploring structure/property research. Herein, we proposed a concept of macro-latent monomer to achieve the controlled growth of polymer topologies.The macro-latent monomer was installed by a dynamic furan/maleimide covalent bond at the chain terminal. One-shot reversible additionfragmentation chain transfer(RAFT) polymerization of styrene and the macro-latent monomer created controlled growth of polymer topologies.Low temperature such as 40 ℃ could not activate the macro-latent monomer and thus the polymerization created the homo-polystyrene. By contrast, high temperature of ～110 ℃ activated the macro-latent monomer, and a maleimide-terminated macro-monomer was released via the retro-Diels Alder reaction. This macro-monomer immediately joined the cross polymerization with styrene and thus produced the side chains. By delicately manipulating the polymerization temperature, the predetermined placement of the macro-latent monomer-derived polymeric sidechains created controllably growing topologies, including star-, π-shaped, and density-variable grafting copolymers. This work paved a new way for creating on-demand topologies and would greatly enrich the topology synthesis.     

磷酸酯类前药的合成方法与应用

磷酸酯类前药与原药相比,不仅能够提高药物靶向性、稳定性和生物利用度,减少药物毒副作用,还能掩蔽药物不适气味、提高水溶性从而改善给药途径。含羟基药物的磷酸酯化是该类药物前药设计的重要方法之一。本文根据中心磷原子的价态和化合物结构进行分类,综述了各种P(Ⅴ)四配位分子、P(Ⅲ)三配位分子和H-亚磷酸酯类化合物作为磷酸酯化试剂在磷酸酯类前药合成方法中的研究进展,并阐述了这些磷酸酯类药物的应用,最后总结了各类磷酸酯化试剂的优势与局限,并结合连续流反应技术应用案例展望了其发展趋势。     

DNA microarray: a high throughput approach for methylation detection

We described a DNA microarray-based method combined with bisulphite treatment of DNA and regular PCR to examine hyper-methylation in promoter 1A of APC gene. A set of oligonucleotide probes were designed and immobilized on the aldehyde-coated glass slides for detecting the methylation pattern of 15 selected CpG sites in the region. The methylation status of 30 colorectal tumor samples have been examined by both of methylation-specific PCR (MS-PCR) and the present microarray method. The methylation pattern of the 15 CpG sites for the samples have been obtained with the microarray. A total of 19 samples out of 30 were methylated by microarray, in which five samples cannot be detected by MS-PCR due to the methylated CpG patterns not accordant to the MS-PCR primers. The detecting ratio for methylation of APC gene of colorectal tumor samples increased from 46.7% with MS-PCR to 63.3% with the microarray, which successfully demonstrated that DNA microarray-based method not only can obtained the methylation patterns for the related genes, but also decrease the false-negative results of methylation status by the conventional MS-PCR for the investigated genes.     

Development and validation of a liquid chromatography/tandem mass spectrometry procedure for the quantification of adefovir in human plasma

To investigate the pharmacokinetics of adefovir as an anti-hepatitis B virus drug, a sensitive and specific liquid chromatography/tandem mass spectrometry method was developed and validated. After a simple protein precipitation using methanol, the post-treatment samples were analyzed on a C(18) column interfaced with a triple-quadrupole tandem mass spectrometer using positive electrospray ionization. A structural analogue, PMPA, was used as the internal standard. The method was linear in the concentration range 0.25-100 ng/mL. The lower limit of quantification was 0.25 ng/mL. The intra- and inter-day relative standard deviation over the entire concentration range was 5.7% or less. The accuracy determined at three concentrations (0.75, 10 and 80 ng/mL for adefovir) was within +/-2.5% relative error. The method described here was successfully applied for the evaluation of pharmacokinetic profiles of adefovir after single oral administration doses of 5, 10 and 20 mg adefovir dipivoxil to ten healthy volunteers.     

N-(5,5-二甲基-1,3,2-二氧杂己内磷酰基)取代苯甲醛腙的合成及其阻燃性能

环状磷酸酯;水合肼;膨胀型阻燃剂;N-(5;5-二甲基-1;3;2-二氧杂己内磷酰基)取代苯甲醛腙的合成及其阻燃性能     

ATR-FTIR investigation on the complexation of myo-inositol hexaphosphate with aluminum hydroxide

The adsorption isotherm of and the pH effect on the adsorption of myo-inositol hexaphosphate (myo-IP6) on amorphous aluminum hydroxide was investigated. It was found that the adsorption isotherm of myo-IP6 on aluminum hydroxide could be well fitted with the Freundlich isotherm. The amount of myo-IP6 adsorbed remained almost constant in the range of pH 4.0 to 7.0, but it decreased considerably as the initial pH was over 7. The adsorption of myo-IP6 resulted in an increase in the pH level due to the release of OH(-) ions, which suggested that the adsorption of myo-IP6 on aluminum hydroxide was caused by a ligand exchange reaction. ATR-FTIR analysis of myo-IP6 in solution and adsorbed on aluminum hydroxide at different pH were performed. The ATR-FTIR investigation indicated that myo-IP6 was adsorbed onto aluminum hydroxide by forming inner-sphere complexes and adsorption facilitated the deprotonation of phosphate groups. The asymmetric vibration of the PO bond in AlPO(-)(3) appearing at a lower frequency than that in the terminal HPO(-)(3) indicated that Al bound to the O atom not as strongly as the H atom did. The ATR-FTIR investigation and theoretical calculation (with the Gaussian 03 program) revealed that three of the six phosphate groups in myo-IP6 molecules were bound to aluminum hydroxide while the other three remained free when myo-IP6 was adsorbed on aluminum hydroxide.