Electrochemical-Induced C-N Bond Formation: A New Method to Synthesis (Z)-Quinazolinone Oximes Using Primary Amines and Quinazolin-4(3H)-one.

A novel and highly selective electrochemical method for the synthesis of diverse quinazolinone oximes via direct electrooxidation of primary amines/C(sp2)-H functionalization of oximes has been developed. The reaction is conducted in an undivided cell under constant current conditions and is oxidant-free, open-air, and eco-friendly. Notably, the protocol shows good functional group tolerance, providing versatile quinazolinone oximes in good yields. Moreover, the mechanism is investigated through control experiments and cyclic voltammogram (CV) experiments.

Selective and effective separation of five condensed arenes from a high-temperature coal tar by extraction combined with high pressure preparative chromatography.

An environmentally benign and cost-effective method was designed for isolating and purifying condensed arenes from acetone-extractable portion (AEP) of a high-temperature coal tar through a high pressure preparative chromatograph (HPPC) with different packings, including silica gel, octadecyl silane, octyl bonded silica gel, and diol bonded silica gel. In total, 196 compounds were detected with a gas chromatograph/mass spectrometer from AEP and its eluates. From the eluates, naphthalene, anthracene, phenanthrene, fluoranthene, and pyrene were successfully isolated and purified, and their structures were confirmed by their 1H and 13C nuclear magnetic resonance spectra in addition to their mass spectra. Extraction-HPPC device and solvent recovery process were designed and developed, which can potentially be applied to industrial production because the process is easy-to-operate and ecofriendliness. In addition, the solvents used can be easily recovered and reused, and neither waste water nor other pollutions are emitted.

Optimization of Ultrasonic-Microwave Assisted Extraction and Hepatoprotective Activities of Polysaccharides from Trametes orientalis.

Ultrasonic-microwave assisted extraction (UMAE) of Trametes orientalis polysaccharides was optimized by response surface methodology. Hepatoprotective effects of a purified T. orientalis polysaccharide (TOP-2) were evaluated by alcohol-induced liver injury model mice. The optimal UMAE parameters were indicated as below: ratio of water to raw material 28 mL/g, microwave power 114 W, extraction time 11 min. The polysaccharides yield was 7.52 ± 0.12%, which was well consistent with the predicted value of 7.54%. Pre-treatment with TOP-2 effectively increased the liver index and spleen index in alcohol-treated mice. The elevated serum alanine aminotransferase (ALT) and aspartate aminotransferase (AST) levels of mice after alcohol exposure were inhibited by TOP-2 administration. The liver tumor necrosis factor-α (TNF-α), interleukin-1ß (IL-1ß) levels have decreased significantly as a result of alcohol exposure, while pre-treatment with TOP-2 could mitigate these consequences. Furthermore, pre-treatment with TOP-2 could efficiently boost the superoxidase dismutase (SOD), catalase (CAT) and glutathione peroxidase (GSH-Px) activities, and observably constrain the malondialdehyde (MDA) level. The findings suggest that TOP-2 might be useful for alleviating the alcohol-induced hepatotoxicity via its antioxidant and anti-inflammatory potential.

A novel galactose-PEG-conjugated biodegradable copolymer is an efficient gene delivery vector for immunotherapy of hepatocellular carcinoma.

Successful immunogene therapy depends not only on the therapeutic gene but also on the gene delivery vector. In this study, we synthesized a novel copolymer consisting of low-molecular-weight polyethylenimine (PEI) cross-linked by myo-inositol (INO) and conjugated with a galactose-grafted PEG chain, named LA-PegPI. We characterized the chemical structure and molecular weight of the copolymer and particle properties of LA-PegPI/pDNA. Furthermore, we showed that LA-PegPI/pDNA polyplexes possessed excellent stability in physiological salt solution, low cytotoxicity, and high transfection efficiency in the asialoglycoprotein receptor (ASGPR)-positive liver cells in vitro. Importantly, we also showed that through intraperitoneal injection of LA-PegPI/pDNA nanoparticles, the reporter gene was forcefully expressed in the liver hepatocytes of mice. Finally, we documented that intraperitoneal injection of LA-PegPI/pIL15 nanoparticles effectively suppressed tumor growth and prolonged survival time of tumor-bearing mice via activation of CD8+ T cells and NK cells and upregulation of the cytokines IFN-γ, TNF, and IL12 in an orthotopic hepatocellular carcinoma mouse model. Interestingly, LA-PegPI/pluc nanoparticles could effectively stimulate the proliferation of NK cells and inhibit tumor growth in this model. In summary, LA-PegPI is a useful gene vector for immunogene therapy of hepatocellular carcinoma, and its potential for clinical application warrants further study.

Rapid analysis of carboxylic acids and esters with a direct analysis in real time ion source.

RATIONALE: Coal oxidation produces carboxylic acids (CAs), including aliphatic acids, benzoic acids, and benzenepolycarboxylic acids, which are important fine chemicals which could be used to understand the structural features of coals. However, detecting CAs usually presents great challenges due to extremely troublesome pretreatments. Therefore, it is essential to develop an analytical method for the rapid detection of CAs from coal oxidation. METHODS: A series of model compounds (MCs) of oxidation products and two practical samples were investigated by direct analysis in real time time-of-flight mass spectrometry (DART-TOFMS) under three different analytical conditions (ionizing gas temperature, organic solvent, and MC concentration). RESULTS: Ionizing methyl benzoate, dimethyl phthalate, and dimethyl adipate produces typical ions of methyl esters, including [M - OCH3 ]+ , [M + H]+ , and [M + NH4 ]+ . In contrast, the characteristic ions generated from CAs are polymer ions, such as [2 M + NH4 ]+ , [3 M + NH4 ]+ , [4 M + NH4 ]+ , and [5 M + NH4 ]+ , indicating the strong intermolecular hydrogen-bond interaction among CAs. CONCLUSIONS: Results suggest that DART-TOFMS could rapidly analyze CAs or esters in coal oxidation products according to their typical ions to further gain deep insights into the coal structure.

Ameliorative effect of Trametes orientalis polysaccharide against immunosuppression and oxidative stress in cyclophosphamide-treated mice.

The present study evaluated the ameliorative effects of Trametes orientalis polysaccharide (TOP-2) against cyclophosphamide (CP) induced toxicity in mice. Intraperitoneal administration of TOP-2 not only effectively increased the thymus, spleen, heart, liver, and kidney indices, but also significantly enhanced the phagocytic activities of macrophages and splenocyte proliferation, dose-dependently. The lowered nitric oxide level of macrophages after CP treatment was elevated by TOP-2 administration. Impaired splenic natural killer cells and cytotoxic T lymphocytes activities were remarkably enhanced by TOP-2. Furthermore, the levels of interleukin-2, interferon-γ, Immunoglobulin A, immunoglobulin G, and immunoglobulin M were notably reduced by CP, while TOP-2 abolished these effects. TOP-2 could also effectively increase the total antioxidant capacity, superoxidase dismutase, catalase and glutathione peroxidase activities, and inhibit the increase in malondialdehyde level. These results indicate that TOP-2 may be of therapeutic value in ameliorating the immunosuppression and oxidative stress caused by CP treatment, through its immunomodulatory and antioxidant potential.

Application of mass spectrometry in the characterization of chemicals in coal-derived liquids.

Coal-derived liquids (CDLs) are primarily generated from pyrolysis, carbonization, gasification, direct liquefaction, low-temperature extraction, thermal dissolution, and mild oxidation. CDLs are important feedstocks for producing value-added chemicals and clean liquid fuels as well as high performance carbon materials. Accordingly, the compositional characterization of chemicals in CDLs at the molecular level with advanced analytical techniques is significant for the efficient utilization of CDLs. Although reviews on advancements have been rarely reported, great progress has been achieved in this area by using gas chromatography/mass spectrometry (GC/MS), two-dimensional GC-time of flight mass spectrometry (GC × GC-TOFMS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This review focuses on characterizing hydrocarbon, oxygen-containing, nitrogen-containing, sulfur-containing, and halogen-containing chemicals in various CDLs with these three mass spectrometry techniques. Small molecular (< 500 u), volatile and semi-volatile, and less polar chemicals in CDLs have been identified with GC/MS and GC × GC-TOFMS. By equipped with two-dimensional GC, GC × GC-TOFMS can achieve a clearly chromatographic separation of complex chemicals in CDLs without prior fractionation, and thus can overcome the disadvantages of co-elution and serious peak overlap in GC/MS analysis, providing much more compositional information. With ultrahigh resolving power and mass accuracy, FT-ICR MS reveals a huge number of compositionally distinct compounds assigned to various chemical classes in CDLs. It shows excellent performance in resolving and characterizing higher-molecular, less volatile, and polar chemicals that cannot be detected by GC/MS and GC × GC-TOFMS. The application of GC × GC-TOFMS and FT-ICR MS to chemical characterization of CDLs is not as prevalent as that of petroleum and largely remains to be developed in many respects. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 36:543-579, 2017.

Removal of hexavalent chromium from aqueous solution by calcined Zn/Al-LDHs.

In this study, Zn/Al-layered double hydroxides (Zn/Al-LDHs) were synthesized by a co-precipitation method and characterized with X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. Then the hexavalent chromium Cr(VI) adsorption experiments on calcined Zn/Al-LDHs were carried out to analyze the effects of pH, temperature, adsorption time, initial Cr(VI) concentration and adsorbent dosage on the removal of Cr(VI) from aqueous solutions. The maximum adsorption capacity for Cr(VI) on calcined Zn/Al-LDHs under optimal conditions was found to be over 120 mg/g. The kinetic and isotherm of Cr(VI) adsorption on calcined Zn/Al-LDHs can be described with the pseudo-second-order kinetic model and Langmuir isotherm, respectively.

Bottom-up synthesis of nitrogen-doped graphene sheets for ultrafast lithium storage.

A facile bottom-up strategy was developed to fabricate nitrogen-doped graphene sheets (NGSs) from glucose using a sacrificial template synthesis method. Three main types of nitrogen dopants (pyridinic, pyrrolic and graphitic nitrogens) were introduced into the graphene lattice, and an inimitable microporous structure of NGS with a high specific surface area of 504 m(2) g(-1) was obtained. Particularly, with hybrid features of lithium ion batteries and Faradic capacitors at a low rate and features of Faradic capacitors at a high rate, the NGS presents a superior lithium storage performance. During electrochemical cycling, the NGS electrode afforded an enhanced reversible capacity of 832.4 mA h g(-1) at 100 mA g(-1) and an excellent cycling stability of 750.7 mA h g(-1) after 108 discharge-charge cycles. Furthermore, an astonishing rate capability of 333 mA h g(-1) at 10,000 mA g(-1) and a high rate cycle performance of 280.6 mA h g(-1) even after 1200 cycles were also achieved, highlighting the significance of nitrogen doping on the maximum utilization of graphene-based materials for advanced lithium storage.

Synergic effect of methanol and water on pine liquefaction.

Pine liquefaction (PL) and re-liquefaction of its liquefaction residues in sub- and supercritical methanol, water or methanol/water mixed solvents (MWMSs) was investigated. The results show that isometric MWMS has the highest synergic effect on PL. Moreover, the total yield of bio-oil (BO) and conversion from pine and its residue both liquefied in the MWMS were obvious higher than those from PL in methanol (water) and re-liquefaction of its residue in water (methanol), suggesting that the interaction between the two solvents is responsible for synergic effect. This approach facilitates understanding the mechanism for biomass liquefaction in mixed solvents and developing efficient utilization process of biomass.

Investigation on infrared laser desorption of solid matrix using scanning electron microscope and fast photography.

Infrared light from a pulsed optical parametric oscillator laser system was used to irradiate succinic acid (SA), a usual solid matrix used in matrix-assisted laser desorption ionization, under vacuum. Ablated SA particles were trapped using a silica plate mounted 3.0 mm above and parallel to the sample surface. The morphology and particle size of ablated particles at different laser fluences were investigated using a scanning electron microscope (SEM). The dynamics of plume propagation for SA desorption process was studied with fast photography at atmospheric pressure. Plume expanding at 1.12 J/cm(2) laser fluence was recorded using a high-speed CMOS camera and corresponding propagation distance was measured. The solid matrix desorption was driven by phase explosion according to plume model fitting, which was consistent with the results of SEM.

Characterization of a bio-oil from pyrolysis of rice husk by detailed compositional analysis and structural investigation of lignin.

Detailed compositional analysis of a bio-oil (BO) from pyrolysis of rice husk was carried out. The BO was extracted sequentially with n-hexane, CCl(4), CS(2), benzene and CH(2)Cl(2). In total, 167 organic species were identified with GC/MS in the extracts and classified into alkanes, alcohols, hydroxybenzenes, alkoxybenzenes, dioxolanes, aldehydes, ketones, carboxylic acids, esters, nitrogen-containing organic compounds and other species. The benzene ring-containing species (BRCCs) were attributed to the degradation of lignin while most of the rests were derived from the degradation of cellulose and hemicellulose. Along with guaiacyl and p-hydroxyphenyl units as the main components, a new type of linkage was suggested, i.e., C(ar)-CH(2)-C(ar) in 4,4'-methylenebis(2,6-dimethoxyphenol). Based on the species identified, a possible macromolecular structure of the lignin and the mechanism for its pyrolysis are proposed. The BO was also extracted with petroleum ether in ca. 17.8% of the extract yield and about 82.1% of the extracted components are BRCCs.

Heat shock protein 72 inhibits c-Jun N-terminal kinase 3 signaling pathway via Akt1 during cerebral ischemia.

Although recent researches show that Heat Shock Protein 72 (HSP72) plays an important role in neuronal survival, little knowledge is known about the precise mechanisms during cerebral ischemia/reperfusion (I/R). Our present study investigated the neuroprotective mechanisms of HSP72 against ischemic brain injury induced by cerebral I/R. Mild heat shock pretreatment was employed to induce the overexpression of HSP72 by immersing rats into the water bath at 42°C for 20 min before cerebral I/R. HSP72 antisense oligodeoxynucleotides (ODNs) were used to inhibit HSP72 expression by intracerebroventricular infusion once per day for 3 days before cerebral I/R animal model was induced by four-vessel occlusion for 15 min transient ischemia and then reperfused for various time in Sprague-Dawley rats. Immunoprecipitation and immunoblotting were used to detect the expression of the related proteins. HE-staining and TUNEL-staining were carried out to examine the neuronal death of hippocampal CA1 region. Results showed that mild heat shock could increase the phosphorylation of protein kinase B (Akt), inhibit the assembly of MLK3-MKK7-JNK3 signaling module, diminish the phosphorylation of JNK3 and c-Jun, and decrease the activation of caspase-3. Furthermore, mild heat shock could significantly protect neurons against cerebral I/R. Whereas, all of the aforementioned effects of mild heat shock were reversed by HSP72 antisense ODNs. In summary, our results imply that Akt1 activation is involved in the neuroprotection of HSP72 against ischemic brain injury via suppressing JNK3 signaling pathway and provide a new experimental foundation for stroke therapy.

Heme oxygenase-1 regulates the JNK signaling pathway through the MLK3-MKK7-JNK3 signaling module in brain ischemia injury.

Although previous researches indicated that heme oxygenase-1 (HO-1) plays a conspicuous role in neuronal injury induced by reperfusion following the brain ischemia, reasonable mechanisms for the role of HO-1 are not clear. In this work, we investigated whether HO-1 was involved in the regulation of the c-Jun N-terminal kinase (JNK) signaling pathway and neuronal cell injury induced by the brain ischemia followed by reperfusion. Cobaltic protoporphyrin (CoPP), an activator of HO-1, was administrated to induce the overexpression of HO-1 by intracerebroventricular infusion 20 min before ischemia. The results showed that the combination of HO-1-mixed lineage kinase 3 (MLK3), MLK3-mitogen-activated kinase kinase 7 (MKK7) and MKK7-JNK3 increased to a peak at 6h of reperfusion following 15 min of ischemia induced by four-vessel occlusion in rats, and these effects were downregulated by CoPP. In addition, CoPP could inhibit the activation of JNK3, c-Jun and caspase-3. Furthermore, pretreatment with CoPP significantly increased the survival of neurons after 5 days of reperfusion. In contrast, all of the above effects of CoPP were reversed by zinc protoporphyrin (ZnPP), a selective inhibitor of HO-1. Our results suggested that HO-1 could protect neurons against brain ischemic injury by downregulating the JNK signaling pathway through the MLK3-MKK7-JNK3 signaling module.

Molecular cloning, characterization and function analysis of the gene encoding HMG-CoA reductase from Euphorbia Pekinensis Rupr.

A new full-length cDNA encoding 3-hydroxy-3-methylglutoryl-Coenzyme A reductase (HMGR; EC1.1.1.34), which catalyzes the first committed step of isoprenoids biosynthesis in MVA pathway, was isolated from young leaves of Euphorbia Pekinensis Rupr. by rapid amplification of cDNA ends (RACE) for the first time. The full-length cDNA of HMGR (designated as EpHMGR, GenBank Accession NO. EF062569) was 2,200 bp containing a 1,752 bp ORF encoding 583 amino acids. Bioinformatic analyzes revealed that the deduced EpHMGR had extensive homology with other plant HMGRs and contained two transmembrane domains and a catalytic domain. The predicted 3-D model of EpHMGR had a typical spatial structure of HMGRs. Southern blot analysis indicated that at most two copies of EpHMGR gene existed in E. Pekinensis genome. Tissue expression analysis revealed that EpHMGR expressed strongly in roots, weakly in stems and leaves. The functional colour complementation assay indicated that EpHMGR could accelerate the biosynthesis of carotenoids in the Escherichia coli transformant, demonstrating that EpHMGR plays an influential role in isoprenoid biosynthesis.

A novel one-dimensional complex: catena-poly[[manganese(III)-di-mu-2-[(2-hydroxyethyl)iminomethyl]phenolato-kappa2O1,N:kappaO2;kappaO2:kappa2O1] chloride].

In the title one-dimensional complex, [[Mn(III)(C9H10NO2)2]Cl]n, the Schiff base ligand 2-[(2-hydroxyethyl)iminomethyl]phenolate (Hsae-) functions as both a bridging and a chelating ligand. The Mn(III) ion is six-coordinated by two N and four O atoms from four different Hsae- ligands, yielding a distorted MnO4N2 octahedral environment. Each [Mn(III)(Hsae)2]+ cationic unit has the Mn atom on an inversion centre and each [Mn(III)(Hsae)2]+ cation lies about another inversion centre. The chain-like complex is further extended into a three-dimensional network structure through Cl...H-O hydrogen bonds and C-H...pi contacts involving the Hsae- rings.

[Spectral analysis of the structure of 1, 1'-and 1, 2'-dinaphthyl methanone].

The structure of 1, 1'-and 1, 2'-dinaphthyl methanone synthesized by the reaction of naphthalene with oxalyl chloride in the presence of AlCl3 were studied by using UV and FTIR in this paper. The analysis results showed that the difference of structures (symmetry) of 1,1'-and 1, 2'-dinaphthyl methanone were represented on the obvious difference of the spectra of UV and FTIR.