Stability and chemical bonding in a series of inverse sandwich actinide boride clusters (An2B8) with δ bonding.

An inverse sandwich structure has been computationally predicted for uranium boride and extended to the series of actinide elements (An) from Th to Cm. The electronic structure and chemical bonding of these novel compounds have been analyzed using density functional theory and multireference wave-function based methods. We report the trends in electronic structure and bonding for An2B8, and found that (d-π)π and (d-p)δ are the most important factors in the stability of An2B8. The (f-p)δ bond provides extra stabilization for Pa2B8 and U2B8, owing to the extensive interactions of An-B8-An, resulting in a short distance for the Pa-Pa and U-U bonds.

Algal/bacterial uptake kinetics of dissolved organic nitrogen in municipal wastewater treatment facilities effluents.

The simulation and analysis of the degradation process of organic nitrogen contaminants in wastewater treatment facility effluent is important to the estimation of its actual contribution to eutrophication, and it is crucial to the developing of watershed protection plan. In this study, algal and algal/bacterial based bioassay was conducted to study the bioavailability of dissolved organic nitrogen contaminants in wastewater treatment plants effluents, and 4 kinetic models were used to describe the mineralization process. The traditional 1-pool model that was commonly used in water quality models showed poor correlation (r2 = 0.613 ± 0.261), while the other three models performed much better (r2 > 0.950). The model coefficient and simplicity were studied using Akaike information criterion and Bayesian information criterion, and Gamma model was indicated to be the best model since it presented the most parsimonious fit to the data with the fewest terms. This study exhibited that the bioavailability and degradation rate of organic nitrogen in wastewater effluent varied greatly, and this variation should be considered in water quality models. Besides, Gamma model could be used to modify the current Total Maximum Daily Load models to provide a scientific basis for making watershed protection plans and controlling eutrophication.

Evaluation of ursolic acid derivatives with potential anti-Toxoplasma gondii activity.

Toxoplasma gondii is an important pathogen that causes serious public health problems. Currently, therapeutic drugs for toxoplasmosis cause serious side effects, and more effective and novel substances with relatively low toxicity are urgently needed. Ursolic acid (UA) has many properties that can be beneficial to healthcare. In this study, we synthesized eight series of UA derivatives bearing a tetrazole moiety and evaluated their anti-T. gondii activity in vitro using spiramycin as a positive control. Most of the synthesized derivatives exhibited better anti-T. gondii activity in vitro than UA, among which compound 12a exhibited the most potent anti-T. gondii activity. Furthermore, the results of biochemical parameter determination indicated that 12a effectively restored the normal body weight of mice infected with T. gondii, reduced hepatotoxicity, and exerted significant anti-oxidative effects compared with the findings for spiramycin. Additionally, our molecular docking study indicated that the synthesized compounds could act as potential inhibitors of T. gondii calcium-dependent protein kinase 1 (TgCDPK1), with 12a possessing strong affinity for TgCDPK1 via binding to the key amino acids GLU129 and TYR131.

Synthesis and evaluation of the HIF-1α inhibitory activities of novel ursolic acid tetrazole derivatives.

The hypoxia-inducible factor-1α (HIF-1α) pathway has been implicated in tumor angiogenesis, growth, and metastasis. Therefore, the inhibition of this pathway is an important therapeutic target for the treatment of various types of cancers. Here, we designed and synthesized 31 ursolic acid (UA) derivatives containing a tetrazole moiety and evaluated them for their potential anti-tumor activities as HIF-1α transcriptional inhibitors. Of these, compound 14d (IC50 0.8 ±â€¯0.2 µM) displayed the most potent activity and compounds 14a (IC50 4.7 ±â€¯0.2 µM) exhibited the most promising biological profile. Analysis of the structure-activity relationships of these compounds with HIF-1α suggested that the presence of a tetrazole group located at C-28 of the UA derivatives was critical for their inhibitory activities.

Design, synthesis, evaluation, and molecular docking of ursolic acid derivatives containing a nitrogen heterocycle as anti-inflammatory agents.

Ursolic acid derivatives containing oxadiazole, triazolone, and piperazine moieties were synthesized in an attempt to develop potent anti-inflammatory agents. Structures of the synthesized compounds were elucidated by 1H NMR, 13C NMR, and HRMS. Most of the synthesized compounds showed pronounced anti-inflammatory effects at 100 mg/kg. In particular, compound 11b, which displayed the most potent anti-inflammatory activity of all of the compounds prepared, with 69.76% inhibition after intraperitoneal administration, was more potent than the reference drugs indomethacin and ibuprofen. The cytotoxicity of the compounds was also assessed by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2-H-tetrazolium bromide (MTT) assay, and no compounds showed any appreciable cytotoxic activity (IC50 >100 µmol/L). Furthermore, molecular docking studies of the synthesized compounds were performed to rationalize the obtained biological results. Overall, the results indicate that compound 11b could be a therapeutic candidate for the treatment of inflammation.

Design, synthesis, and evaluation of novel ursolic acid derivatives as HIF-1α inhibitors with anticancer potential.

Hypoxia-inducible factor-1α (HIF-1α), a key mediator in tumor metastasis and angiogenesis, is associated with poor patient prognosis and has been recognized as an important cancer drug target. In this work, four novel series of ursolic acid derivatives containing oxadiazole, triazolone, and piperazine moieties were designed, synthesized, and evaluated for anti-tumor activity as HIF-1α inhibitors. The majority of the compounds showed an excellent ability to inhibit the expression of HIF-1α. In particular, 11b inhibited HIF-1α transcriptional activity under hypoxic conditions with IC50=36.9µM. The cytotoxicity of these compounds was also assessed in human colon cancer cell HCT116 cells by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2-H-tetrazolium bromide (MTT) assay, and no compounds showed any appreciable cytotoxic activity (IC50>100µmol/L), which was lower than that of ursolic acid (IC50=23.8µmol/L). The mechanism of action of the representative compound 11b was also investigated.

Synthesis and Positive Inotropic Activity of [1,2,4]Triazolo[4,3-a] Quinoxaline Derivatives Bearing Substituted Benzylpiperazine and Benzoylpiperazine Moieties.

In an attempt to search for more potent positive inotropic agents, two series of [1,2,4]triazolo[4,3-a] quinoxaline derivatives bearing substituted benzylpiperazine and benzoylpiperazine moieties were synthesized and their positive inotropic activities evaluated by measuring left atrial stroke volume in isolated rabbit heart preparations. Several compounds showed favorable activities compared with the standard drug, milrinone. Compound 6c was the most potent agent, with an increased stroke volume of 12.53% ± 0.30% (milrinone: 2.46% ± 0.07%) at 3 × 10-5 M. The chronotropic effects of compounds having considerable inotropic effects were also evaluated.

Synthesis and biological evaluation of chalcone derivatives containing aminoguanidine or acylhydrazone moieties.

Three novel series of chalcone derivatives containing an aminoguanidine or acylhydrazone moiety were designed, synthesized and evaluated in terms of their antibacterial, antifungal and anti-inflammatory activities. Most of the synthesized compounds showed potent inhibitory activity towards various bacteria and one fungus with minimum inhibitory concentrations (MICs) ranging from 1 to 8µg/mL. Compared with our previously reported chalcone derivatives (MICs >64µg/mL), these compounds exhibited improved antibacterial activities (MICs=2µg/mL) against Gram-negative bacterial strains (Escherichia coli 1924 and 1356). Compounds 4f and 4h were found to be the most potent with an MIC value of 1µg/mL against the Gram-negative bacterial strains Salmonella typhimurium 1926 and the fungus Candida albicans 7535. In addition, compound 4f displayed the most potent anti-inflammatory activity of all of the compounds prepared in the current study with 92.45% inhibition after intraperitoneal administration, making it more potent than the reference drugs indomethacin and ibuprofen. The cytotoxic activity of the compound 4f was assessed in HeLa, Hep3B and L02 cells.

Bioconversion of pinoresinol into matairesinol by use of recombinant Escherichia coli.

Lignans, a class of dimeric phenylpropanoid derivative found in plants, such as whole grains and sesame and flax seeds, have anticancer activity and can act as phytoestrogens. The lignans secoisolariciresinol and matairesinol can be converted in the mammalian proximal colon into enterolactone and enterodiol, respectively, which reduce the risk of breast and colon cancer. To establish an efficient bioconversion system to generate matairesinol from pinoresinol, the genes encoding pinoresinol-lariciresinol reductase (PLR) and secoisolariciresinol dehydrogenase (SDH) were cloned from Podophyllum pleianthum Hance, an endangered herb in Taiwan, and the recombinant proteins, rPLR and rSDH, were expressed in Escherichia coli and purified. The two genes, termed plr-PpH and sdh-PpH, were also linked to form two bifunctional fusion genes, plr-sdh and sdh-plr, which were also expressed in E. coli and purified. Bioconversion in vitro at 22°C for 60 min showed that the conversion efficiency of fusion protein PLR-SDH was higher than that of the mixture of rPLR and rSDH. The percent conversion of (+)-pinoresinol to matairesinol was 49.8% using PLR-SDH and only 17.7% using a mixture of rPLR and rSDH. However, conversion of (+)-pinoresinol by fusion protein SDH-PLR stopped at the intermediate product, secoisolariciresinol. In vivo, (+)-pinoresinol was completely converted to matairesinol by living recombinant E. coli expressing PLR-SDH without addition of cofactors.

Transformation mechanisms of the antidepressant citalopram in a moving bed biofilm reactor: Substrate-depended pathways, eco-toxicities and enantiomeric profiles.

Citalopram (CIT) is one of the most consumed antidepressants and frequently detected in aquatic environments worldwide. Conventional wastewater treatment cannot remove this neuronal active pharmaceutical efficiently. Past studies showed that moving bed biofilm reactors (MBBRs) can degrade CIT but the exact transformation pathways and toxicity reduction remained unclear. In this study, the effects of substrate stimulation on CIT transformation in an MBBR were systematically investigated. The results showed that a co-metabolic stimulation by acetate increased the transformation rate by 54 % and 24 % at high (300 µg/L) and environmental concentration (1.8 µg/L) of CIT, respectively. Conversely, the complex substrates in raw wastewater reduced the reaction rates by 44 %, suggesting a competitive inhibition on the enzymatic sites. The substrate stimulation changed the enantiomeric fraction (EF) of CIT from racemic (EF=0.5) to 0.60 at the high CIT concentrations, while those at lower concentrations resulted in an EF of 0.33, indicating that probably different enantioselective enzymes degraded CIT at high concentrations than at low concentrations, i.e., the presence of 300 µg/L CIT was possibly sufficient to induce the synthesis of different enantioselective enzymes, than those originally present. Through non-target and target analysis, in total 19 transformation products (TPs) including 7 TPs that were hitherto not mentioned in the literature were identified. Among these were quaternary amines, alkenes and conjugate TPs. The major transformation pathways were a) nitrile hydrolysis (up to 43 %), b) amide hydrolysis, and c) N-oxidation. Dosing acetate up-regulated significantly the amide hydrolysis, N-oxidation and conjugation pathways but inhibited the N-demethylation and α-carbon hydroxylation pathways. The in-silico toxicity assessment of CIT and its TPs suggested the overall eco-toxic potential of TPs was reduced by MBBR. Furthermore, the degradation under carbon-limited (famine) conditions favored the formation of the more toxic carboxamide, N-desmethyl and alkene TPs, while carbon-rich conditions, promoted the production of the less toxic carboxylic acid, N-oxide and ester TPs. Therefore, this study demonstrated that a) the co-metabolic stimulation of CIT metabolization by dosing a simple carbon source or b) inhibition of CIT metabolization by complex substrates; c) substrate stimulation made a difference on CIT transformation rates, enantiomeric profiles, pathways and toxic potentials. Overall, a simple-carbon co-metabolic stimulated MBBR was an efficient up-regulation strategy to minimize hazardous CIT and CIT-TPs as much as possible.

Micro-electrolysis based nitrate reduction from aqueous solution by CNTs-Al-Cu composite under alkaline environment.

CNTs-Al was prepared by ball milling combined with sintering process and then used for CNTs-Al-Cu synthesis with chemical deposition method. The obtained CNTs-Al-Cu composite was systematically characterized and its NO3--N reduction performance under alkaline condition was also evaluated. As indicated by the reduction batch experiment, 80.2% of NO3--N removal efficiency was obtained in 90 min at pH of 9. The product of the reduction process was dominated by NO2--N, which was further reduced to harmless N2. The reusability of CNTs-Al-Cu composite was evaluated, and the experiment results showed that 68.1% of NO3--N removal efficiency was maintained after 3 cycles of regeneration. Finally, based on the characterization results and kinetic analysis, it was concluded that micro-electrolysis was mainly responsible for the removal of NO3--N by CNTs-Al-Cu.

Quantitative study on the structure-bioavailability relationship of dissolved organic nitrogen in wastewater treatment plant effluent.

This study systematically investigated the relationship between the structure properties and biological characteristics of dissolved organic nitrogen (DON) in the effluents from municipal wastewater treatment plants. Ultrafiltration, Fourier transform infrared (FTIR) spectroscopy, ultraviolet (UV) spectroscopy, and excitation-emission matrix (EEM) fluorescence spectroscopy were used to characterize the structure of organic matters in the effluent samples, and the bioavailability of DON was determined by algal/bacterial-based bioassay. The quantitative analysis of EEM spectra conducted by fluorescence regional integration method showed that the organic portion of all samples was mainly consistent with fulvic acid and protein. Combined with the bioassay results, a positive correlation between the DON bioavailability and the protein content (sum of region I and region II) (r = 0.80, P < 0.02) and soluble microbial byproduct-like materials (region IV) (r = 0.76, P < 0.03) were observed. Nevertheless, the humic substances content represented by the region III and V would negatively affect the DON bioavailability. High humification degree (high HIX value) (r = - 0.77, P < 0.03) was related to low bioavailability. Furthermore, according to UV spectroscopy results, strong aromaticity (high UV254 values) (r = - 0.78, P < 0.03) suggested low DON bioavailability. One protein-like component (C3) and two humic-like components (C1 and C2) were identified via fluorescence excitation-emission matrices-parallel factor analysis (EEM-PARAFAC), and component C3 values were positively correlated to the BAN/DON ratio (r = 0.74, P < 0.03). The ultrafiltration showed that the low molecular weight DON (< 3 kDa) accounted for 30-73% of the total DON, and no notable relationship was observed for DON molecular weight and its bioavailability.

Robust Optimal Control Design for Performance Enhancement of PWM Voltage Source Inverter.

PWM (pulse-width modulation) voltage source inverters are used in a wide range of AC power systems where the output voltage must be controlled to follow a sinusoidal reference waveform. In order to achieve precision and fast-tracking control, restrictive sliding mode control (RSMC) provides a fast system state convergence time. However, the RSMC still suffers from the chattering problem, which leads to high harmonic distortion and slow response of the inverter output state. Furthermore, the load of the inverter may be severe load changing and the control parameters become difficult to adjust, worsening the adaptability to achieve the desired control of the inverter output. In this paper, a robust optimal control design comprised of an enhanced restrictive sliding mode control (ERSMC) and density particle swarm optimization (DPSO) algorithm is proposed, and then applied to PWM voltage source inverters. The ERSMC not only has finite time convergence but also provides chatter elimination. The DPSO is highly adaptable for acquiring the control parameters of the ERSMC and finding the best solution in the global domain. The proposed controller is realized for the actual PWM voltage source inverter controlled by a TI DSP-based development platform, so that the inverter output voltage has fast dynamic response and satisfactory steady-state behavior despite high load changing and non-linear disturbances.

Prospective contributions of biomass pyrolysis to China's 2050 carbon reduction and renewable energy goals.

Recognizing that bioenergy with carbon capture and storage (BECCS) may still take years to mature, this study focuses on another photosynthesis-based, negative-carbon technology that is readier to implement in China: biomass intermediate pyrolysis poly-generation (BIPP). Here we find that a BIPP system can be profitable without subsidies, while its national deployment could contribute to a 61% reduction of carbon emissions per unit of gross domestic product in 2030 compared to 2005 and result additionally in a reduction in air pollutant emissions. With 73% of national crop residues used between 2020 and 2030, the cumulative greenhouse gas (GHG) reduction could reach up to 8620 Mt CO2-eq by 2050, contributing 13-31% of the global GHG emission reduction goal for BECCS, and nearly 4555 Mt more than that projected for BECCS alone in China. Thus, China's BIPP deployment could have an important influence on achieving both national and global GHG emissions reduction targets.

Application of biomass pyrolytic polygeneration by a moving bed: Characteristics of products and energy efficiency analysis.

In order to overcome the shortcoming of batch production in the retort and improve the quality of three-state products, a moving bed as pyrolysis furnace and torrefaction pretreatment were both used in a demonstration of biomass pyrolytic polygeneration. The bench and demonstration scale experiments were both investigated in this work. The results show that when the pyrolysis temperature between 550 °C and 750 °C, it can not only maintain the relative stability of the tri-state products yield, but also guarantee the quality. When the demonstration ran at this temperature, it can continuously deal with biomass for about 7E+03 kg/h, and reach 5.42E+07 kg/yr, which can be converted into 1.12E+07 Nm3 of bio-gas, 3.78E+06 kg of tar, 7.63E+06 kg of vinegar and 1.14E+07 kg of biochar. The lower heating value of bio-gas and biochar were respectively 12.5 MJ/m3 and 30.5 MJ/kg, which showed the great potential as gas and solid fuel.

Design, synthesis, and negative inotropic evaluation of 4-phenyl-1H-1,2,4-triazol-5(4H)-one derivatives containing triazole or piperazine moieties.

In this study, four novel series of 4-phenyl-1H-1,2,4-triazol-5(4H)-one derivatives containing triazole or piperazine moieties were designed, synthesized, and evaluated for negative inotropic activity by measuring the left atrium stroke volume in isolated rabbit heart preparations. Almost all of the compounds showed an ability to moderate the cardiac workload by decreasing the heart rate and contractility. Among them, 7h was found to be the most potent with a change in stroke volume of -48.22 ± 0.36% at a concentration of 3 × 10-5  mol/L (metoprolol: -9.74 ± 0.14%). The cytotoxicity of these compounds was evaluated using the human cervical cancer cell line HeLa, the liver cancer cell line Hep3B, and the human normal hepatic cell line LO2. A preliminary study of the mechanism of action for the compound 7h on the regulation of atrial dynamics with ATP-sensitive K+ channel and L-type Ca2+ channel blockers glibenclamide and nifedipine was performed in the isolated perfused beating rabbit atria.

Synthesis and Antimicrobial Evaluation of (Z)-5-((3-phenyl-1H-pyrazol-4- yl)methylene)-2-thioxothiazolidin-4-one Derivatives.

BACKGROUND: An alarming increment in pathogenic resistance to existing anti-microbial agents is a serious problem and the treatment of these bacterial infections is becoming increasingly challenging. Therefore, there is an urgent need to develop novel antimicrobial agents. OBJECTIVE: As a part of our ongoing studies toward the development of novel antibacterial agents, the synthesis and antibacterial activity of a series of (Z)-5-((3-phenyl-1H-pyrazol-4-yl)methylene)-2-thioxothiazolidin-4-one derivatives will be discussed in this study. METHOD: (Z)-5-((3-phenyl-1H-pyrazol-4-yl)methylene)-2-thioxothiazolidin-4-one derivatives were designed, synthesized and evaluated for antibacterial activity. The structures were confirmed by IR, 1H NMR, 13C NMR and mass spectrometry. All of the synthesized compounds were evaluated in vitro using a 96-well microtiter plate and a serial dilution method to obtain their minimum inhibitory concentration (MIC) values against a variety of different strains, including multidrug-resistant clinical isolates. RESULTS: The antibacterial test in-vitro showed that most compounds in series 7 and 9 exhibited significant inhibitory activities against anaerobic bacteria (Streptococcus mutans) strains with a MIC value of 1 µg/mL. Compounds 7c and 9c showed the most potent activity against MRSA (3167 and 3506) with a minimum inhibitory concentration (MIC) value of 1 µg/mL, which is equivalent to moxifloxacin and greater than gatifloxacin, oxacillin and norfloxacin. Additionally, compound 9c showed potent antibacterial activity against Bacillus subtilis (aerobic bacteria) with a MIC value of 2 µg/mL. CONCLUSION: The work suggests that these type of rhodanine compounds had a better potent activity against MRSA compared with other perviously reported rhodanine derivatives, which might provide a valuable information for the development of new antibacterial agents against multidrug-resistant clinical isolates MRSA.

Synthesis and Antibacterial Evaluation of (S,Z)-4-methyl-2-(4-oxo-5-((5-substituted phenylfuran-2-yl) methylene)-2-thioxothiazolidin-3-yl)Pentanoic Acids.

The microbial resistance has become a global hazard with the irrational use of antibiotics. Infection of drug-resistant bacteria seriously threatens human health. Currently, there is an urgent need for the development of novel antimicrobial agents with new mechanisms and lower levels of toxicity. In this paper, a series of (S ,Z)-4-methyl-2-(4-oxo-5-((5-substitutedphenylfuran-2-yl) methylene)-2-thioxothiazolidin-3-yl)pentanoic acids via a Knoevenagel condensation were synthesized and evaluated for their antibacterial activity in - vitro. The synthesized compounds were characterized by IR, (1)H NMR and MS. The antibacterial test in - vitro showed that all of the synthesized compounds had good antibacterial activity against several Gram-positive bacteria (including multidrug-resistant clinical isolates) with minimum inhibitory concentration (MIC) values in the range of 2-4 µg/mL. Especially compounds 4c, 4d, 4e and 4f were the most potent, with MIC values of 2 µg/mL against four multidrug-resistant Gram-positive bacterial strains.

Synthesis and antibacterial evaluation of rhodanine-based 5-aryloxy pyrazoles against selected methicillin resistant and quinolone-resistant Staphylococcus aureus (MRSA and QRSA).

With an intention to synergize the anti-bacterial activity of 5-aryloxy pyrazole and rhodanine derivatives, eight series of hybrid compounds have been synthesized and evaluated for their antibacterial activity. The majority of the synthesized compounds showed good inhibitory activity against selected methicillin resistant and quinolone-resistant Staphylococcus aureus (MRSA, QRSA) with minimum inhibitory concentration (MIC) values in the range of 1-32 µg/mL. The cytotoxicity test suggests that these compounds exhibited in vitro antibacterial activity at non-cytotoxic concentrations. These studies therefore suggest that rhodanine-based 5-aryloxy pyrazoles are interesting scaffolds for the development of novel Gram-positive antibacterial agents.