污水除磷技术现状及发展趋势

综述除磷不同方法的原理、特点及其适用范围。物化除磷法由于其除磷效果好、运行稳定、易实现自动化等特点,适用于处理流量不是很大的含磷废水;生物除磷法可减少活性污泥的膨胀、污泥产出量少、节约能源、运行费用较低,是目前流行的除磷方法;膜技术除磷可克服生物除磷法的缺陷、回收纯净的磷盐,是当前研究的热点。提出物化除磷法与生物除磷法相结合必将成为今后的研究趋势。

Catalytic wet oxidation of aniline over Ru catalysts supported on a modified TiO_2

The catalytic wet air oxidation of aniline over Ru catalysts supported on modified Ti 2 （Ti 2, Ti0.9Ce0.1O2, Ti0.9Zr0.1O2） is investigated. A series of characterization techniques are conducted to determine the relationship between the physico-chemical properties and the catalytic performance. As a result of the good metal dispersion and large number of surface oxygen species, the Ru/Ti0.9 Zr0.1O2 catalyst presents the best catalytic activity among the tested samples. The effects of the operating conditions on the reaction are investigated and the optimal reaction conditions are determined. Based on the relationship between the by-products concentration and the reaction time, the reaction path for the catalytic oxidation of aniline is established. Carbonaceous deposits on the surface of the support are known to be the main reason for catalyst deactivation. The catalysts maintain a constant activity even after three consecutive cycles.

Systemic chemotherapy for hepatocellular carcinoma in non-cirrhotic liver:A retrospective study

AIM:To investigate the efficacy and toxicity of systemic chemotherapy in a retrospective study of patients with hepatocellular carcinoma(HCC)occurring in normal or fibrotic liver without cirrhosis. METHODS:Twenty-four patients with metastatic or locally advanced HCC in a normal or a fibrotic liver were given systemic chemotherapy(epirubicin,cis- platin and 5-fluorouracil or epirubicin,cisplatin and capecitabine regimens).Tumor response,time to pro- gression,survival,and toxicity were evaluated. RESULTS:There were 7 women and 17 men,mean age 54±10 years;18 patients had a normal liver and 6 had a fibrotic liver(F1/F2 on biopsy).Mean tumor size was 14 cm,5 patients had portal vein thrombosis and 7 had metastasis.Patients received a median of 4 chemotherapy sessions.Overall tolerance was good. There were 5 partial responses(objective response rate =22%),and tumor control rate was 52%.Second line surgical resection was possible in two patients.Median survival was 11 mo,and 1-and 2-year overall survival rates were 50%±10%and 32%±11%,respectively. CONCLUSION:In patients with HCC in a non-cirrhotic liver,chemotherapy was well tolerated and associated with an objective response rate of 22%,including two patients who underwent secondary surgical resection.

Synthesis of poly[methyl(3,3,3-trifluoropropyl)siloxane]-b-poly(ethylene oxide) block copolymers

A series of new amphiphilic poly[methyl（3,3,3-trifluoropropyl）siloxane]-b-poly（ethylene oxide） （PMTFPS-b-PEO） diblock copolymers with different ratios of hydrophobic segment to hydrophilic segment were prepared by coupling reactions of end-functlonal PMTFPS and PEO homopolymers. Copolymers were shown to be well defined and narrow molecular weight distribution （MWD） （1.07-1.3） by characterizations such as gel permeation chromatography （GPC） and ^1H-nudear magnetic resonance （^1H-NMR）.

A direct electrochemical route from oxides to TiMn_2 hydrogen storage alloy

This study is for investigating the direct electro-deoxidation of mixed TiO2-Mn02 powder to prepare TiMn2 alloy in molten calcium chloride. The influences of process parameters, such as sintering temperature, cell voltage, and electrolysis time, on the electrolysis process were examined to investigate the mechanism of alloy formation. The composition and morphology of the products were analyzed by XRD and SEM, respectively. The electrochemical property of TiMn2 alloy was investigated by cyclic voltammetry measurements. The results show that pure TiMn2 can be prepared by direct electrochemical reduction of mixed TiO2/Mn02 pellets at a voltage of 3.1 V in molten calcium chloride of 900 ℃ for 7 h. The electro-deoxidation proceeds from the reduction of manganese oxides to Mn, which is reduced by Ti02 or CaTiOB to form TiMn2 alloy. The cyclic voltammetry measurements using pow- der microelectTode show that the prepared TiMn2 alloy has good electrochemical hydrogen storage property.

Antioxidant power of phytochemicals from Psidium guajava leaf

Dried ground leaves of Psidium guajava L. (guava) were extracted by water and aqueous ethyl alcohol 50% (1:10) ratio, and the total phenolic content in the extracts was determined spectrophotometrically according to Folin- Ciocalteu’s phenol method and calculated as gallic acid equivalent (GAE). Remarkably high total phenolic content 575.3 ±15.5 and 511.6±6.2 mg of GAE/g of dried weight material (for ethanol guava leaf extracts and water guava leaf extracts, respectively) were obtained. The antioxidant activity of lyophilized extracts was determined at ambient temperature by means of a 2,2-diphenyl-1-picrylhydryzyl (DPPH˙) colorimetry with detection scheme at 515 nm. The activity was evalu- ated by the decrease in absorbance as the result of DPPH˙ color change from purple to yellow. The higher the sample concentration used, the stronger was the free radical-scavenging effect. The results obtained showed that ascorbic acid was a substantially more powerful antioxidant than the extracts from guava leaf. On the other hand, the commercial guava leaf extracts and ethanol guava leaf extracts showed almost the same antioxidant power whereas water guava leaf extracts showed lower antioxidant activity. The parameter EC50 and the time needed to reach the steady state to EC50 concentration ( TEC50 ) affected the antiradical capacity of the sample. The antioxidant efficiency (AE) has been shown to be a more ade- quate parameter for selecting antioxidants than the widely used EC50. This study revealed that guava leaf extracts comprise effective potential source of natural antioxidants.

Thermodynamic Calculation on the Formation of Titanium Hydride

A modified Miedema model, using interrelationship among the basic properties of elements Ti and H, is employed to calculate the standard enthalpy of formation of titanium hydride TiHx （1≤x≤2）. Based on Debye theories of solid thermal capacity, the vibrational entropy, as well as electronic entropy, is acquired by quantum mechanics and statistic thermodynamics methods, and a new approach is presented to calculate the standard entropy of formation of TiH2. The values of standard enthalpy of formation of TiHx decrease linearly with increase of x. The calculated results of standard enthalpy, entropy, and free energy of formation of TiH2 at 298.16 K are -142.39 kJ/mol, -143.0 J/（mol·K） and -99.75 kJ/mol, respectively, which is consistent with the previously-reported data obtained by either experimental or theoretical calculation methods. The results show that the thermodynamic model for titanium hydride is reasonable.

Water Energy and Antioxidant Properties of Water

The possibilities of changes of ORP （oxidation-reduction water potential） with the help of chemical and physical-chemical methods were explored. Distillation and membrane technology were used as physical-chemical methods. In the case of application of chemical methods well-soluble substances were added into water. It was ascertained that the application of membrane technology makes it possible to obtain antioxidant water with negative ORR. Different energy change in a time unit can be applied in a whole number of technological processes and reveals new possibilities for many branches of industry.

Oxidative stress and hypoxia-induced factor 1α expression in gastric ischemia

AIM:To investigate the relation of reactive oxygen species (ROS) to hypoxia induced factor 1α (HIF-1α) in gastric ischemia. METHODS:The animal model of gastric ischemia reperfusion was established by placing an elastic rubber band on the proximal part of the bilateral lower limb for ligature for 3 h and reperfusion for 0,1,3,6,12 or 24 h. Ischemic post-conditioning,three cycles of 30-s reperfusion and 30-s femoral aortic reocclusion were conducted before reperfusion. Histological and immunohistochemical methods were used to assess the gastric oxidative damage and the expression of HIF1-α in gastric ischemia. The malondialdehyde (MDA) content and superoxide dismutase (SOD),xanthine oxidase (XOD) and myeloperoxidase (MPO) activities were determined by colorimetric assays. RESULTS:Ischemic post-conditioning can reduce post-ischemic oxidative stress and the expression of HIF-1α of gastric tissue resulting from limb ischemia reperfusion injury. MDA,SOD,XOD and MPO were regarded as indexes for mucosal injuries from ROS,and ROS was found to affect the expression of HIF-1α under gastric ischemic conditions. CONCLUSION:ROS affects HIF-1α expression under gastric ischemic conditions induced by limb ischemia reperfusion injury. Therefore,ROS can regulate HIF-1α expression in gastric ischemia.

The expression and clinical significance of β-catenin and colorectal cancer stem cells marker EpCAM^(high)/CD44^+ in colorectal cancer

Objective： The aim of the study was to explore the role of Wnt βcatenin signalling pathway in the maintenance, invasion and metastasis of colorectal cancer stem cells. Methods： Double immunohistochemical staining was used to detect the expression of EpCAMhigh/CD44~ which is regarded as the marker of colorectal cancer stem cells in 80 cases of colorectal cancer and their corresponding liver metastases. The SP method of immunohistochemistry was used to detect the expression of the key protein βcatenin in the Wnt pathway in these tissue. The expression and correlation of ^-catenin and EpCAMh^gh/ CD44＋ in colorectal cancer were analyzed and their role on the biological behavior of colorectal cancer was explored. Results： The abnormal expression of βcatenin was significantly higher in colorectal cancer than in the paraneoplastic normal intes- tinal mucosa [55% （44/80） vs 10% （2/20）, P 〈 0.05]. The positive expression of EpCAMhigh/CD44＋ was significantly higher in colorectal cancer than in the paraneoplastic normal intestinal mucosa [66.25% （53/80） vs 0% （0/20）, P 〈 0.05]. In the 80 cases of colorectal cancer, the abnormal expression of ^-catenin has no correlation with gender （P = 0.079）, age （P = 0.416） and the magnitude （P = 0.816） of the tumor （P 〉 0.05）, but it was significantly correlated with degree of differentiation （P = 0.001）, depth of invasion （P = 0.001）, clinical stage （P = 0.000） and metastasis （P = 0.000）. In the colorectal cancer, the expression of EpCAMhi^h/CD44~ cells has no correlation with gender （P = 0.934） and the magnitude （P = 0.160） of the tumor （P 〉 0.05）, but was significantly correlated with age （P = 0.021）, degree of differentiation （P = 0.013）, depth of invasion （P = 0.000）, clinical stage （P = 0.000） and metastasis （P = 0.000）. In the corresponding liver metastases, we could also detecte EpCAMhih/CD44＋ cells. In cases with abnormal expression of βcatenin, the positive expression rate of EpCAMhigh/CD44＋ was significantly higher than those with normal expression of β-catenin （84.1% vs 44.4%）, and the difference was statistically significant （P 〈 0.05）. Conclusion： The abnormal activation of Wnt β-catenin signalling pathway may prompt the abnormal proliferation of the colorectal cancer stem cells, which leads to the recurrence and metastasis of the cancer.

Electrochemical Polymerization of Acrylamide Film on Mild Steel Electrode for Corrosion Protection

Polyacrylamide （PAM） film was electrosynthesized on mild steel by cyclic voltammetry using Ce （IV） salt-oxalic acid as supporting electrolyte. Polymerization was initiated by a free radical that was formed by the fast reaction of oxalic acid and Ce （IV）. The electrolysis of the reaction solution resulted in regeneration of Ce （IV）, which could oxidize oxalic acid to produce radicals. The effect of temperature on the yield of electroinitiated polymerization was performed. The potential sweep rates were changed to achieve the polymer film with different thickness. Protective properties of the PAM film for corrosion of mild steel in 1 M NaCI aqueous solution were investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy （EIS）. The structure of PAM film on mild steel was investigated by using physicochemical methods such as elemental analysis of C, H, N, physical chemical methods and FTIR spectrometer. The influence of scan repetition and scan rate on the formation of polymer film was studied at a current density of 1 mA/cm2. The results of these studies reveal that the corrosion resistance of the PAM-coated mild steel was significantly higher and the corrosion rate was considerably lower than that of uncoated steel. The PAM film was formed with lower sweep rate leading to more positive shift of corrosion potential and greater charge transfer resistance, reflecting higher inhibition for corrosion of the mild steel.

Effects of gemcitabine and cisplatin chemotherapy in advanced non-small cell lung cancer patients with RRM1 low protein expression

Objective： The aim of this study was to observe the efficacy of gemcitabine combined with cisplatin （GP） in advanced non-smaU cell lung cancer （NSCLC） patients with low expression of ribonucleotide reductase 1 （RRM1） protein using immunohistochemistry. Methods： RRM1 protein expression in tumor tissue was detected by streptavidin-peroxidase （SP） method of immunohistochemistry. GP regimen （gemcitabine 1000-1250 mg d1, d8, cisplatin 75 mg/m2） was given to advanced NSCLC patients with low expression of RRM1 protein. Results： In the total of 40 patients, these patients with RRM1 low expression performing GP chemotherapy had a good response rate, the objective response rate （ORR） was 47.5% （95% CI, 32.02%- 62.98%）, and the disease control rate （DCR） was 72.5% （95 % CI, 65.44%-79.56%）. ORR is 45.45% （5/11） in the squamous cell carcinoma patients while 48.15% （13/27） in the adenocarcinoma patients. Conclusion： Supedor ORR and DCR were found in advanced NSCLC patients with low expression of RRM1 protein expression performing GP regimen.

Photochemical Method to Evaluate Oxidation Levels in Heat-Treated Vegetable Oil： Comparison with Peroxide-Value and Acid-Value

To determine the degree of oxidation in vegetable oil, a photochemical method using the electron spin resonance （ESR） spin trapping technique was developed, and the results were compared with those obtained using conventional peroxide-value （PV） and acid-value （AV） methods. Vegetable oil heat-treated were subjected to short UV illumination, and the produced alkyl-oxyl radicals were identified and quantified using the ESR spin trapping technique. ESR signal intensity was used as an indicator of oil oxidation, which monotonically increased as a function of the heat-treatment time. Commercially, available oils were selected and analyzed. The results were compared with those obtained using the PV and AV methods. The present method displayed some analogies with the PV method at least in the early stage of heating. Overall, the present method had highly sensitive and capable of detecting early-stage oxidation in vegetable oil.

Redox potentials of trifluoromethyl-containing compounds

Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is thought to be involved in many recently tested catalytic trifluoromethylation reactions. To provide helpful physical chemical data for mechanistic studies on trifluoromethylation reactions, the redox potentials of a variety of trifluoromethyl-containing compounds and trifluoro- methylated radicals were studied by quantum-chemical methods. First, eoB97X-D was found to be a reliable method in predicting the ionization potentials, electron affinities, bond dissociation enthalpies and redox potentials of trifluoromethylcontaining compounds. One-electron absolute redox potentials of 79 trifluoromethyl substrates and 107 trifluoromethylated radicals in acetonitrile were then calculated with this method. The theoretical results were found to be helpful for interpreting experimental observations such as the relative reaction efficiency of different trifluoromethylation reagents. Finally, the bond dissociation free energies （BDFE） of various compounds were found to have a good linear relationship with the related bond dissociation enthalpies （BDE）. Based on this observation, a convenient method was proposed to predict one-electron redox potentials of neutral molecules.

Integration of Chemical Methods and Biomarkers for Assessment of Chlorimuron-Ethyl Bioavailability in Soil

Bioavailability is a critical factor for assessing the environmental risk of organic pollutants in soil. In this study, extractions with 3 different solvents, including 2 aqueous solutions, calcium chloride(CaCl_2) and a phosphate buffer solution(PBS), and a mixture of aqueous solution and organic solvent, a PBS-methanol(8:2,volume/volume) mixture(PBS-M), were performed to assess the bioavailability of chlorimuron-ethyl in soil in comparison to a battery of toxicity tests in wheat seedlings. The results indicated that the peroxidase(POD) activity in wheat leaves after 7 d of exposure was one of the sensitive biomarkers of chlorimuron-ethyl in soil.The extractability of chlorimuron-ethyl by all the 3 solvents decreased with exposure time, and the rate of decrease of the PBS-M extraction between 1 and 7 d of exposure was substantially higher than those of the aqueous solution extractions. Chlorimuron-ethyl gradually changed from a water-soluble form into a soil organic matter(SOM)-bound form in the soil. The PBS extraction correlated best with the POD activity in the leaves after 7 d of exposure.

Dolphin swarm algorithm

By adopting the distributed problem-solving strategy, swarm intelligence algorithms have been successfully applied to many optimization problems that are difficult to deal with using traditional methods. At present, there are many well-implemented algorithms, such as particle swarm optimization, genetic algorithm, artificial bee colony algorithm, and ant colony optimization. These algorithms have already shown favorable performances. However, with the objects becoming increasingly complex, it is becoming gradually more difficult for these algorithms to meet human＇s demand in terms of accuracy and time. Designing a new algorithm to seek better solutions for optimization problems is becoming increasingly essential. Dolphins have many noteworthy biological characteristics and living habits such as echolocation, information exchanges, cooperation, and division of labor. Combining these biological characteristics and living habits with swarm intelligence and bringing them into optimization problems, we propose a brand new algorithm named the ‘dolphin swarm algorithm＇ in this paper. We also provide the definitions of the algorithm and specific descriptions of the four pivotal phases in the algorithm, which are the search phase, call phase, reception phase, and predation phase. Ten benchmark functions with different properties are tested using the dolphin swarm algorithm, particle swarm optimization, genetic algorithm, and artificial bee colony algorithm. The convergence rates and benchmark function results of these four algorithms are compared to testify the effect of the dolphin swarm algorithm. The results show that in most cases, the dolphin swarm algorithm performs better. The dolphin swarm algorithm possesses some great features, such as first-slow-then-fast convergence, periodic convergence, local-optimum-free, and no specific demand on benchmark functions. Moreover, the dolphin swarm algorithm is particularly appropriate to optimization problems, with more calls of fitness functions and fewer individuals.

Cracked bark-inspired ternary metallic sulfide(NiCoMnS_(4)) nanostructure on carbon cloth for high-performance aqueous asymmetric supercapacitors

In this paper,we report a high-performance selfsupported supercapacitor electrode composed of a cracked bark-shaped Ni-Co-Mn ternary metallic sulfide(NiCoMnS4)nanostructure on carbon cloth prepared by a simple one-step hydrothermal process and subsequent electrochemical treatment.The electrode delivers a high specific discharge capacity of up to 2470.4 F g^(-1) at 1 A g^(-1) and high rate performances of1635.6 F g^(-1) at 10 A g^(-1) and 910.2 F g^(-1) even at 32 A g^(-1).Cycling tests indicate that NiCoMnS_(4) could maintain >91.1% of its initial capacity and nearly 100% Coulombic efficiency over10,000 cycles at 8 A g^(-1).An aqueous asymmetric supercapacitor assembled with NiCoMnS_(4) as the cathode,activated carbon as the anode,and 1 mol L^(-1) KOH as the electrolyte delivers an energy density of 68.2 W h kg^(-1)at 850.1 W kg^(-1) and capacity retention of 92.5% after 10,000 cycles at 4 A g^(-1).Given the excellent performance and simple material preparation of our proposed device,this study provides a valuable foundation for the development of self-supported metallic sulfide-based electrodes with high electrochemical properties for potential application in aqueous asymmetric supercapacitors.

Methodology and Foreground of Metallomics

Metallomics is proposed as a new omics to fol- low genomics, proteomics and metabolomics. This paper gives an overview of the development of met- allomics based on the introduction of the concept of metallomics and its methodology.

Facile synthesis of nickel cobalt selenide hollow nanospheres as efficient bifunctional electrocatalyst for rechargeable Zn-air battery

Designing high active,low cost and bifunctional electrocatalysts is urgent for developing clean energy storage and conversion systems.Transition metal selenides exhibit optimal electronic conductivity and tunable physicochemical properties,which endow them with potential for efficient electrocatalysts to facilitate the oxygen reduction and oxygen evolution reactions(ORR and OER).Herein,hollow NixCo0.85-xSe nanospheres were synthesized using a facile polyol based solution chemical method.The NixCo0.85-xSe exhibits an onset overpotential of 0.89 V for ORR,and an overpotential of 305 mV to achieve 10 mA cm^-2 for OER.Moreover,the NixCo0.85-xSe based Zn-air battery displays remarkable specific capacity and durability.Such superior catalytic performances can be attributed to the synergistic effect,large specific surface area and enhanced electron transfer rate.This approach provides a new way to design highly efficient bifunctional electrocatalysts for electrochemical energy storage and utilization.

Direct visualization of the charge transfer in conjugated polymers

Ion-induced charge-transfer states in conjugated polyelectrolytes were experimentally investigated by Justin M.Hodgkiss and his co-workers [J Am Chem Soc,2009,131(25):8913].In this work,charged and neutral conjugated polyelectrolytes were further studied with quantum chemistry methods.The calculation result shows that the absorption spectra are roughly in visible and ultraviolet light regions,and the two absorption peaks are located in the wavelength span 300-400 nm for charged polyelectrolytes.However,in neutral conjugated polyelectrolytes,the peaks of the absorption spectra showed a blue shift compared with those of the charged polyelectrolytes.Charge transfer (CT) properties of the studied compounds were also investigated with both the three-dimensional real-space analysis method of transition and charge difference densities,and the two-dimensional real-space analysis method of transition density matrices based on the simulated absorption spectra.The calculation results revealed the charge transfer in conjugated polyelectrolytes on the excitation states.