Dec 2013, Volume 7 Issue 4

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    Xin ZHANG, Zichen LI

    Bismaleimides bearing 2,5-diphenyl-1,3,4-oxadiazole chromophores at para, meta, ortho position and corresponding saturated bissuccinimides were synthesized. Several synthetic strategies for these bismaleimides were discussed in detail. Almost no or very weak fluorescence was observed for these bismaleimides, however, the bissuccinimides show a strong fluorescence. The effect of molecular geometry on optical behavior and fluorescence quenching mechanism were investigated by UV-vis absorption and fluorescence emission spectroscopy. The electron coupling of ground state of p-bismaleimide is stronger than those of m- and o-bismaleimides. p-Bissuccinimide displays increasing fluorescence quantum yields with red shifts of 22–24 nm, compared to m-bissuccinimide. Polymerizable C=C bonds play a key role in the intramolecular fluorescence quenching.

    Yang YU, Hong ZHANG, Hong SUN, Dandan XING, Fanglian YAO

    With the excellent biocompatibility and osteoconductivity, nano-hydroxyapatite (nHA) has shown significant prospect in the biomedical applications. Controlling the size, crystallinity and surface properties of nHA crystals is a critical challenge in the design of HA based biomaterials. With the graft copolymer of chitosan and poly(N-isopropylacrylamide) in coil and globule states as a template respectively, a novel composite from chitosan-g-poly(N-isopropylacrylamide) and nano-hydroxyapatite (CS-g-PNIPAM/nHA) was prepared via co-precipitation. Zeta potential analysis, thermogravimetric analysis and X-ray diffraction were used to identify the formation mechanism of the CS-g-PNIPAM/nHA composite and its morphology was observed by transmission electron microscopy. The results suggested that the physical aggregation states of the template polymer could induce or control the size, crystallinity and morphology of HA crystals in the CS-g-PNIPAM/nHA composite. The CS-g-PNIPAM/nHA composite was then introduced to chitosan-gelatin (CS-Gel) polyelectronic complex and the cytocompatibility of the resulting CS-Gel/composite hybrid film was evaluated. This hybrid film was proved to be favorable for the proliferation of MC 3T3-E1 cells. Therefore, the CS-g-PNIPAM/nHA composite is a potential biomaterial in bone tissue engineering.


    Waste frying oil (WFO) is a very important feedstock for obtaining biodiesel at low cost and using WFO in transesterification reactions to produce biodiesel helps eliminate local environmental problems. In this study biodiesel was produced from WFO in sub- and super-critical methanol on a zeolite Y solid acid catalyst. The procedure was optimized using a design of experiments by varying the methanol to WFO molar ratio, the reaction temperature, and the amount of catalyst. Typical biodiesel yields varied from 83 to nearly 100% with methyl esters content ranging from 1.41–1.66 mol·L-1 and typical dynamic viscosities of 22.1-8.2 cP. Gas chromatography was used to determine the molecular composition of the biodiesel. The reaction products contained over 82 wt-% methyl esters, 4.2 wt-% free acids, 13.5 wt-% monoglycerides, and 0.3 wt-% diglycerides. The transesterification of WFO with methanol around its critical temperature combined with a zeolite Y as an acid catalyst is an efficient approach for the production of biodiesel with acceptable yields.

    Lili ZHANG, Ming LIU, Shijun MA, Yaodong HUANG, Yongmei WANG

    Two new C1-symmetric primary-secondary diamines were synthesized via the reaction of (S,S)-1,2-diphenyl ethylene diamine with 3,5-ditert-butyl salicylaldehyde and salicylaldehyde, respectively, followed by reduction with NaBH4. The combination of the ligand from 3,5-ditert-butyl salicylaldehyde with CuBr could effciently catalyze the Henry reaction to afford β-nitroalkanols in moderate to good yields (up to 87%) and high enantioselectivities (up to 88% ee). A possible mechanism of the reaction was proposed.

    Rekha M., H. Kathyayini, N. Nagaraju

    Two catalysts, alumina and manganese oxide supported on alumina, have been prepared by calcination and precipitation-impregnation methods, respectively. The catalysts are characterised by the following techniques: Brunner-Emmett-Teller-N2 adsorption-desorption for surface area, temperature programmed desorption of NH3 and n-butyl amine back titration methods for surface acidity, powder X-ray diffraction for textural properties, and Fourier transform infrared spectroscopy for the anionic radicals. The catalytic activity has been determined under heterogeneous conditions in the condensation reaction between o-phenylenediamine and benzil. The product purity is checked by thin-layer chromatography and melting point. The products are also analysed by LC-MS and 1H-NMR techniques. The yields of the products have been found to be good and catalysts exhibited excellent recyclability. The effect of changing the reaction parameters such as temperature, reaction time, amount of the catalyst, nature of solvent and molar ratio of reactants on the yield of the product has been studied. The surface acidity of the catalysts plays an important role in activating the reaction.

    Liyan LIU, Yu ZHANG, Wei TAN

    Phosphotungstic acid/activated carbon (PTA/AC) catalysts with various AC sizes or PTA content have been synthesized and characterized by N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy and temperature programmed desorption of ammonia. These catalysts were then evaluated in terms of the removal of dibenzothiophene (DBT) by ultrasound-assisted oxidative desulfurization process. The results showed that the DBT conversion obviously increased with the decrease of AC support size and the increase of PTA content. After supporting PTA on AC, the DBT conversion can be improved by 38.9% after ultrasound irradiation for 10 min. In addition, the stability tests of PTA/AC showed that the catalytic oxidative activity of PTA/AC was nearly kept constant after ultrasound irradiation for 20 min, which makes it a promising catalyst to use in ultrasound-assisted oxidative desulfurization process.

    Jasmin Shah, M. Rasul Jan, Attaul Haq, Younas Khan

    An adsorption study of Rhodamine B (RB) dye from aqueous solutions was carried out using walnut shells pretreated by different methods. In addition to the effects of the pretreatment, the effects of various parameters like pH, adsorbent dose, contact time, initial dye concentration and temperature on the adsorption of RB was studied. The adsorption process was highly pH dependent and a maximum adsorption was achieved at pH 3.0. The best fit for the rates of dye adsorption was a pseudo-second-order kinetic model with good correlation coefficients (R2>0.99). Langmuir isotherms were used to determine that the maximum loading capacity of the different walnut shells and the RB capacities ranged from 1.451–2.292 mg·g-1. The dye adsorption was also evaluated thermodynamically. Positive standard enthalpy (?H°) values were obtained indicating that the RB adsorption process is endothermic as well as ?G° and ?S° values showed that adsorption process is spontaneous with an increased randomness at the solid-liquid interface. Desorption studies were carried out to explore the feasibility of regenerating the used walnut shells and it was found that 97.71%–99.17% of the retained RB was recovered with 0.1 mol?L-1 NaOH solution. The walnut shells were also successfully used to remove RB from industrial effluents.

    Xingang LI, Canwei LIN, Lei WANG, Hong LI

    This paper aims to investigate the multi-stage effect on crude distillation units (CDUs) in thermodynamics. In this regard, we proposed three-, four-, five-, and six-stage CDU processes with all variables constrained to be almost the same except for the number of stages. We also analyzed the energy and exergy to assess the energy consumed by each process. Because additional distillation units would share the processing load and thus prevent products with low boiling points from overheating, the heat demand of the CDUs decreases with increasing stages and thus reduces the heat supply. Exergy loss is considered as a key parameter to assess these processes. When the exergy losses in heat exchangers are disregarded, the three- and four-stage CDUs have lower exergy losses than the five- and six-stage CDUs. When the overall exergy losses are considered, the optimum number of stages of CDUs depends on the exergy efficiency of heat integration.

    Jingcai ZHAO, Xingfu SONG, Ze SUN, Jianguo YU

    This study on thermodynamic property of NH3-CO2-H2O system provided the basic data for ammonia carbonation. Simulations on vapor-liquid equilibrium (VLE) of ammonia carbonation with different physical properties were discussed in NH3-H2O and NH3-CO2-H2O systems, respectively. The results indicated that at low temperature (303.15 K–363.15 K) and pressure (0.1–0.4 MPa), the PR (Peng-Robinson) equation was suitable for the description of the thermodynamic state in NH3-H2O system. NRTL (Non-Random-Two-Liquid) series models were selected for NH3-CO2-H2O mixed electrolyte solution system. VLE data regression results showed that NRTL series models were suitable for describing thermodynamic properties of NH3-CO2-H2O system, because average relative error fitting with each model was about 1%. As an asymmetric electrolytes model in NRTL model, E–NRTLRK (Electrolyte NRTL Redlich Kwong) could most accurately fit VLE data of NH3-CO2-H2O system, with fitting error less than 1%. In the extent temperature range of 273.15 K–363.15 K, the prediction of product component using E-NRTLRK model for ammonia carbonation agreed well with the data reported in literature.

    Lin ZHANG, Yan SUN

    Hydrophobic charge induction chromatography (HCIC) is a mixed-mode chromatography which is advantageous for high adsorption capacity and facile elution. The effect of the ligand chain length on protein behavior in HCIC was studied. A coarse-grain adsorbent pore model established in an earlier work was modified to construct adsorbents with different chain lengths, including one with shorter ligands (CL2) and one with longer ligands (CL4). The adsorption, desorption, and conformational transition of the proteins with CL2 and CL4 were examined using molecular dynamics simulations. The ligand chain length has a significant effect on both the probability and the irreversibility of the adsorption/desorption. Longer ligands reduced the energy barrier of adsorption, leading to stronger and more irreversible adsorption, as well as a little more unfolding of the protein. The simulation results elucidated the effect of the ligand chain length, which is beneficial for the rational design of adsorbents and parameter optimization for high-performance HCIC.

    Asghar Azizi, Seid Ziaoddin Shafaei, Mohammad Noaparast, Mohammad Karamoozian

    The role of pH, solid content, water chemistry and ore mineralogy on the galvanic interactions between chalcopyrite and pyrite and low alloy steel balls were investigated in the grinding of Sarcheshmeh porphyry copper sulfide ore. All these factors strongly affect the galvanic current between the minerals and the steel during the grinding process. The galvanic current density decreased as the solution pH and percent solids increased. In addition, changing the water in the ball mill from tap to distilled water reduced the galvanic current between the minerals and the balls. Potentiodynamic polarization curves showed that pyrite and chalcopyrite demonstrated typical active-passive-transpassive anodic behavior in the grinding of copper ore. However, the nature of their transitions from the active to the passive state differed. This behavior was not seen in the grinding of pure minerals. In addition, an EDTA extraction technique was employed to quantify the amount of oxidized iron in the mill discharge. The amount of extractable iron was influenced by the same experimental factors and in the same way as the galvanic current.

    Shuna LI, Huawei YANG, Donghui ZHANG

    Cu(I)Y adsorbent was prepared by reduction of Cu(II)Y which was prepared by ion exchange between the NaY zeolite and a solution of Cu(II) chloride. The dynamic adsorption capacity of Cu(I)Y for CO was calculated by adsorption breakthrough curve measured on a fixed bed at 30°C and 0.006 MPa (g) of CO partial pressure. The calculated CO adsorption capacity was 2.14 mmol/g, 37.5 times as much as that of NaY zeolite. The adsorption breakthrough curve experiment was also simulated with Aspen Adsorption software and the results were approximately consistent with experimental results. Then a five-bed VPSA process for separating CO from syngas on this adsorbent was dynamically simulated with Aspen Adsorption software with the adsorption pressure of 0.68 MPa (g) and the desorption pressure of -0.075 MPa (g). The results showed that CO was enriched from 32.3% to 95.16%–98.12%, and its recovery was 88.47%–99.44%.

    Jacqueline CONCHA, Caroline WEINSTEIN, María Elvira Zú?IGA

    In the last years, sugar beet pectins have been the subject of several investigations involving extraction methodologies, chemical composition and functional properties. The structure of pectins, which depends on the extraction method, is decisive in their capacity to induce apoptosis on several cancer cell lines like colon, prostate and breast. In this work, sugar beet pectin extraction was performed in the following steps: lipid extraction with hexane, removal of soluble complex carbohydrates and proteins, and enzymatic treatment with amyloglucosidase, protease, and pectinase. The enzymatic treatment was carried out with Rohapect DA6L under the following conditions: 50°C, pH 4.0, 2% enzyme/substrate (E/S) ratio, 15 h, and a solid to liquid ratio of 1 ∶ 10. The pectic extract showed a degree of polymerization (DP) profile of 55.8% with DP≥7; 4.9% with DP6; 5.8% between DP2 and DP6 ; 4.7% with DP2; and 28.8% with DP1. The pectic extract was examined for its antiproliferative activity on the MCF-7 breast cancer cell line. At a concentration range of 12.5–25 mg/mL the pectic extract killed 80.6% of the cells, exhibiting a higher antiproliferative activity than 4-hydroxytamoxifen (4-OHT), a classical anticancer drug, which killed 56.5% of the cells.

    Xinwei ZHANG, Shudong ZHANG, Xiaodan SUN, Zequn YIN, Quanjie LIU, Xiwen ZHANG, Qiuxiang YIN

    The induction time of cefodizime sodium was measured in ethanol-water at different solvent compositions by the laser technology measurement. The results indicate that the solvent composition played an important role in the supersaturation and the nucleation process of cefodizime sodium solution. According to the modified classical nucleation theory, the nucleation and growth mechanism were identified. The correlation results show that heterogeneous nucleation dominated the nucleation process at lower supersaturation, where homogeneous nucleation is the most important mechanism at higher supersaturation. Based on the correlated results, the 2D mediated growth mechanism had the highest correlation coefficients (R2), so this mechanism was selected as the proper growth mechanism for cefodizime sodium.

    Huining HE, Qiuling LIANG, Meong Cheol SHIN, Kyuri LEE, Junbo GONG, Junxiao YE, Quan LIU, Jingkang WANG, Victor YANG

    Successful development of a new drug is prohibitively expensive, and is estimated to cost approximately $100–500 million US dollars for a single clinical drug. Yet, a newly developed drug can only enjoy its patent protection for 18 years, meaning that after this protected time period, any company can manufacture this product and thus the profit generated by this drug entity would reduce dramatically. Most critically, once a drug is being synthesized, its physical, chemical, and biological attributes such as bioavailability and in vivo pharmacokinetics are all completely fixed and cannot be changed. In principal and practice, only the application of an appropriately designed drug delivery system (DDS) is able to overcome such limitations, and yet the cost of developing a novel drug delivery system is less than 10% of that of developing a new drug. Because of these reasons, the new trend in pharmaceutical development has already begun to shift from the single direction of developing new drugs in the past to a combined mode of developing both new drugs and innovative drug delivery systems in this century. Hence, for developing countries with relatively limited financial resources, a smart strategic move would be to focus on the development of new DDS, which has a significantly higher benefit/risk ratio when comparing to the development of a new drug.

    Because of the unmatched reaction efficiency and a repetitive action mode, the therapeutic activity of a single bio-macromolecular drug (e.g., protein toxins, gene products, etc.) is equivalent to about 106–108 of that from a conventional small molecule anti-cancer agent (e.g., doxorubicin). Hence, bio-macromolecular drugs have been recognized around the world as the future “drug-of-choice”. Yet, among the>10000 drugs that are currently available, only ~150 of them belong to these bio-macromolecular drugs (an exceedingly low 1.2%), reflecting the difficulties of utilizing these agents in clinical practice. In general, the bottleneck limitations of these bio-macromolecular drugs are two-fold: (1) the absence of a preferential action of the drug on tumor cells as opposed to normal tissues, and (2) the lack of ability to cross the tumor cell membrane. In this review, we provide strategies of how to solve these problems simultaneously and collectively via the development of innovative drug delivery systems. Since worldwide progress on bio-macromolecular therapeutics still remains in the infant stage and thus open for an equal-ground competition, we wish that this review would echo the desire to industrialized countries such as China to set up its strategic plan on developing delivery systems for these bio-macromolecular drugs, thereby realizing their clinical potential.