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01 February 2013, Volume 29 Issue 1

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Cover and Content of Chemical Research in Chinese Universities Vol.29 No.1(2013)

2013, 29(1):  0-0. 

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Facile Chemical Conversion Synthesis and Luminescence Properties of Uniform YF₃ Nanowires

XU Zhen-he, GAO Yu, GE Xin, SUN Ya-guang

2013, 29(1):  1-5.  doi:10.1007/s40242-013-2311-8

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Well-dispersed YF₃ nanowires were synthesized by a designed hydrothermal conversion method with Y(OH)₃ nanowires as precursor. Various equipments were used to characterize the samples. The results show that Y(OH)₃ nanowires precursor was prepared through a simple hydrothermal process, which then served as the precursor for the fabrication of YF₃ nanowires by a hydrothermal process. The whole process was carried out under aqueous conditions without any organic solvent, surfactant or catalyst. The conversion process from Y(OH)₃ precursor to YF₃ nanowires was investigated by time-dependent experiments. The possible formation mechanism of YF₃ nanowires was presented in detail. Under UV excitation, 5%(mass fraction) Eu³⁺ or 5%(mass fraction) Tb³⁺ doped YF₃ samples exhibit strong red or green emission, corresponding to the characteristic lines of Eu³⁺ and Tb³⁺, respectively. Moreover, the luminescence colors of the Eu³⁺ and Tb³⁺ codoped YF₃ samples can be tuned from red, yellow and green-yellow to green by simply adjusting the relative doping concentrations of the activator ions under a single wavelength excitation, which might find potential applications in the fields of, such as, light display systems and opto- electronic devices.



Construction of Two Chiral Bilayer Coordination Polymers Based on 2-(Pyridine-3-yl)-1H-4,5- imidazoledicarboxylate Ligand

ZHOU Xiao-ying, JING Xue-min, XU Da, YAN Wei-wei, LI Guang-hua, ZHANG Li-rong

2013, 29(1):  6-9.  doi:10.1007/s40242-013-2194-8

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Two novel isomorphic coordination polymers [Zn(HPyImDC)H₂O](1) and [Co(HPyImDC)H₂O](2) were synthesized from 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid (H₃PyImDC) under hydrothermal conditions. Both the compounds crystallized in P2₁2₁2₁ chiral space group, possessing left-hand helical chains and right-hand helical chains. Two types of helical chains connected with each other to form an interesting 2D bilayer structure which extended to a 3D supermolecular structure via the hydrogen-bonding interactions. Topology analysis shows that H₃PyImDC ligand and metal center can be regarded as 3-connected T-shaped nodes, thus leading to a (3,3)-connected network with vertex symbol of (8²·10).



Two New Piperazine Templated Lanthanide Sulfates with 2D Corrugated Layered Crystal Structures

ZHANG Deng, FAN Xin-rong, LU Yun, XU Yan

2013, 29(1):  10-14.  doi:10.1007/s40242-013-2110-2

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Two new piperazine templated lanthanide sulfates (C₄N₂H₁₂)_1.5[Ln(SO₄)₃(H₂O)]·H₂O[Ln=Gd(1), Tb(2)] have been synthesized solvothermally and structurally characterized by single crystal X-ray diffraction(XRD), infrared(IR) spectroscopy, thermal analysis, fluorescent spectra and inductively coupled plasma(ICP). Single crystal X-ray diffraction reveals that both compounds 1 and 2 crystallized in the monoclinic crystal system, with space group P2₁/c and cell dimensions: a=0.64468(19) nm, b=2.9979(9) nm, c=0.9818(3) nm, β=101.271(4)°, V=1.8608(10) nm³, Z=4 for compound 1; a=0.64259(19) nm, b=3.0010(9) nm, c=0.9812(3) nm, β=101.229(4)°, V=1.8560(10) nm³, Z=4 for compound 2. Compounds 1 and 2 are isomorphous and have similar 2D corrugated inorganic frameworks fabricated via the connection of single chains and S2O₄ groups, while fully protonated piperazine cations and water molecules are located between the inorganic layers. The solid state luminescent properties of compound 2 were investigated and it displayed a typical luminescent property of Tb³⁺ with excitation wavelength at 371 nm.



Portable Analyzer for Rapid Analysis of Total Protein, Fat and Lactose Contents in Raw Milk Measured by Non-dispersive Short-wave Near-infrared Spectrometry

FENG Xu-dong, SU Rui, XU Nan, WANG Xing-hua, YU Ai-min, ZHANG Han-qi, CAO Yan-bo

2013, 29(1):  15-19.  doi:10.1007/s40242-013-2191-y

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A novel portable analyzer for raw milk quality control during the material purchase at dairy plants was developed, by which the percentages(mass fraction) of main components including total protein, fat, and lactose of an unhomogenized milk sample could be determinated in 1 min with the help of non-dispersive short-wave near-infrared (NDSWNIR) spectrometry in a wavelength range from 600 nm to 1100 nm and multivariate calibration. The analyzer was designed with a single-beam optical system, which comprised a temperature control module, a multi-channel narrow-band light source(16 wavelengths), a glass absorption cell with 15 mm sample thickness, a silicon photodiode detector, several compound lenses and a recorder module. A total of 80 raw milk samples were collected at a dairy farm twice a month for 4 months. The samples were scanned with a common UV-Vis-NIR spectrometer and analyzed according to China GB standard methods. The uninformative variables elimination(UVE) method was carried out on the spectrum data and the percentages of main components of all the samples to choose the peak emitting wavelength of each channel of the light source. Another 90 raw milk samples were collected from the same dairy farm thrice a month for 3 months. The samples were analyzed according to China GB standard methods and with the proposed analyzer. The percentages of the main components and the NDSWNIR absorption data of the samples were used for the construction and validation of the multivariate calibration model with partial least squares(PLS) method. The root-mean-square errors of prediction(RMSEP) of total protein, fat and lactose were 0.201, 0.172 and 0.247 and the coefficients of correlation(R) were 0.932, 0.981 and 0.933, respectively.



Interaction Between Baicalein and Amyloid-β Fibrils Studied by Fluorescence Spectroscopy

SONG Sheng-mei, WANG Yong-xiang, XIONG Li-min, QU Ling-bo, XU Mao-tian

2013, 29(1):  20-25.  doi:10.1007/s40242-013-2180-1

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The interaction between baicalein and amyloid-β(Aβ) polypeptide was investigated by fluorescence and UV-Vis absorbance spectroscopy. The absence of the characteristic peak of tyrosinate(Tyr) in the absorption spectra of Aβ-baicalein complexes provided evidence that the sole Tyr residue in Aβ is not bound to baicalein, but remains close to it. The intrinsic fluorescence of Tyr residues in Aβ_1―42 aggregates was quenched strongly by the excited-state ionization of baicalein. In this complex the hydroxyl group was not ionized, but to ionize immediately upon excitation. Absorbance, fluorescence and synchronous spectroscopies show that the formation of Schiff base between the quinone of baicalein and the lysine(Lys) side chains of Aβ_1―42 is another major reason in the depolymerization of Aβ_1―42 aggregates by baicalein. It is desirable that our research would offer some valuable reference for the application of flavonoid derivants in Alzheimer's disease(AD) treatment.



Novel Method for Indirect Determination of Iodine in Marine Products by Atomic Fluorescence Spectrometry

LU Jian-ping, TAN Fang-wei, TANG Qiong, JIANG Tian-cheng

2013, 29(1):  26-29.  doi:10.1007/s40242-013-2171-2

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A method for the determination of iodine based upon compound H₂HgI₄, formed between I^- and Hg²⁺ in nitric acid and extracted in methyl isobutyl ketone(MIBK), was developed via atomic fluorescence spectrometry(AFS). After the compound is reduced with potassium borohydrid(KBH₄), the resultant mercury vapor was injected into the instrument and iodine was, therefore, indirectly determined. Experimental parameters such as the conditions of extraction reagents, aqueous phase acidity, elemental mercury diffusion temperature in a vial and other factors were investigated and optimized. Under the optimum experimental conditions, this method shows a detection limit of 0.038 μg/L iodine and a linear relationship between 0.04―20 μg/L. The method was applied to determining the iodine content in marine duck eggs, kelps, laver and Ganoderma lucidum spirulina, showing a relative standard deviation(RSD) of 2.15% and the recoveries in the range of 98.1%―102.5%.



Determination of Dioxins in Blood Using Nano-baskets Doped in EmulsionLiquid Membranes

MOKHTARI Bahram, POURABDOLLAH Kobra

2013, 29(1):  30-36.  doi:10.1007/s40242-013-2048-4

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Extraction of dioxins from blood samples was carried out by inclusion-facilitated emulsion liquid membrane process. The novelty of this work is the application of nano-baskets of calixarene and emulsion liquid membranes in the selective and efficient preconcentration of dioxin. For this aim, four derivatives of p-tert-calix[4]arene bearing different sulfonamide moieties were synthesized and their inclusion-extraction parameters were optimized including the calixarene's scaffold and concentration(as the carrier/demulsifier), the diluent type in membrane, the phase and the treat ratio, mixing speed, and initial solute concentration. Determinations were followed by a gas chromatograph and the results reveal that under the optimized operating conditions, the preconcentration of dioxins was improved and the method achieved lower limit of detections(LODs). Under optimal conditions, the figures of merits were determined to be LOD 1.0 pg/L, dynamic range 0.6―112.0 pg/L, RSD 5.5%(n=5), and the maximum enrichment factor and recovery were determined to be 3.3 and 99%, respectively.



In situ Remediation of Petroleum Contaminated Groundwater by Permeable Reactive Barrier with Hydrothermal Palygorskite as Medium

ZHANG Sheng-yu, ZHANG Yu-ling, SU Xiao-si, ZHANG Ying

2013, 29(1):  37-41.  doi:10.1007/s40242-013-2303-8

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The permeable reactive barrier(PRB) has proven to be a cost-effective technique to remediate the petroleum contaminated groundwater at a northeast field site in China. In this study, the geology, hydrogeology and contamination characterization of the field site were investigated and the natural hydrothermal palygorskite was chosen as a reactive medium. Furthermore, the adsorption of the total petroleum hydrocarbons(TPH) in the groundwater onto hydrothermal palygorskite and the adsorption kinetics were investigated. The results indicate that the removal rates of TPH, benzene, naphthalene and phenantharene could all reach up to 90% by hydrothermal palygorskite with a diameter of 0.25―2.00 mm that had been thermally pretreated at 140 ℃. The adsorption of TPH onto hydrothermal palygorskite after pretreatment followed a pseudo-second-order kinetic model and a Langmuir adsorption isotherm, suggesting that the theoretic adsorption capacity of hydrothermal palygorskite for adsorbate could be 4.2 g/g. Scanning electron microscopy(SEM), infrared spectroscopy(IR), X-ray diffraction(XRD) and X-ray fluorescence spectroscopy(XRF) were carried out to analyze the adsorption mechanism. The results reveal that hydrothermal palygorskite is a fibrous silicate mineral enriched in Mg and Al with large surface area and porosity. The dense cluster acicular and fibrous crystal of hydrothermal palygorskite, and its effect polar group ―OH played an important role in the physical and chemical adsorption processes of it for contaminants. This study has demonstrated hydrothermal palygorskite is a reliable reactive medium for in situ remediation of petroleum contaminated groundwater at field sites.



Thermodynamic Characteristics and Mechanisms of Heavy Metals Adsorbed onto Urban Soil

LI Yue-ming, KANG Chun-li, CHEN Wei-wei, MING Lian, ZHANG Sai, GUO Ping

2013, 29(1):  42-47.  doi:10.1007/s40242-013-2200-1

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The thermodynamic characteristics of heavy metals adsorbed onto urban soil and the relative adsorption mechanisms were studied by the batch experiment. The results show that there existed dynamic adsorption-desorption equilibrium processes of cationic and anionic ions of heavy metals onto urban soil, which may have an impact on the pH of the adsorption system. The amounts of heavy metals adsorbed onto urban soil increased with the increase of the equilibrium concentration, but their adsorption amounts were not the maximum adsorption amounts. The higher the pH was, the greater the adsorption capacity of the urban soil at the same equilibrium concentration was, and the adsorption amounts of heavy metals onto urban soil followed the order of Pb>Cu>Cd>Zn>Ni. There were coordination reaction, hydrolysis reaction, exchange reaction in the adsorption processes of heavy metals onto urban soil. With the increase of pH, the influencing degree of pH on the different reactions of heavy metals in the soil increased, meanwhile the effects of other physicochemical properties of soil on the adsorption of heavy metals were weakened.



Anilido-imine Zinc Complexes: Efficient Catalysts for Ring-opening Polymerization of L-Lactide

YAO Wei, CUI Ning, XUE Ying-zhao, LIU Tian-tian, WANG Yan

2013, 29(1):  48-50.  doi:10.1007/s40242-013-2229-1

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A series of anilido-imine zinc complexes ortho-C₆H₄(CH=NAr)(NAr)ZnEt[Ar=2,6-Me₂C₆H₃(2a); Ar=2,6-Et₂C₆H₃(2b)] was synthesized, characterized and used as catalysts for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol. The effects of the structures of catalysts and reaction conditions on the reactivity were investigated. The polymerization of L-lactide initiated by each of these complexes was found to take place with a controlled manner.



Design, Syntheses and Biological Activities of Novel Anthranilic Diamide Insecticides Containing N-Pyridylpyrazole

ZHAO Yu, LI Yong-qiang, XIONG Li-xia, XU Li-ping, PENG Li-na, LI Fang, LI Zheng-ming

2013, 29(1):  51-56.  doi:10.1007/s40242-013-2167-y

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In search of environmentally benign insecticides with high activity, low toxicity and low residue, a series of novel anthranilic diamide derivatives containing N-pyridylpyrazole was designed and synthesized. All the compounds were characterized by ¹H NMR spectroscopy and elemental analysis. The single crystal structure of compound 8j was determined by X-ray diffraction. The insecticidal activities of the new compounds were evaluated. The results show that some compounds exhibited moderate insecticidal activities against Lepidoptera pests. Among this series of compounds, compounds 8o and 8p showed 100% larvicidal activity against Mythimna separate Walker, Plutella xylostella Linnaeus and Laphygma exigua Hubner at a test concentration of 200 mg/kg, which is equal to the commercial chlorantraniliprole.



A New Synthetic Approach to Elvucitabine

ZHANG Ling-yu, LOU Yuan-yuan, ZHAO Gui-long, ZHANG Lin-shan, CHEN Yan

2013, 29(1):  57-61.  doi:10.1007/s40242-013-2161-4

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A new synthetic approach to elvucitabine started from L-xylose via the reactions of 10 steps in an overall yield of 20% was developed. The key steps included trimethylsilyl trifluoromethanesulfonate(TMSOTf)-mediated stereocontrolled β-glycosidation and exquisite choice of chloroacetyl group for the protection of hydroxyl groups as well as the corresponding deprotection under notably mild conditions. The structure of elvucitabine, in particular, the stereochemistry thereof, was unambiguously determined by comparison of the physical properties, such as ¹H NMR data and the specific rotation, of the synthesized sample with those reported.



Syntheses and Antiproliferative Activities of Novel Diarylthiosemicarbazide Derivatives

ZHAI Xin, HE Ying, YANG Zhen, GONG Ping

2013, 29(1):  62-66.  doi:10.1007/s40242-013-2136-5

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A series of novel N-methylpicolinamide-moiety containing diarylthiosemicarbazide derivatives was prepared and evaluated for their in vitro antiproliferative activity against three cancer cell lines(human alveolar epithelial cell A549, human lung cancer cell H460 and human colorectal cancer cell HT-29) by 3-(4,5-dimethyl)thiazolyl-diphenyltetrazoliumromide(MTT) assay. Six compounds(7b―7g) with halogen substituents exhibited preferable cytotoxicity against one or more cell lines in a low micromolar range. Especially, the most promising compound 7g exhibited remarkable antiproliferative activity with the IC50 values of 2.2, 1.8 and 5.2 μmol/L against A549, H460 and HT-29 cell lines respectively, which is comparable to sorafenib.



Design, Synthesis and Evaluation of 6-Oxo-1, 6-dihydropyrimidine-2, 5-dicarboxamide Derivatives as MMP 13 Inhibitors

LU Hai-bin, WANG Shi-han, LI Qing-min, WANG Yong-sheng

2013, 29(1):  67-70.  doi:10.1007/s40242-012-2131-2

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We designed and synthsized a series of novel 6-oxo-1,6-dihydropyrimidine-2,5-dicarboxamide derivatives and evaluated their inhibition effects on MMP 3, MMP 12 and MMP 13. The pharmacological results show that they have potent and highly selective activity of inhibiting MMP 13.



Rapid Synthesis of Glycosyl Bromides by Ultrasound Irradiation

ZHAO Jin-zhong, ZHANG Xue-qin, WU Xin, XING Ze-bing, YUE Ai-qin, SHAO Hua-wu

2013, 29(1):  71-75.  doi:10.1007/s40242-012-2102-7

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A convenient and environmentally friendly reactor for the synthesis of glycosyl bromides via ultrasound irradiation was designed. Peracetylated glycosyl bromides were synthesized from free saccharides by means of a one-pot method. Benzoylated and 6-subsituted glycosyl bromides were prepared from protected saccharides. The glycosyl bromides were obtained in isolated yields of 83% to 96%.



Synthesis and Antitussive Effect of New Hydantoin Compounds

ZHANG Qun-li, SONG Li-jun, WANG En-si

2013, 29(1):  76-81.  doi:10.1007/s40242-012-2064-9

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A series of new hydantoin compounds was synthesized with 3-bromo phenylacetic acid and 3,4-dimethylbromobenzene as starting material, 7-bromo-2-tetralone and 2-bromo-5,6,8,9-tetrahydro-7-benzocyclo- heptenone as intermediate and Ullmann reaction, Suzuki reaction and Bucherer-Berg's reaction as key steps. The structures of the key intermediate and target compounds were confirmed by ¹H NMR, ¹³C NMR, IR and MS. Bioactivity research showed that target compounds 6a, 6c, 6d, 6e and 15i had significant antitussive effect on the ammonia-induced cough of mice.



Efficient One-pot Synthesis of 12-Aryl-8, 9, 10, 12- tetrahydrobenzo[a]xanthen-11-ones Under Solvent-free Conditions

JIA Xu-dong, HAN Song-yang, DUAN Hai-feng, LIN Ying-jie, CAO Jun-gang, LIANG Da-peng, WU Mao-cheng

2013, 29(1):  82-86.  doi:10.1007/s40242-013-0001-1

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Multi-component condensation of 2-naphthol, aromatic aldehydes, and cyclic 1,3-dicarbonyl compounds catalyzed by ionic liquid [NSPTEA][HSO₄] was accomplished for the synthesis of a series of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-ones under solvent-free conditions. High yields, ease recovery, short reaction time and reusability of catalyst are significant advantages. ZrOCl₂·8H₂O was also found to act as an effective catalyst towards this transformation.



Effects of Combinatorial Expression of selA, selB and selC Genes on the Efficiency of Selenocysteine Incorporation in Escherichia coli

XU Ya-wei, JIANG Zhi-hua, MU Ying, ZHANG Lei, ZHAO Si-qi, LIU Shu-jun, WANG Cheng, ZHAO Yang, Lü Shao-wu, YAN Gang-lin, LUO Gui-min

2013, 29(1):  87-94.  doi:10.1007/s40242-013-2250-4

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In Escherichia coli, four gene products(selA, selB, selC and selD) and a selenocysteine(Sec) insertion sequence(SECIS) are required for the correct translation of UGA codons encoding Sec. Previous studies have shown that the stoichiometry of selenoproteine mRNA and elongation factor SelB affect the efficiency of Sec incorporation. Herein lies a detailed analysis of the effects of co-expressing selA, selB and selC genes under inducible promoters on the incorporation efficiency of Sec. Over-expression of either selA or selB reduced the efficiency of Sec incorporation by 61.1% or 11.6%, respectively, compared to the over-expression of the reporter vector alone did. Concomitant over-expression of selC with selA or selB completely reversed the reduce of the efficiency of Sec but still reduced the efficiency of the incorporation relative to that observed for expression of selC alone. Over-expression of selC gene alone under L-arabinose induction reduced the efficiency of the incorporation relative to that observed for co-expressing selC with selA and selB under the control of its endogenous promoter in the absence of L-arabinose. Co-expression of selA, selB and selC with selA or selB under the control of inducible promoters increased the efficiency of Sec incorporation by 69.7%. Moreover, inducing selenoprotein-related gene expression during the late exponential phase increased the efficiency of Sec incorporation by a factor of 5.4 relative to that observed for the reporter vector alone. These results suggest that the co-expression of selA, selB and selC in Escherichia coli under the control of inducible promoters is a viable and promising strategy for increasing the yields of selenoproteins.



Preparation of Optically Active Alkoxy-serines from Amino-amide Racemate Catalyzed by Escherichia coli Cells with Peptidase B Activity

WANG Zhi-yuan, LIU Jun-zhong, XU Li-sheng, ZHANG Hong-juan, LIU Qian, JIAO Qing-cai

2013, 29(1):  95-98.  doi:10.1007/s40242-012-2249-2

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Alkoxy-L-serines are useful for peptide syntheses. The demand for alkoxy-L-serines in the pharmaceutical industries continues to increase because of their multiple physiological effects. In this research, an improved method for alkoxy-L-serines synthesis is reported. A series of substrates, DL-β-alkoxy-α-amino propionamides, was used for the synthesis of alkoxy-serines catalyzed by Escherichia coli cells with peptidase B(PepB) activity. The results show that PepB has a high resolution activity with DL-β-alkoxy-α-amino propionamides as substrate. Reaction conditions were optimized, i.e., DL-β-methoxy-α-amino propionamide as substrate at pH=9.0, 40 ℃ and 14 h, and the optimal reaction concentration is 400 mmol/L. The results also show that divalent metal cations exhibit different effects on the PepB activity, for example, Zn²⁺ and Cu²⁺ can obviously inhibit the activity of PepB, whereas Co²⁺, Ca²⁺, Mn²⁺ and Mg²⁺ at low concentrations can activate PepB. This research provides access to enantiomerically enriched and valuable alkoxy-L-serines from a simple amino-amide racemate.



Anti-diabetic Effects of Polysaccharides from Ethanol-insoluble Residue of Schisandra chinensis(Turcz.) Baill on Alloxan-induced Diabetic Mice

ZHAO Ting, MAO Guang-hua, ZHANG Min, LI Fang, ZOU Ye, ZHOU Ye, ZHENG Wei, ZHENG Da-heng, YANG Liu-qing, WU Xiang-yang

2013, 29(1):  99-102.  doi:10.1007/s40242-012-2218-9

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The ethanol-insoluble residue of Schisandra generated during lignans industrial production is usually treated as solid waste. However, there is active polysaccharide which could be used in it. In this work, the water-soluble polysaccharides from the ethanol-insoluble residue of Schisandra(ESCP) were obtained and their anti-diabetic effect was evaluated. The results indicate that ESCP could significantly reduce the blood glucose level in alloxan-induced diabetic mice. Moreover, the ESCP could significantly improve the lipid metabolism and increase the content of liver glycogen in alloxan-induced diabetic mice. The results indicate that ESCP could be developed into a potential natural hypoglycemic agent.



Fabrication of a Magnetite Nanoparticle-loaded Polymeric Nanoplatform for Magnetically Guided Drug Delivery

DING Guo-bin, LIU Hui-ying, WANG Yan, Lü Yan-yun, WU Yi, GUO Yi, XU Li

2013, 29(1):  103-109.  doi:10.1007/s40242-013-2134-7

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We developed a magnetite nanoparticle-loaded polymeric nanoplatform for magnetically guided 10-hydroxycamptothecin(HCPT) delivery. The nanoplatform was fabricated by simultaneously incorporating magnetite nanoparticles(NPs) and HCPT into the polymer micelle self-assembled from methoxy polyethylene glycol- poly(D,L-lactide-co-glycolide)(MPEG-PLGA) copolymer. Successful loading of HCPT into the nanoplatform was confirmed by Fourier transform infrared(FTIR) spectroscopy. Subsequently, we examined the in vitro antitumor efficacy of free HCPT and nanoplatform against three different cancer cell lines—HeLa, A549 and HepG2. Flow cytometric analysis was conducted to reveal the cell apoptosis caused by free HCPT and nanoplatform. Finally, the magnetic targeting property of the nanoplatform was evaluated by a self-designed in vitro experiment.



Thermal and Optoelectronic Properties of Anthracene andDibenz[a,c]Anthracene

MUDDASIR Hanif, WANG Zhi-ming, YANG Bing, LU Ping, MA Yu-guang

2013, 29(1):  110-115.  doi:10.1007/s40242-013-2264-y

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The basic characteristics of anthracene(AN) and dibenz[a,c]anthracene(D[a,c]A) derivatives, important semiconductors, were systematically studied. Differential scanning calorimetry(DSC) shows that D[a,c]A has the reversibility of solid and liquid phases. Thermalgravimetric analysis(TGA) shows that D[a,c]A exhibits higher T_d(decomposition temperature), which indicates D[a,c]A, as active layers, should be more suitable to being made into stable devices. D[a,c]A shows blue-shifted UV-Vis absorption and emission despite increased conjugation compared to anthracene due to different symmetries. Both the compounds are planar and show weak blue fluorescence in the tetrahydrofuran(THF) solution and higher fluorescence in the solid-state, due to different energy levels in solution and solid-state, explained via Jablonski diagram.



Optimization of Electrolyte Conductivity for Li-ion Batteries Based on Mass Triangle Model

REN Yong-huan, WU Bo-rong, MU Dao-bin, YANG Chun-wei, ZHANG Cun-zhong, WU Feng

2013, 29(1):  116-120.  doi:10.1007/s40242-013-2179-7

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Mass triangle model was applied to lithium ion battery for electrolyte conductivity forecasting. Seven kinds of electrolytes with different proportions of 3 solvents were prepared. The solvent proportions of the seven electrolytes varied so as to make the seven coordinate points distribute in the ternary coordinate system to form a forcasting region by the connection of them. Their conductivities were tested and the conductivity value in the forecasting region was calculated based on the tested value by mass triangle model. Conductivity isolines formed in the region and blank area showing no forecasted value existed simultaneously. Optimized electrolyte with superior conductivity was selected according to conductivity variation trendency combined with the attention paid to the no-value-shown blank area. The conductivity of optimized electrolyte{m[ethyl carbonate(EC)]:m[propylene carbonate(PC)]:m[ethylmethyl carbonate(EMC)]=0.19:0.22:0.59} was 0.745 mS/cm at -40 ℃, increased by a factor of 51.4% compared to 0.492 mS/cm of common electrolyte[m(EC):m(PC):m(EMC)=1:1:1]. The accuracy of mass triangle model was demonstrated from the perspective that the maximum value existed in the blank area. Batteries with this optimized electrolyte exhibited a better performance.



Effect of Magnetic Carrier NiFe₂O₄ Nanoparticles on Physicochemical and Catalytic Properties of Magnetically Separable Photocatalyst TiO₂/NiFe₂O₄

XU Shi-hong, TAN Dong-dong, BI De-fu, SHI Peng-hui, LU Wei, SHANGGUAN Wen-feng, MA Chun-yan

2013, 29(1):  121-125.  doi:10.1007/s40242-013-2143-6

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A series of magnetically separable photocatalyst TiO₂/NiFe₂O₄(TN) with different mass ratios of NiFe₂O₄ to TiO₂ was prepared by sol-gel method. The X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM), ultraviolet-visible spectroscopy(UV-Vis), Brunauer-Emmett-Teller(BET) surface analysis and photoluminescence spectroscopy(PL) were used to characterize the photocatalyst TN. The XRD patterns of TN indicate that adulterating a smidgen of NiFe₂O₄ into TiO₂(about 0.1%, mass ratio) can promote the phase transformation of TiO₂, however, when the doped amount of NiFe₂O₄ surpasses 1%, the introduction of NiFe₂O₄ can inhibit the growth of TiO₂ crystal grain and reduce the size of TiO₂ crystal grain. The XPS results of TN indicate that some Fe³⁺ replace Ti⁴⁺ of the TiO₂ lattice forming Fe―O―Ti bonds. The PL analysis of TN shows that the NiFe₂O₄ nanoparticles in photocatalyst TN play the role of the effective recombination centre of the photogenerated electrons and holes, leading to the decrease in photocatalytic activity.



Adsorption of Heavy Metal Ions from Aqueous Solutions by Zeolite Based on Oil Shale Ash: Kinetic and Equilibrium Studies

BAO Wei-wei, ZOU Hai-feng, GAN Shu-cai, XU Xue-chun, JI Gui-juan, ZHENG Ke-yan

2013, 29(1):  126-131.  doi:10.1007/s40242-013-2139-2

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Na-A zeolite was successfully synthesized via the alkaline fusion method with oil shale ash as the raw material. The adsorption capacity of it was tested by removing Cu²⁺, Ni²⁺, Pb²⁺ and Cd²⁺ from aqueous solutions. The results reveal the maximum adsorption capacity of adsorbent for Pb²⁺, Cu²⁺, Cd²⁺ and Ni²⁺ were 224.72, 156.74, 118.34 and 53.02 mg/g, respectively. The effects of contact time and pH value of solutions on the adsorption efficiency of the zeolite were evaluated. Besides, The equilibrium adsorption data and the batch kinetic data were correlated with Langmuir and Freundlich models and the pseudo-first-order and pseudo-second-order models separately. The results show that the Langmuir isotherm and the pseudo-second-order equation were more suitable for the adsorption of Na-A zeolite for the metal ions. In addition, Thermodynamic parameters of the adsorption(the Gibbs free energy, entropy, and enthalpy) were also evaluated and discussed. The results demonstrate that the adsorption process was spontaneous and endothermic under natural conditions and the synthesized zeolite was an effective adsorbent for the removal of metal ions from aqueous solution.



Highly Sensitive and Selective Amperometric Sensor for Iodate Based on 9,10-Phenanthrenequinone Derived Graphene

WANG Hong-juan, CHENG Na-na, YANG Xiao-yang, LI Xiao-meng, ZHU Lian-de

2013, 29(1):  132-138.  doi:10.1007/s40242-013-2118-7

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We reported on a new amperometric sensor for the sensitive and selective determination of iodate in table salt. The iodate sensor was constructed by the integration of a novel nanocomposite which was made from 9,10-phenanthrenequinone(PQ) and graphene(GP) with a glassy carbon electrode(GCE). The synthesized graphene and the nanocomposite were well characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), Fourier transform infrared(FTIR) spectroscopy and Raman spectroscopy. We fully studied the electrochemical behavior and kinetic characteristics of the PQ/GP nanocomposite at GCE. The PQ/GP electrode shows a good electrochemical catalytic activity towards the reduction of iodate, which makes itself a sensitive and selective electrochemical sensor for iodate. The iodate sensor displays a high sensitivity(1.04 mA·mmol·L^-1), a low detection limit(1.0×10^-8 mol/L), a rapid response(less than 2 s), and a broad linear range(from 5.0×10^-8 mol/L to 6.0×10^-3 mol/L ). In addition, the sensor is interference free. The practical application of the proposed sensor was tested by the detection of iodate in table salt.



Using Homology Modeling, Molecular Dynamics and Molecular Docking Techniques to Identify Inhibitor Binding Regions of Somatostatin Receptor 1

LAN Hai-nan, WANG Yue-xi, ZHENG Ming-zhu, HAN Wei-wei, ZHENG Xin

2013, 29(1):  139-143.  doi:10.1007/s40242-013-2103-1

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The G protein coupled receptor(GPCR), one of the members in the superfamily, which consists of thousands of integral membrane proteins, exerts a wide variety of physiological functions and responses to a large portion of the drug targets. The 3D structure of somatostatin receptor 1(SSTR1) was modeled and refined by means of homology modeling and molecular dynamics simulation. This model was assessed by Verify-3D and Vadar, which confirmed the reliability of the refined model. The interaction between the inhibitor cysteamine, somatostatin(SST) and SSTR1 was investigated by a molecular docking program, Affinity. The binding module not only showed the crucial residues involved in the interaction, but also provided important information about the interaction between SSTR1 on the one hand and ligands on the other, which might be the significant evidence for the structure-based design.



Adsorption of Zinc and Cyanide from Cyanide Effluents on Anionic Ion-exchange Resin

ZHANG Ya-li, FANG Tao, YU Xian-jin

2013, 29(1):  144-149.  doi:10.1007/s40242-013-2070-6

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The adsorption of zinc and cyanide from cyanide effluents onto strong and weak basic anion exchange resins was studied in a batch adsorption system. Factors influencing the adsorption rates such as resin selection, resin amounts, contact time and temperature were studied and scanning electron microscopy-energy disperse spectroscopy(SEM-EDS) was used in the analysis. The present study shows that the adsorption capacity of resin 201×7 is better than that of resin 301. The adsorption process was relatively fast and came to equilibrium after 60 min. The kinetic data were analyzed with three models and the pseudo-second-order kinetic model was found to agree with the experimental data well. The equilibrium data could also be described well by Langmuir isotherm model. Thermodynamic parameters such as enthalpy change(ΔH⁰), free energy change(ΔG⁰) and entropy change(ΔS⁰) were calculated and the adsorption process was spontaneous and endothermic.



Research Note

Theoretical Studies on Structures and Stabilities of C₄H₂⁺ Isomers

ZHAO Ying, WAN Su-qin, LIU Hui-ling, HUANG Xu-ri, SUN Chia-chung

2013, 29(1):  150-153.  doi:10.1007/s40242-013-2060-8

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The structures, energies, stabilities and spectroscopies of doublet C₄H₂⁺ cations were explored at the DFT/B3LYP/6-311G(d,p), CCSD(T)/6-311+G(2df,2pd)(single-point), and G3B3 levels. Ten minimum isomers including the chainlike, three-member-ring, and four-member-ring structures are interconverted by means of 15 interconversion transition states. The potential energy surface was investigated. At the CCSD(T)/6-311+G(2df,2pd) and G3B3 levels, the global minimum isomer was found to be a linear HCCCCH. The structures of the stable isomer and its relevant transition state are further optimized at the QCISD/6-311G(d,p) level. The bonding nature and structure of isomer HCCCCH were analyzed.



Effect of Molar Ratio of Citric Acid to Metal Nitrate on the Structure and Catalytic Activity of NiO Nanoparticles

WU Gang, TAN Xiao-yan, LI Gui-ying, HU Chang-wei

2013, 29(1):  154-158.  doi:10.1007/s40242-013-2059-1

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NiO nanoparticles were prepared by means of sol-gel method via varying the ratio of citric acid to nickel nitrate. The samples were characterized by powder X-ray diffraction(XRD), Fourier transform infrared(FTIR) spectroscopy, transmission electron microscopy(TEM) and X-ray photoelectron spectroscopy(XPS). It was found that the molar ratio of citric acid to nickel nitrate has a great effect on the crystal structure and particle size of NiO. The increase of the molar ratio of citric acid to nickel nitrate is favorable to the formation of NiO smaller particles within the range tested. Compared to bulk NiO obtained by thermal decomposition, NiO nanoparticles possess more surface oxygen species O^-. The activity test indicates that surface oxygen species O^- plays a crucial role in the hydroxylation of benzene to phenol with hydrogen peroxide as oxidant. The active site may be originated from Ni²⁺ on the surface of the samples, while Ni⁰ does not contribute to the hydroxylation reaction.



Kinetics of Atom Transfer Radical Polymerization of Methyl Methacrylate Initiated by Cellulose Chloroacetate in BMIMCl

LIN Chun-xiang, ZHAN Huai-yu, LIU Ming-hua, FU Shi-yu, LUCIA Lucian,

2013, 29(1):  159-165.  doi:10.1007/s40242-013-2058-2

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The kinetics of atom transfer radical polymerization(ATRP) of methyl methacrylate(MMA) initiated by cellulose based macroinitator, cellulose chloroacetate, performed in ionic liquid(1-N-butyl-3-methylimidazolium chloride, BMIMCl), dimethyl sulfoxide(DMSO) and dimethyl formamide(DMF) were respectively studied in detail. The polymerizations were carried out under homogeneous conditions with CuBr as catalyst and 2,2′-bipyridine(bpy) as ligand. The dependences of the rate of polymerization on solvent, temperature, monomer/initiator ratio and catalyst/ligand ratio were presented. Plots of ln([M]₀/[M]_t) vs. time and molecular weight vs. conversion showed a linear dependence, indicating a constant number of propagating species throughout the polymerization as well as a negligible contribution of termination or transfer reactions. On the basis of an Arrhenius plot, the apparent energy of activation(ΔE_a^app) for ATRP of MMA in BMIMCl was 16.6 kJ/mol which is much lower than that in diphenyl ether.



Judd-Ofelt Analysis on Trifluoroacetate Europium Complexes for Liquid Laser Media

SHE Jiang-bo, LI Dong-dong, GAO Fei, QIAO Ze-bang, LIU Huan-huan, WEI Wei, PENG Bo

2013, 29(1):  166-170.  doi:10.1007/s40242-013-2046-6

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Four europium trifluoroacetate complexes, Eu(CF₃COO)₃·bpy(bpy=2,2′-bipyridine)(1), Eu(CF₃COO)₃· phen(phen=1,10-phenanthroline)(2), Eu(CF₃COO)₃·2bp(bp=benzophenone)(3) and Eu(CF₃COO)₃·2tppo(tppo=triphenyl-phosphine oxide)(4) were synthesized and characterized by elemental analysis, Fourier transform infrared(FTIR) spectroscopy, photoluminescence(PL) spectroscopy and thermogravimetric analysis(TGA). The PL spectra of the complexes at room temperature show the strong typical Eu³⁺ ion red emission, due to the efficient energy “antenna absorption” of ligands and transitions of Eu³⁺ ion between ⁵D₀→⁷F_J(J=0―4). The long lifetime and high quantum yield reflect that the multiphonon relaxations by coupling to O―H and C―H vibrations were reduced. According to the photoluminescent spectra, the Judd-Ofelt parameters Ω₂ and Ω₄ of the complexes were calculated and the radiative properties were also presented. The ⁵D₀ radiative lifetime, quantum yield and the stimulated emission cross-section of the complexes are excellent, which prove that they have promising optical properties for liquid laser. The thermal analyses indicate that they are quite stable to heat.



Dissipative Particle Dynamics Simulation of Onion Phase in Star-block Copolymer

WU Shao-gui, DU Ting-ting

2013, 29(1):  171-176.  doi:10.1007/s40242-013-2042-x

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A dissipative particle dynamics simulation technique was used to investigate the effect of molecular architecture of star-block copolymer on the patterned structure in a nanodroplet. With increasing the ratio of solvophilic to block length to solvophobic block length(R_H/T), solvophobic sphere, ordered hexagonal phase, onion phase, perforated onion phase and flocculent phase are formed, respectively. Since onion phase has potential application in controlled drug release, it has received wide attention experimentally and theoretically. Our simulation indicates onion phase forms at a certain R_H/T(close to but less than 1). A star-block copolymer molecule has two conformations in onion phase: either fully located in a shell or shared by two neighboring shells. Central structure affects onion's final shape. The molecular number of the copolymer in each shell is a quadratic function of the shell's radius. The arm number of star-block copolymer has little influence on onion's structure, but slightly affects the solvent content. Additionally, we studied the influence of arm length on onion's structure.



Preparation of Poly(serine ester)s by Ring-opening Polymerization of N-Trityl Serine Lactone Under Catalysis of ZnEt₂

WEI Ying, LI Xiao-yuan, JING Xia-bin, CHEN Xue-si, HUANG Yu-bin

2013, 29(1):  177-182.  doi:10.1007/s40242-013-2355-9

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Poly(N-trityl serine lactone)(PTSL) and mPEG-block-poly(N-trityl serine lactone)(mPEG-b-PTSL, PEG=polyethylene glycol) were synthesized via the ring-opening polymerization of N-trityl serine lactone(TSL) with diethyl zinc(ZnEt₂) as catalyst. The structures of these polymers were confirmed with hydrogen nuclear magnetic resonance(¹H NMR) spectroscopy, carbon nuclear magnetic resonance(¹³C NMR) spectroscopy and infrared(IR) spectrometer. The thermal decomposition temperature and glass transition temperature of PTSL were 241 and 161 ℃, respectively. A series of mPEG-b-PTSL with different molecular weights(M_n's from 7000 to 32000) was obtained by tuning the TSL/mPEG feed ratio. After the removal of the trityl groups, mPEG-block-poly(serine lactone)(mPEG- b-PSL) was obtained as a new kind of cationic block copolymer. Low cytotoxicity of these polymers to L929 cells was confirmed via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide(MTT) assay.



Interventional Radionuclide Therapy of Hepatocellular Carcinoma: Assessment of Intratumoral Retention of HPMA Copolymers

YUAN Jian-chao, MIAO Cheng-ping, ZENG Xian-wu, GUO Hong-yun, WANG Xiao-qi, LIAO Shi-qi, XIE Xiao-li

2013, 29(1):  183-188.  doi:10.1007/s40242-013-2089-8

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To develop new radiopharmaceuticals for the interventional radionuclide therapy of recurrent hepatocellular carcinoma, poly(HPMA)-APMA-DTPA[HPMA=N-(2-hydroxypropyl) methacrylamide; APMA=N-(3-aminopro-pyl)methacrylamide; DTPA=diethylenetriaminepentaacetic acid] was synthesized by free radical precipitation polymerization in acetone/dimethylsulfoxide with N,N′-azobis(isobutyronitrile) as the initiator. The copolymers were characterized with nuclear magnetic resonance(NMR) spectroscopy and gel permeation chromatography(GPC, M_n=2.2×10⁴, M_w/M_n=1.38). Subsequently, poly(HPMA)-APMA-DTPA was conjugated with ^99mTc radionuclide. Prolonged retention of poly(HPMA)-APMA-DTPA conjugate within the tumor tissues was demonstrated by single-photon emission computed tomography computed tomography(SPECT-CT) at 1, 2, 4 and 24 h following intra-tumoral injection of the conjugate to hepatocellular carcinoma xenografts in mice. DTPA-^99mTc was also synthesized and characterized for comparison. The data suggest that the poly(HPMA)-APMA-DTPA conjugates might be useful for the interventional radionuclide therapy of recurrent hepatocellular carcinoma in humans.



Facile Preparation and Cellular Imaging of Photoluminescent Carbogenic Nanoparticles Derived from Defoliations

XIU Yang, ZHOU Yan, GAO Qian, CHEN Jie-sheng, LI Guo-dong

2013, 29(1):  189-192.  doi:10.1007/s40242-013-2031-0

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