Research of Inclusion Complexation of 4,4'-Thiodiphenol Effected by β-Cyclodextrin in Aqueous Solutions and the Effect on Photodegradation

The inclusion behavior of 4,4′ -Thiodiphenol (TDP),a typical bisphenol and endocrine disruptor,reacts with β-cyclodextrin (β-CD) in aqueous solutions has been investigated by means of UV absorption spectrum and quantum-chemical calculation with Gaussian 98 software. The results show that the inclusion behavior of TDP is quite different in acidic solutions (pH 5.9) from that in alkaline solutions (pH 10.0). This behavior difference is attributed to the different formula structures in aqueous solutions at acidic and alkaline pH values that are demonstrated by quantumchemical modeling and calculation. TDP forms a 1∶1 β-CD inclusion complex in aqueous solutions. The equilibrium constant K was calculated to be 553.49 L/mol at pH 5.9 and 1 318.20 L/mol at pH 10.0 respectively for the inclusion complex reaction by using the modified Benesi-Heldbrand equation. After inclusion TDP's structure is changed especially at the inclusion part with the bond order becoming larger,which results in inhibitive photodegradation during direct photooxidation and H2O2 assisted photooxidation.     

Research of Inclusion Complexation of 4,4＇-Thiodiphenol Effected by β-Cyclodextrin in Aqueous Solutions and the Effect on Photodegradation

The inclusion behavior of 4, 4＇ -Thiodiphenol （TDP）, a typical bisphenol and endocrine disruptor, reacts with β-cyclodextrin （β-CD） in aqueous solutions has been investigated by means of UV absorption spectrum and quantum-chemical calculation with Gaussian 98 software. The results show that the inclusion behavior of TDP is quite different in acidic solutions （pH 5.9） from that in alkaline solutions （pH 10.0）. This behavior difference is attributed to the different formula structures in aqueous solutions at acidic and alkaline pH values that are demonstrated by quantum- chemical modeling and calculation. TDP forms a 1 ： 1 fl-CD inclusion complex in aqueous solutions. The equiiibrium constant K was calculated to be 553.49 L/mol at pH 5.9 and 1 318.20 L/mol at pH 10.0 respectively for the inclusion complex reaction by using the modified Benesi-Heldbrand equation. After inclusion TDP＇s structure is changed especially at the inclusion part with the bond order becoming larger, which results in inhibitive photodegradation during direct photooxidation and H2O2 assisted photooxidation.     

Some Remarks on the Degree of Crystallinity Measured on DSC

A modified mathematical model based on the melting and recrystallization of an initial distribution of melting temperatures predicts the melting behavior of polymer in differential scanning calorimetry ( DSC ) , taking into account of changes in heat of fusion with melting temperature of crystal and average heat capacity of sample. It has been used to analytically prove that the crystallinity measured on a DSC diagram could not be equal to the weight percentage of crystalline state in the initial specimen. The deviation of the measured crystallinity, as observed relevant to the melting and recrystallization processes, is caused by the changes of the heat of fusion with the melting temperature of crystals, as well as the difference of heat capacities of liquid and solid state polymer. Furthermore, upper and lower limits of the deviation have been discussed.     

Synthesis and micellization behavior of stimuli-responsive polypeptide hybrid triblock copolymer

Polypeptide hybrid triblock copolymer, poly（L-glutamic acid）-b-poly（propylene oxide）-b-poly （L-glutamic acid） （PLGA-b-PPO-b-PLGA）, was synthesized by the ring-opening polymerization of benzyI-L- glutamic N-carboxyanhydride （BLG-NCA） using poly（propylene glycol） bis（2-aminopropyl ether） as initiator, followed by the subsequent deprotection step. The obtained double hydrophilic triblock co- polymer exhibits ＂schizophrenic＂ micellization behavior in aqueous solution upon dually playing with solution pH and temperature. The multi-responsive micellization behavior of this polypeptide hybrid triblock copolymer has been thoroughly investigated by 1H NMR, laser light scattering （LLS）, tempera- ture-dependent optical transmittance, and circular dichroism spectroscopy （CD）.     

Preparation and characterization of Ni/Co bimetallic nano-clusters

Ni/Co bimetallic nano-cluters have been prepared from the aqueous solution by reducing their corresponding metal salts under suitable conditions. The experimental conditions including the type and concentration of protective agent, feeding order and the pH of the solution that influence the average particle size have been studied in detail. Transmission electron microscopy (TEM)indicates that the shape of those bimetallic nano-cluster particles is spheroid. The alloy structure has been shown by X-ray powder diffraction (XRD). The X-ray photoelectron spectroscopic (XPS) data have confirmed that the nickel and cobalt in the bimetallic nano-clusters are in the zero-valence state.     

Molecular recognition study on a supramolecular system (ⅩⅤ)──Molecular recognition of aliphatic alcohols by some phenyl-selenium modified β-cyclodextrins

The spectrophotometric titrations have been performed at 298.15 K in buffered aqueous solution (pH 7.20) to give the stability constants (logK-s) for the supramolecular system formed by mono-[6-(phenylseleno)-6-deoxy]-β-cyclodextrin (2), mono-[6-(p-tolylseleno)-6-deoxy]-β-cyclodextrin (3), mono-[6-(o-tolylseleno)-6-deoxy]-β-cyclodextrin (4), mono-[6-(m-tolylseleno)-6-deoxy]-β-cyclodextrin (5) with a series of aliphatic alcohols. The results were compared with the data reported for the parent β-cyclodextrin. The molecular binding ability and selectivity for aliphatic alcohols of modified β-cyclodextrins (2_5) were discussed from the viewpoints of the induced-fit and geometrical complement. The results obtained indicate that the phenylseleno moiety of β-cyclodextrin derivatives (2_5) as a probe for spectrometry can enhance not only the molecular binding ability but also the molecular recognition ability.     

Enhanced Removal of Tetracycline from Aqueous Solution by Graphene Oxide Hydrogel Doped with TiO_2 Nanotubes

The detection on tetracycline( TC) in drinking water poses an environmental issue since TC has been widely used to prevent animal disease and promote their growth. In addition,TC was difficult to remove or biodegrade,which posed a challenge to the conventional techniques. In this work,the batch experiments on TC adsorption in aqueous solution of hydrogel( HG) consisting of graphene oxide( GO) and TiO_2 nanotubes( TN) were successfully conducted. HG composite( HG-TN-GO) was prepared with TN and GO with self-assembly method during the oxidation-reduction reaction,and criogel( CG) with TN and GO was characterized by pH at point of zero charge( pH_(pzc)), transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy( XPS). The adsorption capacity of HG-TN-GO on TC was evaluated by analyzing its isotherms. The maximum adsorption capacity reached 751. 3 mg/g. Besides,the adsorption isotherms were well fitted by the Langmuir model, with the theoretical maximum( q_m) of 797. 0 mg/g. The adsorption process was systematically studied by varying pH during the whole adsorption process. The adsorption occurred probably via π-π interaction and cation-π bonding between TC and the HG-TN-GO surface. The composite could be regenerated in 50% ethanol aqueous solution,without significant capacity loss. After 6 recycles,the decrease of adsorption capacity was less than 10%.     

Low-heating solid state synthetic reactions of cyclopeantadienyl organolanthanide complexes

A novel and simple one-step,solid state reaction of multicomponent systems has been developed to synthesize cyclopentadienyl-containing organolanthanide complexes,in which the effects of the coordinated solvent molecules and the nature of the reactants were also studied.We also studied the solid state decomposition reaction of Cp2 YbPz(HPz),and the formation of [CpYb(Pz)2|2 may indicate that the constrained environment in solid state can lead to a novel chemical transformation,with product selectivity possibly different from that in the liquid phase.     

Electrosynthesis of poly（o-phenylenediamine） in ionic liquid and its properties

Ionic liquid 1-ethyl-3-methylimidazolium bromide (EMIMBr) and N-methylimidazolium tetrafluorobo-rate (HMIMBF4) have been used as solvent and electrolyte for the electropolymerization of o-phenylenediamine at glassy carbon electrode by cyclic voltammetry. It was found that monomer was more easily oxidized in ionic liquid than acidic aqueous solution,and oxidative potential was reduced by 0.725 and 0.455 V,respectively. Electrode modified with poly(o-phenylenediamine) (PPD) has obvi-ous electrochemical activity in acid solution (pH 1-4). The apparent diffusion coefficient (Dapp) of PPD film is measured by chronocoulometry and chronoamperometry. The polymer structure is measured by UV and IR. IR spectrometry reveals that poly(o-phenylenediamine) has phenazine ring structure. The heat stability of polymer is observed from thermogravimetry.     

Synthesis of L-cystine bridgedbis（β-cyclodextrin） and its cooperative binding toward guest molecules

A novel p-cyclodextrin derivative, L-cystine bridged bis(β-cyclodextrin) 1 has been synthesized and characterized by 1H NMR, 13C NMR, IR, Raman and combustion analyses. Spectrofluorometric titrations have been performed in aqueous phosphate buffer solution (pH=7.20) at 25℃ to give the complex stability constants (Ks) and Gibbs free energy changes (-△G°) for the stoichiometric 1 : 1 inclusion complexation of 1 with four dyes. The binding abilities and molecular selectivities are discussed from the viewpoint of size/shape-fit and electrostatic interactions between hosts and guests. 2D ROESY investigation for the complexation between host and guest further confirms the cooperative binding of bridged cyclodextrin 1 with guest.     

Mechanical properties and constitutive behaviors of as-cast 7050 aluminum alloy from room temperature to above the solidus temperature

The mechanical properties and constitutive behaviors of as-cast AA7050 in both the solid and semi-solid states were determined using the on-cooling and in situ solidification approaches, respectively. The results show that the strength in the solid state tends to increase with decreasing temperature. The strain rate plays an important role in the stress–strain behaviors at higher temperatures, whereas the influence becomes less pronounced and irregular when the temperature is less than 250°C. The experimental data were fitted to the extended Ludwik equation, which is suitable to describe the mechanical behavior of the materials in the as-cast state. In the semi-solid state, both the strength and ductility of the alloy are high near the solidus temperature and decrease drastically with decreasing solid fraction. As the solid fraction is less than 0.97, the maximum strength only slightly decreases, whereas the post-peak ductility begins to increase. The experimental data were fitted to the modified creep law, which is used to describe the mechanical behavior of semi-solid materials, to determine the equivalent parameter f_GBWL, i.e., the fraction of grain boundaries covered by liquid phase.     

Preparation,Characterization and Antioxidant Activity of Inclusion Complex of Bakuchiol with Hydroxypropyl-β-cyclodextrin

Bakuchiol isolated from Psoralea corylifolia is a naturally occurring prenylated phenolic monoterpene with a variety of bioactivities. The aim of this study was to improve the water solubility and thermal stability of bakuchiol through complexing it with hydroxypropyl-β-cyclodextrin(HP-β-CD). The bakuchiol/HP-β-CD inclusion complex's behavior and characterization were investigated by ultraviolet-visible(UV-vis) spectroscopy, Fourier transform infrared spectroscopy(FT-IR), thermogravimetric analysis(TGA),X-ray diffraction(XRD),~1H nuclear magnetic resonance(NMR), and two-dimensional(2 D) NMR. The obtained results indicated the formation of 1∶1 inclusion complex for bakuchiol with HP-β-CD. Water solubility of bakuchiol was significantly improved by complexation with HP-β-CD as demonstrated by phase solubility studies. The encapsulation of bakuchiol was confirmed by UV-vis, FT-IR, and XRD. The thermal stability was effectively enhanced by TGA and derivative thermogravimetry(DTG) analysis. In vitro antioxidant activity showed that bakuchiol/HP-β-CD inclusion complex had a little higher antioxidant ability than free bakuchiol. Moreover, we got the possible inclusion mode for the bakuchiol/HP-β-CD inclusion complex through NMR analysis. These results suggest that the inclusion complex can be a potentially useful approach in the design of novel formulations of bakuchiol for medical applications.     

Synthesis of Thermoresponsive Poly（ diethyleneglycol methacrylate-co-6-Ovinyladipoyl-D-glucopyranose） Glycopolymer via RAFT Polymerization

The monomer 6-O-vinyladipoyl-D-glucopyranose（ VAG）was synthesized by lipase catalyzed trans-esterification of divinyladipate with D-glucopyranose. A novel double hydrophilic glycopolymer poly（ diethyleneglycol methacrylate-co-6-Ovinyladipoyl-D-glucopyranose）（ P（ DEGMA-co-VAG）） with narrow polydispersity（ PDI） and thermosensitivity was prepared by reversible addition-fragmentation chain transfer（ RAFT）polymerization. P（ DEGMA-co-VAG） was characterized by1 H NMR,FTIR and gel permeation chromatography（ GPC）. The characterization of UV-visible spectroscopy showed that the micelles from glycopolymer P（ DEGMA-co-VAG） were thermo-responsive and the low critical solution temperature（ LCST） could be controlled by the molar ratio of monomers. When the molar ratio of DEGMA and VAG was 2∶ 1,the LCST of P（ DEGMA-co-VAG） was36 ℃ in aqueous solution,which could form nano micelles in the human body environment. It was found that P（ DEGMA-co-VAG）was non-toxic at 0. 1-1 mg / m L concentrations when incubated with pig iliac endothelial cells（ PIECs） for 24 h. Thus,the synthesized glycopolymers has great potential as drug delivery carriers.     

A Composite of Electrospun Nylon-6 Nanofibers and in-situ Polymerized Polypyrrole as an NH3 Gas Sensor

1 Results Electrospinning provides a simple and versatile method for preparing nanofibers with different morphology, such as porous fibers and nanotubes. It has been widely used for preparing nanomaterials with unique properties and potential applications in medicine, catalyst, photonics and sensors[1, 2]. In this study, uniform Nylon-6 nanofibers with diameter of ≈300 nm by electrospun from formic acid solution containing 15%wt Nylon-6. Polypyrrole (PPy) was then deposited on the nanofibers by in-situ polymerization with different kinds of doped acid, and the composite so prepared was characterized by UV and FT-IR spectra. The morphology of the Nylon-6 nanofibers before and after deposition of PPy was observed by SEM.     

Porous SiC ceramics fabricated by quick freeze casting and solid state sintering

Porous SiC ceramics with uniform microstructure were fabricated by quick freezing in liquid nitrogen and solid state sintering.Poly(vinyl alcohol)(PVA) was added as binder and pore morphology controller in this work.The microstructure and mechanical properties of porous SiC ceramics could be controlled by the composition of the aqueous slurries.Both solid content of the slurries and PVA content impacted on the pore structures and mechanical properties of the porous SiC ceramics.The solid content of slurries and PVA content varied from 60 to 67.5 wt%and 2-6 wt%,respectively.Besides,the grain morphology of ceramics was also tailored by changing the sintering temperature from 2050 to 2150 ℃.Porous SiC ceramics with an average porosity of 42.72%,flexural strength of 59.28 MPa were obtained at 2150 ℃ from 67.5 wt% slurries with 2 wt% PVA.     

Effects of 1,7-Bromine Substitution at Bay Area on Self-assembly Behavior and Photo Physical Properties of Perylene Diimide

N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A comparison of the two samples by measuring their photo physical properties using UV visible absorption and fluorescence emission spectra revealed that bay substitutions of bromine do not have significant effect on the perylene diimide( PDI) photo physical properties in solution. However,the solid state fluorescence properties were enhanced by brominating at bay areas. The solid fluorescence quantum yield of 1,7-Br-PDI-C12 was 2. 83%( Фf= 2. 83%) and 1,7-H-PDI-C12 was only 0. 02%( Фf= 0. 02%). This behavior was also reflected in the steady-state fluorescence spectra. This work shows that solid state photo physical properties of PDI could be improved without changing the other properties by simply using bromine substitution at bay areas. These types of materials are useful intermediate for further synthesis of PDI with tunnable optoelectronic properties.     

Dynamic constitutive modeling of frozen soil under impact loading

In this study, an isotropic hardening constitutive model is presented to study the behavior of frozen soil under impact loading. In plasticity, a modified Drucker–Prager yield function is adopted. Based on the experimental investigations at different strain rates and different temperatures by means of split Hopkinson pressure bar, the Drucker–Prager criterion has been modified with consideration in the effect of strain rate, and the model parameters have been determined. Compared the constitutive model with the experimental results, the predicted tendencies of the model corresponded well to the test curves.     

Studies on the interactions of 2,5-diphenyl 1,3,4-oxadiazole and 2,5-diphenyl 1,3-oxazole with β-cyclodextrin

Interactions of 2,5-diphenyl 1,3,4-oxadiazole (PPD) and 2,5-diphenyl 1,3-oxazole (PPO) with β-cyclodextrin (β-CD) are studied by 1H-NMR and steady-state fluorescence measurements, and the stoichiometries and the association constants are estimated. It is found that the hydrophobic interaction is the main driving force for the formation of inclusion complexes of PPD and PPO with β-CD. In the presence of aliphatic alcohols (from 1-propanol to 1-pentanol), PPD and PPO transfer from the CD cavity to the aqueous phase. Quenching experiments of PPD and PPO by iodide further prove the above conclusions. The results suggest that stereo effect is the crucial factor to the inexistence of nanotube in PPD (or PPO)-β-CD systems.     

Three-Dimensional Stress and Stress Intensity for Tensioned Flat Plates with Edge Cracks

The stress in the thickness direction is an important factor influencing the fracture behavior of structural members. A stress σy tensioned flat plate with edge cracks is widely used as an analysis model. The stresses σx and σy for the plate model can be acquired from Neuber＇s solution. However, the solution is applicable only for a perfect plane stress or plane strain state. As a consequence of the thickness of the plate a three-dimensional （3-D） stress state will arise near the crack tip, resulting in a variation of the distribution of σx and σy stresses. A full analysis for the 3-D stress fields for a tensioned flat plate with edge cracks has been therefore carried out. The results show that the 3-D stress field near the crack tip is mainly determined by two factors： the thickness of the plate and the curvature radius at the crack tip. A further analysis has been carried out for the stress intensity near the crack tip. In this paper we give some equations matching to the 3-D stress and stress intensity, which describe precisely the stress state near the crack tip, and which can be applied effectively in engineering analysis.     

Corrosion-wear behavior of nanocrystalline Fe88Si12 alloy in acid and alkaline solutions

The corrosion-wear behavior of a nanocrystalline Fe₈₈Si₁₂ alloy disc coupled with a Si₃N₄ ball was investigated in acid (pH 3) and alkaline (pH 9) aqueous solutions. The dry wear was also measured for reference. The average friction coefficient of Fe₈₈Si₁₂ alloy in the pH 9 solution was approximately 0.2, which was lower than those observed for Fe₈₈Si₁₂ alloy in the pH 3 solution and in the case of dry wear. The fluctuation of the friction coefficient of samples subjected to the pH 9 solution also showed similar characteristics. The wear rate in the pH 9 solution slightly increased with increasing applied load. The wear rate was approximately one order of magnitude less than that in the pH 3 solution and was far lower than that in the case of dry wear, especially at high applied load. The wear traces of Fe₈₈Si₁₂ alloy under different wear conditions were examined and analyzed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the tribo-chemical reactions that involve oxidation of the worn surface and hydrolysis of the Si₃N₄ ball in the acid solution were restricted in the pH 9 aqueous solution. Thus, water lubrication can effectively improve the wear resistance of nanocrystalline Fe₈₈Si₁₂ alloy in the pH 9 aqueous solution.