A new cross‐linked system of silicone rubber based on silicone‐polyurea block copolymer

A new cross‐linked system of silicone rubber (SR) was obtained from silicone‐polyurea block copolymers that was synthesized with aminopropyl terminated polydimethylsiloxane and (4‐isocyanatocyclohexyl)‐methane. SR possessed self‐reinforced and physical cross‐linked structure. It had better mechanical properties that the hardness, the tensile strength, and the elongation at break could reach 65 Shore A, 3.78 MPa, and 458% with the polyurea segment content ranging from 2.01% to 9.13% by weight . The hydrogen bond that led to the physical cross‐linked structure was proved byFourier transform infrared spectroscopy. The microphase separated structure that caused the self‐reinforcement was illustrated by scanning electron microscopy, X‐ray diffraction analysis, and dynamic mechanical analysis. Fourier transform infrared spectroscopy results showed the hydrogen bond formation between the polyurea units. Scanning electron microscopy, dynamic mechanical analysis, and X‐ray diffraction analysis results proved the microphase separation existed between polyurea units and ―Si―O―Si― chains. The increase of polyurea contents enhanced the binding of hydrogen bond and improved the extent of microphase separation. Accordingly, it decreased the thermal properties and lowered the glass transition temperature (T_g) from −108°C to −114°C. Also, the increase of polyurea contents increased the hydrophobicity of SR that the surface free energy could reach to −24.81 mN/m.     

Preparation and characterization of natural zeolite supported nano TiO2 photocatalysts by a modified electrostatic self‐assembly method

Natural zeolite supported nano TiO₂ photocatalysts were prepared by a modified electrostatic self‐assembly (ESA) method. First, γ‐mercaptopropyltrimethoxysilane with sulfhydryl (―SH) functional groups was modified on the zeolite powders by using a ‘dry process’. Second, silane with ―SH functional groups was oxidized to sulfonate (―SO₃H) groups by using a hydrogen peroxide/glacial acetic acid mixed solution, and the surface of ―SO₃H silane–zeolite was electronegative charged due to the ionization of ―SO₃H. Third, the hydrolytic titanium polycation from TiCl₄ solution assembled onto the electronegative charged zeolite under electrostatic attraction in the reaction solutions. Finally, zeolite supported nano TiO₂ photocatalysts can be obtained after the above compounds calcined at certain temperature. The samples were characterized by X‐ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface areas, Fourier transform infrared spectroscopy (FT‐IR), X‐ray photoelectron spectroscopy (XPS) and X‐ray fluorescence (XRF). The photocatalytic activities of the samples were evaluated by the degradation of methyl orange in aqueous solution. The results showed that ESA method effectively improved the composite efficiency of zeolite with TiO₂. The photocatalysts prepared by ESA method exhibited higher photocatalytic and recycling activities than that of traditional method. Copyright © 2014 John Wiley & Sons, Ltd.     

Mixed bis(morpholine‐4‐dithiocarbamato‐S,S′)antimony(III) complexes: synthesis,characterization and biological studies

Some mixed bis(morpholine‐4‐dithiocarbamato‐S,S′)antimony(III) complexes [(OC₄H₈NCS₂)₂SbL] with oxygen or sulfur donor ligands [L = ―OOCCH₃ ( 1 ), ―OOCC₆H₅ ( 2 ), ―SOCCH₃ ( 3 ), ―SCH₂COOH ( 4 ), ―OOCC₆H₄(OH) ( 5 ), ―SCH₂CH₂CH₃ ( 6 ), ―OC₆H₅ ( 7 ), ½ ―SCH₂CH₂S― ( 8 )] have been synthesized by reacting the chloro‐bis(morpholine‐4‐dithiocarbamato‐S,S′)antimony(III) with corresponding oxygen or sulfur donor ligands in 1:1 or 2:1 stoichiometries. These have been characterized by melting point, molecular weight determination (cryoscopically), antimony (iodometrically) and sulfur (gravimetrically) estimation, elemental analyses (C, H and N), UV–visible, FT‐IR, far IR, multinuclear NMR (¹H and ¹³C)], TG/DTA analysis, ESI–mass and powder X‐ray diffraction studies. The splitting of the strong band observed at 1046–1066 cm^?1 due to υ(C―S) indicated anisobidentate mode of binding of the dithiocarbamate group, which was further supported by a ¹³C NMR signal appearing at around δ 200 due to NCS₂ moiety. The base peak observed at m/z 444.9 supports the strong chelating nature of the morpholine‐4‐dithiocarbamate compared to the other hetero ligands used. TGA revealed that, complexes 21 and 4 were decomposed in three steps; also 6 was decomposed in two steps, followed by the formation of Sb₂S₃. The results obtained by antimicrobial screening tests indicate that complex 3 showed a maximum zone of inhibition (20 mm) against Trichoderma ressie at a concentration of 200 µg ml^?1. Complexes 2 , 3 and 8 are most active (zone of inhibition (ZI) 17–20 mm) against both of the fungal species Aspergillus niger and Trichoderma ressie as well as complex 4 (ZI 17 mm) and 6 (ZI 18 mm) against Trichoderma ressie. Copyright © 2014 John Wiley & Sons, Ltd.     

Fe-N/C-TsOH催化剂应用碱性介质催化氧还原的电催化活性

通过溶剂分散热处理方法制备了一种吡咯和对甲苯磺酸(TsOH)共同修饰的碳载非贵金属复合催化剂(Fe-N/C-TsOH),并采用扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)对催化剂的形貌和组成成分进行表征. 借助循环伏安法(CV)和旋转圆盘技术研究了TsOH对催化剂在0.1 mol·L^-1 KOH介质中催化氧还原性能的影响. 结果表明：TsOH的存在对催化剂催化氧还原反应(ORR)的活性影响很大. 以其制备的气体扩散电极在碱性电解质溶液中催化氧还原过程时转移的电子数为3.899,远比不含TsOH修饰的催化剂催化氧还原的电子数(3.098)高. 此外,研究发现600 ℃热处理过的Fe-N/C-TsOH催化剂表现出最佳的氧还原催化性能. 相比未经热处理过的Fe-N/C-TsOH催化剂,起峰电位和-1.5 mA·cm^-2电流密度对应的电压分别向正方向移动30 和170 mV. XPS研究结果表明吡咯氮是催化剂主要活性中心,提供氧还原活性位,而TsOH加入形成的C―S_n―C和―SO_n―有利于催化剂催化氧还原活性的提高,从而使该催化剂对氧还原表现出很好的电催化性能和选择性.     

Comparative studies of solid‐state synthesized poly(o‐methoxyaniline) and poly (o‐toluidine)

Poly(o‐methoxyaniline) (POMA) and poly(o‐toluidine) (POT) salts doped with different acids (methanesulphonic acid (MeSA), trifluoroacetic acid (TFA), and hydrochloric acid (HCl)) were synthesized by using solid‐state polymerization method. The polymers were characterized by Fourier transform infrared (FTIR) spectra, ultraviolet–visible (UV–Vis) spectrometry, X‐ray diffraction (XRD), cyclic voltammetry (CV), and conductivity measurements. Transmission electron microscopy (TEM) was done to study the morphologies of POMA and POT salts. The FTIR and UV‐Vis absorption spectra revealed that the reduced phase was predominant in POMA salts, and the pernigraniline phase was predominant in POT salts. It was found that POMA salts displayed higher doping level and conductivity. In contrast, POT salts were lower at doping levels and conductivity. In accordance with these results, the electrochemical activity was also found to be lower in POT salts. The XRD patterns showed that the POMA salts displayed higher crystallinity than POT salts. The results from TEM revealed that the morphologies of POMA salts were different from those of POT salts. Copyright © 2008 John Wiley & Sons, Ltd.     

X‐ray induced degradation of surface bound azido groups during XPS analysis

Mesoporous silica SBA‐15 was synthesized and silanized with azidopropyl triethoxysilane in order to design a clickable material. Fourier transform infrared analysis permitted to prove the attachment of the azidopropylene groups to SBA‐15 resulting in the reactive and functional material N₃‐SBA‐15. X‐ray photoelectron spectroscopy was used to determine the surface composition of SBA‐15. However, we unexpectedly found that the surface bound azido groups undergo X‐ray induced decomposition during the X‐ray photoelectron spectroscopy analysis resulting in the formation of nitrenes. These are very reactive groups able to intercalate C―C and C―H bonds of the propylene chains as judged from the N1s peak shape. Possible mechanisms of intercalation are suggested. C1s and N1s peaks were recorded at different exposure time. N/C, N⁺/N and N⁺/C undergo exponential decay. N⁺/N reaches the value of zero in less than 80 min of exposure to the X‐ray source. The N⁺/C decay plot was fitted with first‐order kinetics, and the decomposition kinetic constant (k_dec) was found to equal to 516.4 s^?1. This is a fast X‐ray induced degradation which must be considered with care when examining clickable materials with surface bound alkyl azido groups. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation of Monolithic Ti‐incorporated Mesoporous Silica Materials via Tartaric Acid Templated Sol‐gel Process

Monolithic and transparent Ti‐incorporated mesoporous silica materials of large size (e.g. 2 mm) in dimension have been prepared with tartaric add (TA) as template via sol‐gel reactions of tetraethyl orthosilicate (TEOS) and tetrabutyl titanate (TBT). The materials are characterized by infrared (IR), nitrogen adsorption‐desorption isotherms, powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The results indicate that the monolithic materials exhibit large specific surface areas (ca. 1200 mVg) and pore volumes (ca. 0.900 cm³/g).     

Core–shell SiO2‐coated Fe3O4 with a surface molecularly imprinted polymer coating of folic acid and its applicable magnetic solid‐phase extraction prior to determination of folates in tomatoes

A novel core–shell magnetic surface molecularly imprinted polymer with folic acid as a template was successfully synthesized by the sol–gel method. To generate Lewis acid sites in the silica matrix for the interaction of the metal coordinate with the template, 3‐aminopropyltriethoxysilane was used as a functional monomer, tetraethyl orthosilicate as a cross‐linker, and aluminum ions as a dopant. The magnetite encapsulated by the silica shell plays an important role as a magnetic‐coated polymer. The synthesized product was characterized by powder X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and FTIR and UV/Vis spectroscopy. The powder X‐ray diffraction patterns, FTIR and UV/Vis spectra confirmed the characteristics of the as‐prepared silica coated magnetite and folic acid molecularly imprinted polymer. It was successfully applied for magnetic solid‐phase extraction prior to the determination of folates in tomato samples using high‐performance liquid chromatography with photodiode array detection. The detection limit of the proposed method was 1.67 μg/L, and results were satisfactory, with a relative standard deviation of < 3.94%.     

Fe3O4@SiO2@Im‐bisethylFc [HC2O4] as a novel recyclable heterogeneous nanocatalyst for synthesis of bis‐coumarin derivatives

Nanomagnetic bisethylferrocene‐containing ionic liquid supported on silica‐coated iron oxide (Fe₃O₄@SiO₂@Im‐bisethylFc [HC₂O₄]) as a novel catalyst was designed and synthesized. The described catalyst was recycled and used without change in the time and efficiency of the condensation reaction. The Fourier transform‐infrared spectroscopy (FT‐IR), scanning electron microscopy images, X‐ray diffraction patterns, energy‐dispersive X‐ray spectroscopy, transmission electron microscope and vibrating‐sample magnetometer results confirmed the formation of Fe₃O₄@SiO₂@Im‐bisethylFc [HC₂O₄] magnetic nanoparticle. The novel bis‐coumarin derivatives were identified by ¹H‐NMR, ¹³C‐NMR, FT‐IR and CHNS analysis.     

Synthesis,characterization and catalytic activity of new aminomethyldiphosphine–Pd(II) complexes for Suzuki cross‐coupling reaction

A new range of CF₃‐substituted aminomethyldiphosphine (P―C―N) ligands ((C₆H₅)₂PCH₂)₂NR (R = ―C₆H₄(2‐CF₃) ( 1 ), ―C₆H₄(3‐CF₃) ( 1b ) has been synthesized from 2‐(trifluoromethyl)aniline and 3‐(trifluoromethyl)aniline with diphenylphosphine. The aminomethyldiphosphine ligands were reacted with Pd(cod)Cl₂ to give corresponding metal complexes, PdLCl₂ ( 2a , 2b ). The aminomethyldiphosphine–palladium compounds were characterized by utilizing several methods including NMR (¹H, ¹³C, ³¹P) and elemental analysis. These compounds were used as catalysts in Suzuki cross‐coupling reaction of aryl chlorides and bromides. The effect of base was also investigated in this current project. CF₃‐substituted aminomethyldiphosphine–palladium complexes were found to be efficient catalysts in Suzuki cross‐coupling reaction of activated and deactivated aryl boronic acids. Copyright © 2013 John Wiley & Sons, Ltd.     

Formation mechanism of polyaniline microtubules synthesized by a template‐free method

A template‐like model, which was an aniline salt formed with β‐naphthalene sulfornic acid (β‐NSA) as a dopant, was proposed to interpret the formation mechanism of polyaniline (PANI) microtubules doped with β‐NSA by a template‐free method. Scanning electron microscope (SEM) and X‐ray diffraction measurements confirmed this model. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2359–2364, 2000     

Vinyl polymerization of norbornene catalyzed by 2‐Py‐amidine Ni(II) complex/methylaluminoxane systems

Two 2‐Py‐amidine ligands (2‐Py―NH―C(Ph)═N―Ar, Ar = 2,6‐Me₂C₆H₃ and 2,6‐ⁱPr₂C₆H₃) and the corresponding Ni(II) complexes ( 1 and 2 ) were synthesized and characterized using elemental analysis and FT‐IR, UV–visible, ¹H NMR and ¹³C NMR spectroscopies. X‐ray crystal structures indicate that the chelate ring conformation of the less bulky complex 1 is relatively planar compared with that of the bulky complex 2 . Paramagnetic ¹H NMR and ¹³C NMR studies show that, in solution, the time‐average structures of complexes 1 and 2 have mirror symmetry. Both complexes 1 and 2 were used as catalyst precursors for norbornene polymerization with methylaluminoxane as a co‐catalyst. The effects of Al/Ni ratio, temperature and structure of precursors on the catalytic performance were investigated. Copyright © 2014 John Wiley & Sons, Ltd.     

Solid‐state synthesis of a new core–shell nanocomposite of polyaniline and silica via oxidation of aniline hydrochloride by FeCl3.6H2O

Among the different oxidants used for the preparation of polyaniline in the solid‐state, iron (III) chloride (FeCl₃.6H₂O) can act as both oxidant and dopant. This work reports the synthesis and characterization of novel composite of polyaniline/silica. The polymerization was performed by oxidative polymerization of aniline hydrochloride in the presence of silica and FeCl₃.6H₂O under solid‐state (solvent‐free) condition. The FeCl₃.6H₂O has been chemically supported on silica and generated silica‐supported FeCl₃ ( SSFe ), which plays three important roles simultaneously (a) oxidant, (b) primary dopant, and (c) secondary dopant (Lewis acid). Furthermore, the existence of silica is important for proceeding of polymerization in solid state. In the other words, the surface polymerization and green chemistry in solid state have been coupled. The characterization and doping process are verified by ultraviolet‐visible, Fourier transform infrared, atomic absorption spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and elemental analysis (CHNS). From atomic absorption spectroscopy the ratio of Fe/N in the composite obtained about 1, which confirms the formation of delocalized polarons by SSFe in the composites. The conductivity is in the range of semi‐conductive. Furthermore, contact resistance was determined by circular‐transmission line measurement. According to scanning electron microscopy images silica particles have been thoroughly coated by polyaniline within the range of 0.2 to 1 µm. However, transition electron microscopy images depict the uniform solid nanospheres (no hollow spheres or fibers), and their mean diameters are under of 50 nm. It confirms nanocomposite of core–shell PANI‐SSFe. Copyright © 2016 John Wiley & Sons, Ltd.     

Surface oxidation process of a diamond‐like carbon film analyzed by difference X‐ray photoelectron spectroscopy

Difference X‐ray photoelectron spectroscopy (D‐XPS) revealed the surface oxidation process of a diamond‐like carbon (DLC) film. Evaluation of surface functional groups on DLC solely by the C 1s spectrum is difficult because the spectrum is broad and has a secondary asymmetric lineshape. D‐XPS clarified the subtle but critical changes at the DLC surface caused by wet oxidation. The hydroxyl (C―OH) group was dominant at the oxidized surface. Further oxidized carbonyl (C?O) and carboxyl (including carboxylate) (COO) groups were also obtained; however, the oxidation of C?O to COO was suppressed to some extent because the reaction required C―C bond cleavage. Wet oxidation cleaved the aliphatic hydrogenated and non‐hydrogenated sp² carbon bonds (C―H sp² and C―C sp²) to create a pair of C―OH and hydrogenated sp³ carbon (C―H sp³) bonds. The reaction yield for C―H sp² was superior at the surface, suggesting that the DLC film was hydrogen rich at the surface. Oxidation of aromatic sp² rings or polycyclic aromatic hydrocarbons such as nanographite to phenols did not occur because of their resonance stabilization with electron delocalization. Non‐hydrogenated sp³ carbon (C―C sp³) bonds were not affected by oxidation, suggesting that these bonds are chemically inert. Copyright © 2014 John Wiley & Sons, Ltd.     

DC electrical conduction and morphological behavior of counter anion‐governed genesis of electrochemically synthesized polypyrrole films

Highly conducting polypyrrole (PPY) films, doped with various anions [pTS^?, ClO₄^?, and NO₃^? and mixed electrolyte system (pTS^? + ClO₄^?)], have been electrochemically synthesized in aqueous solution at ～275 K in an inert atmosphere. PPY exhibits metallic order dc conductivity at room temperature and shows variation of conductivity with respect to time of polymerization. Effect of dopant anion on growth mechanism of PPY is evident from its surface morphology. X‐ray photoelectron spectroscopy (XPS), used to examine the surface composition and doping level of various PPY films, confirms the anionic doping into the polymer backbone. Both XPS and ultraviolet–visible spectroscopy give evidence of formation of polarons and bipolarons. The temperature (4.2–320 K)‐dependent dc conductivity data of these PPY films have been explained by Mott's 3D variable‐range hopping conduction model. Mott's parameters have been estimated, and structural disorder with doping is correlated for all the samples. Mott's criterion for distant hopping sites prevails in case of moderately doped samples (PPY3, PPY4, and PPY5), whereas the hopping to nearest neighbor sites is found more suitable in case of highly doped samples (PPY1 and PPY2). The origin of these changes is due to the modification in the molecular structure of PPY, which is governed by different growth mechanisms for organic (pTS^?) and inorganic (ClO₄^? and NO₃^?) counter anions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Efficient One‐Pot Synthesis of Alkyl 2‐(Dialkylamino)‐4‐phenylthiazole‐5‐carboxylates and Single‐Crystal X‐Ray Structure of Methyl 2‐(Diisopropylamino)‐4‐phenylthiazole‐5‐carboxylate

The reaction between secondary amines, benzoyl isothiocyanate, and dialkyl acetylenedicarboxylates (=dialkyl but‐2‐ynedioates) in the presence of silica gel (SiO₂) led to alkyl 2‐(dialkylamino)‐4‐phenylthiazole‐5‐carboxylates in fairly high yields. The structures of the products were confirmed by their IR, ¹H‐ and ¹³C‐NMR, and mass spectra, and by a single‐crystal X‐ray structure determination.     

Vibronic polarons: Self‐trapping,local rotation,and band features

We revisit basic theoretical concepts of local and itinerant vibronic polarons in crystals. The following results may be regarded as novel: (1) The electron self‐trapping rate to a small polaron is calculated via the reaction rate method; subsequently, self‐trapped on‐center small polarons relax to an off‐center vibronic polaron state. (2) The general vibronic Hamiltonian is redefined so as to incorporate both local and itinerant behavior and pairing into bipolarons or Cooper pairs. (3) The planar rotation and diametral tunneling of an off‐center polaron around and across its centrosymmetrical site are dealt with to adiabatic approximation. (4) Variational calculations are made for vibronic polarons itinerant along 1‐D chains by means of a two‐band extension of Merrifield's ansatz. This investigation of vibronic polarons is undertaken in view of their presumed role in high‐temperature superconductivity and colossal magnetoresistance. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Template‐free anion‐controlled synthesis of Pd (II) nano‐aggregates for the antifouling polymerization of CO and ethylene

The reaction of [(domppp) Pd (OAc)₂] [domppp = 1,3‐bis (di‐o‐methoxyphenylphosphino)propane] and imidazolium‐functionalized carboxylic acids containing various anions (Br^?, PF₆^?, SbF₆^? and BF₄^?) resulted in the formation of nano‐sized Pd (II) aggregates under template‐free conditions. The rate of formation of aggregates can be modulated by changing the anion, affecting the rate of polymerization of CO and olefins without fouling. Herein, we describe the analysis of Pd (II) catalysts by dynamic light scattering, atomic force microscopy, X‐ray photoelectron spectroscopy and X‐ray crystallography, and co‐ and terpolymerization results including the catalytic activity, and bulk density and molecular weight of polymers.     

Silica‐Encapsulated Gd3+‐Aggregated Gold Nanoclusters for In Vitro and In Vivo Multimodal Cancer Imaging

Gd³⁺‐aggregated gold nanoclusters (AuNCs) encapsulated by silica shell (Gd³⁺‐A‐AuNCs@SiO₂ NPs) were strategically designed and prepared. The as‐prepared nanoparticles exhibit aggregation‐enhanced fluorescence (AEF), with an intensity that is up to 3.8 times that of discrete AuNCs. The clusters served as novel nanoprobes for in vitro and in vivo multimodal (fluorescence, magnetic resonance, and computed X‐ray tomography) cancer imaging     

Preparation,characterisation and modification of carbon‐based monolithic rods for chromatographic applications

A range of porous carbon‐based monolithic (PCM) rods with flow‐through pore sizes of 1, 2, 5 and 10 μm, were produced using a silica particle template method. The rods were characterised using SEM and energy‐dispersive X‐ray spectroscopy, BET surface area and porous structure analysis, dilatometry and thermal gravimetry. SEM evaluation of the carbon monolithic structures revealed an interconnected rigid bimodal porous structure and energy‐dispersive X‐ray spectroscopy analysis verified the quantitative removal of the embedded silica beads. The specific surface areas of the 1, 2, 5 and 10 μm rods were 178, 154, 84 and 125 m²/g after pyrolysis and silica removal, respectively. Shrinkage of the monolithic rods during pyrolysis is proportional to the particle size of the silica used and ranged from 9 to 12%. Mercury porosimetry showed a narrow distribution of pore sizes, with an average of ～700 nm for the 1 μm carbon monolith. The suitability of bare and surface oxidised PCM rods for the use as a stationary phase for reversed and normal phase LC was explored. The additional modification of PCM rods with gold micro‐particles followed by 6‐mercaptohexanoic acid was performed and ion‐exchange properties were evaluated.