Electroactive oligoaniline-containing self-assembled monolayers for tissue engineering applications

A novel electroactive silsesquioxane precursor, N-(4-aminophenyl)-M-(4'-(3-triethoxysilyl-propyl-ureido) phenyl-1,4-quinonenediimine) (ATQD), was successfully synthesized from the emeraldine form of amino-capped aniline trimers via a one-step coupling reaction and subsequent purification by column chromatography. The physicochemical properties of ATQD were characterized using mass spectrometry as well as by nuclear magnetic resonance and UV-vis spectroscopy. Analysis by cyclic voltammetry confirmed that the intrinsic electroactivity of ATQD was maintained upon protonic acid doping, exhibiting two distinct reversible oxidative states, similar to polyaniline. The aromatic amine terminals of self-assembled monolayers (SAMs) of ATQD on glass substrates were covalently modified with an adhesive oligopeptide, cyclic Arg-Gly-Asp (RGD) (ATQD-RGD). The mean height of the monolayer coating on the surfaces was similar to 3 nm, as measured by atomic force microscopy. The biocompatibility of the novel electroactive substrates was evaluated using PC12 pheochromocytoma cells, an established cell line of neural origin. The bioactive, derivatized electroactive scaffold material, ATQD-RGD, supported PC12 cell adhesion and proliferation, similar to control tissue-culture-treated polystyrene surfaces.

Stable ordered mesoporous silica materials templated by high-temperature stable surfactant micelle in alkaline media

Ordered hexagonal mesoporous silica material (JLU-30) has been successfully synthesized in alkaline media at high temperature (> 160 degreesC, using cationic (1,3-dimethyl-2-imidazolidin-2-ylidene)hexadecylmethyl-ammonium bromide (DIHAB) as a template, and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption isotherms, differential thermal analysis (DTA), and thermogravimetric analysis (TG), as well as Al-27 and Si-29 nuclear magnetic resonance (NMR) spectroscopy. Mesoporous JLU-30 shows much higher hydrothermal stability than MCM-41. Si-29 NMR spectra indicate that the pore walls of JLU-30 samples synthesized at high temperature (160 degreesC) are fully condensed, giving a Q(4)/Q(3) ratio as high as 6.2. In contrast, MCM-41 synthesized at relatively low temperature (100 degreesC) shows the Q(4)/Q(3) + Q(2) ratio at 1.1. Such unique structural feature might be responsible for the observed highly hydrothermal stability of the mesoporous silica materials (JLU-30).

Compositional differences of propylene-ethylene block copolymers manufactured by degradation and hydrogenation techniques

The purpose of the present work is to investigate the compositional difference of polypropylene-polyethylene block copolymers (PP-b-PE) manufactured industrially by the process of degradation and hydrogenation, respectively. Each of the PP-b-PE copolymers was fractionated into three fractions with heptane and chloroform. The compositions of the three fractions were characterized by C-13 nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy, as well as differential scanning calorimetry (DSC) and thermal fractionation. The results showed that the Chloroform-soluble fraction was amorphous ethylene-propylene rubber, and the content of the rubber in PP-b-PE manufactured by hydrogenation was less than that by degradation. The degree of crystallinity of the chloroform-insoluble fraction of the PP-b-PE manufactured by hydrogenation is higher than that of by degradation.

Investigation on acute biochemical effects of Ce(NO3)(3) on liver and kidney tissues by MAS H-1 NMR spectroscopic-based metabonontic approach

High resolution magic angle spinning (MAS)-H-1 nuclear magnetic resonance (NMR) spectroscopic-based metabonomic approach was applied to the investigation on the acute biochemical effects of Ce(No-3)(3). Male Wistar rats were administrated with various doses of Ce (NO3)(3)(2, 10, and 50 mg(.)kg(-1) body weight), and MAS H-1 NMR spectra of intact liver and kidney tissues were analyzed using principal component analysis to extract toxicity information. The biochemical effects of Ce (NO3)(3) were characterized by the increase of triglycerides and lactate and the decrease of glycogen in rat liver tissue, together with an elevation of the triglyceride level and a depletion of glycerophosphocholine and betaine in kidney tissues. The target lesions of Ce (NO3)(3) on liver and kidney were found by MAS NMR-based metabonomic method. This study demonstrates that the combination of MAS H-1 NMR and pattern recognition analysis can be an effective method for studies of biochemical effects of rare earths.

Triphenylmethanethiol: a novel rigid capping agent for gold nanoclusters

In this article, we employed triphenylmethanethiol (TPMT) as a novel rigid agent for capping gold nanoparticles and the TPMT monolayer-protected gold nanoparticles were characterized by various analytical techniques. High-resolution transmission electron microscopy showed a narrow dispersed gold core with an average core diameter of ca. 3.6 nm. The UV/vis spectrum revealed the surface plasmon absorbance at 528 nm. The p-pi conjugated structure of the TPMT ligand was confirmed by nuclear magnetic resonance. Differential scanning calorimetry and Fourier transform infrared spectroscopy revealed the rigid nature of the TPMT chains.

Probing UPD-induced surface atomic rearrangement of polycrystalline gold nanofilms with surface plasmon resonance spectroscopy and cyclic voltammetry

Silver underpotential deposition (UPD)-induced surface atomic rearrangement of polycrystalline gold nanofilms was probed with use of surface plasmon resonance spectroscopy (SPRs) as a novel probe tool in combination with cyclic voltammetry. Interestingly, upon repetitive electrochemical UPD and stripping of Ag, the surface structure of the resulting bare Au film is rearranged due to strong adatom-substrate interactions, which causes a large angle shift of SPR R-theta curves, in a good linear relationship with the number of UPDs, to a lower SPR angle. The n, K values of the surfacial Au monolayers before and after the repetitive Ag UPD and stripping for 27 times are found to be 0.133, 3.60 and 0.565, 9.39, respectively, corresponding to the huge shift of 1.61degrees to the left of the SPR minima. Cyclic voltammetry experiments in 0.10 M H2SO4 are carried out before and after the UPD treatment to examine the quality of the whole electrode surface and confirmed this change. To correlate the angle change in SPRs with the profile change in the cyclic voltammogram, the UPD treatment was also performed on a Au(111) textured thin film. It was therefore confirmed that the resonance position of the SPR spectrum is very sensitive to the surface crystallographic orientation of the bare Au substrates. Some surface atomic rearrangement can cause a pronounced SPR angle shift.

Evaluation of bioeffects of a long-term administering ChangLe on rat by proton NMR method and biochemical examination

High resolution H-1 nuclear magnetic resonance ( NMR) spectroscopy has been employed to assess long-term toxicological effects of ChangLe (a kind of rare earth complex applied in agriculture). Male Wistar rats were administrated orally with ChangLe at doses of 0, 0.1, 0.2, 2.0, 10 and 20 mg/kg body weight daily, respectively, for 6 months. Urine was collected at-day 30, 60, go and serum samples were taken after 6 months. Many low-molecular weight metabolites were identified by H-1 NMR spectra of rat urine. A decrease in citrate and an increase in ketone bodies, creatinine, DMA, DMG, TMAO, and taurine in the urine of the rats. receiving high doses were found by H-1 NMR spectra. These may mean that high-dosage of ChangLe impairs the specific region of liver and kidney, such as renal tubule and mitochondria. The decrease in citrate and the increase in succinate and alpha-ketoglutarate were attributed to a combination of the inhibition of certain citric acid enzymes, renal tubular acidosis and the abnormal fatty acid catabolism. The information of the renal capillary necrosis could be derived from the increase in DMIA, DMG and TMAO. The increase in taurine was due to hepatic mitochondria dysfunction. The conclusions were supported by the results of biochemical measure. merits and enzymatic assay.

Arabinogalactan as a carrier for contrast agent in magnetic resonance imaging

Arabinogalactan-Gd-DTPA was synthesized by the reaction of diethylenetriaminepenta-acetic acid (DTPA) bisanhydride with polysaccharide in dry DMSO and characterized by FTIR, elemental analysis and ICP-AES. Its stability was investigated by competition with Ca2+, EDTA, DTPA. The t(1)-relaxivity is 8.06 mmol(-1) . L . s(-1) in D2O, 8.48 mmol(-1) . L . s(-1) in 0.725 mmol . L-1 BSA, respectively. t(1)-weighted MR imaging of rat kidney and liver showed a remarkable enhancement post injection of Arabinogalactan-Gd-DTPA. The results indicate that the arabinogalactan-Gd-DTPA is a potential contrast agent for MRI.

H-1 NMR analysis for metabolites in serum and urine from rats administrated chronically with La(NO3)(3)

H-1 NMR spectroscopy has been used to assess long-term toxicological effects of a rare earth. Male Wistar rats were administrated orally with La(NO3)(3) at doses of 0.1, 0.2, 2.0, 10, and 20 mg/kg body wt, resp., for 3-6 months. Urine was collected at 1, 2, and 3 months and serum samples were taken after 6 months. Numerous low-M-r metabolites in rats serum and rats urine, including creatinine, citrate, glucose, ketone bodies, trimethylamine N-oxide (TMAO), and various amino acids, were identified on 400- and 500-MHz H-1 NMR spectra. La3+-induced renal and liver damage is characterized by an increase in the amounts of the excreted ketone bodies, amino acids, lactate, ethanol, succinate, TMAO, dimethylamine, and taurine and a decrease in citrate, glucose, urea, and allantoin. Information on the molecular basis of the long-term toxicity of La(NO3)(3) was derived from the abnormal patterns of metabolite excretions. An assay of some biochemical indexes and analysis of some enzymes in plasma supported NMR results.

Poly(3-dodecylthiophenes) polymerized with different amounts of catalyst

The effect of the amount of the catalyst FeCl3, used during the direct oxidation polymerization, on the structure and properties of the obtained poly(3-dodecylthiophene) (P3DDT) was investigated in this paper. Such measurements as gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) spectroscopy, thermal analysis, X-ray diffraction, infrared spectroscopy (FTIR) and ultraviolet-visible (W-vis) spectroscopy were applied. It is found that a suitable addition of FeCl3 can contribute to generate a P3DDT with greater percentage of head-to-tail head-to-tail (HT-HT) linkages, which are generally favored. The reduction of the other linkage defects helps to lengthen conjugation length, thus leading to more orderly chain packing. (C) 2000 Elsevier Science S.A. All rights reserved.

Spectrometric investigation on the thermooxidative degradation of ethylene oxide and tetra-hydrofuran co-polyether

The thermooxidative degradtion of ethylene oxide and tetra-hydrofuran (EO-THF) co-polyether has been studied by electron spin resonance (ESR), Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The initial degradation site was found to be at the a-carbon of the ether bond. Two free radicals which derived from dehydrogenation and oxygen addition were successfully detected by spin-trapping technique which used alpha -phenyl-N-tert-butyl nitrone(PBN) as spin trap. Both FT-IR and NMR have been used to follow structural changes of the copolyether during degradation. Nearly 20 product fragments including formate, carbonate, methyl, alcohol, methylene-dioxy, hydroperoxide and semiformal have been characterized by D-1 and D-2 NMR. The thermooxidtion of co-polyether preferred to occur on the THF units especially at the alternating linkage of EO and THF. Antioxidant (BHT) not only retarded the thermooxidation but also modified the degradation products with less ester and methylene-dioxy groups hut more hydroxyl and methyl groups.

Structure analysis of the fulvic acids extracted from composted corn stalk residue

Chemical structure of fulvic acids extracted from composted corn stalk residue(CSR FA)was studied by Fourier transform infrared (FTIR) spectroscopy, H-1 and C-13 nuclear magnetic resonance(H-1-NMR, C-13-NMR) spectroscopy. The results show that CSR FA mainly consists of four types of carbon: carbonyl, aromatical, alkyl and carbohydrate, the carbohydrate is dominant. Its aromaticity is 15.42%, less than that of CSR HA. This indicates that the construction of CSR FA is simpler than that of CSR HA, FA can not be extracted from undecomposed corn stalk residue. CSR FA may be formed by cellulose or hemicellulosemorties combined with aromatic compound from decomposed lignin.

Probing lanthanide ions binding on tRNA(Phe) by H-1 NMR

The structure of phenylalanine transfer ribonucleic acid (tRNA(Phe)) in solution was explored by H-1 NMR spectroscopy to evaluate the effect of lanthanide ion on the structural and conformational change. It was found that La3+ ions possess specific effects on the imino proton region of the H-1 NMR spectra for yeast tRNA(Phe). The dependence of the imino proton spectra of yeast tRNA(Phe) as a function of La3+ concentration was examined, and the results suggest that the tertiary base pair G(15). C-48, which is located in the terminal in the augmented dihydrouridine helix (D-helix), was markedly affected by La3+ (shifted to downfield by as much as 0.35). Base pair U-8. A(14) in yeast tRNA(Phe), which are stacked on G(15). C-48, was also affected by added La3+ when 1 similar to 2 Mg2+ were also present. Another imino proton that may be affected by La3+ in yeast tRNA(Phe) is that of the tertiary base pair G(19). C-56. The assignment of this resonance in yeast tRNA(Phe) is tentative since it is located in the region of highly overlapping resonances beween 12.6 and 12.2. This base pair helps to anchor the D-loop to the T Psi C loop. The binding of La3+ caused conformational change of tRNA, which is responsible for shifts to upfield or downfield in H-1 NMR spectra.

NMR Spectra of polyimides: Interpretation and local chain motion study

Three kinds of high-performance polyimides 1 (poly(ketone-imide) PKI), 2 (poly(ether-imide) PEI) and 3 (poly(oxy-imide) POI) were studied using nuclear magnetic resonance (NMR). The NMR spectra of the polyimides were assigned according to the comprehensive consideration of the substitution effect of different substituting groups, viz. distortionless enhancement by polarization transfer (DEPT), no nuclear Overhauser effect (NNE), analysis of relaxation time, and two-dimensional correlated spectroscopy (COSY) techniques. The structural units of these three polyimides were determined. Carbon-13 and proton relaxation times for PEI and PKI were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (JS model) and anisotropic group rotation such as phenyl group rotation and methyl group rotation. Correlation times for the main-chain motion are in the tens of picosecond range which indicates the high flexibility of polyimide chains. Correlation times for phenyl group and methyl group rotations are more than 1 order of magnitude lower and approximately 1 order of magnitude higher than that of the main chain, respectively.

MAGNETIC-RESONANCE EXPERIMENTS ON UNDOPED AND DOPED POLY(PARA-PHENYLENE)

We investigated the electron paramagnetic resonance (EPR) spectra of undoped, FeCl3- and iodine-doped poly(para-phenylene) (PPP) prepared by the method of Kovacic. EPR measurements are used to characterize electronic states relevant for carrier transport in doped PPP. We found a novel dependence of room temperature linewidth (DELTAH(pp)) and spin density (N(spin)) on the dopant concentrations for iodine-doped PPP, namely, DELTAH(pp) first decreased and increased, and then decreased and increased again with increasing iodine concentration in the iodine-doped PPP. The corresponding value of N(spin) first increased and decreased, and then increased and decreased again with increasing iodine concentration in PPP. However, the changes in DELTAH(pp) and N(spin) with FeCl3 concentration in FeCl3-doped PPP differ from those of iodine-doped PPP. We explain the different EPR properties in FeCl3-doped and iodine-doped PPP.