Assembly of alternating polycation and DNA multilayer films by electrostatic layer-by-layer adsorption

The assembly of alternating DNA and positively charged poly(dimethyldiallylammonium chloride) (PDDA) multilayer films by electrostatic layer-by-layer adsorption has been studied. The real-time surface plasmon resonance (BIAcore) technique was used to characterize and monitor the formation of multilayer films in solution in real time continuously. Electrochemical impedance spectroscopy (EIS) and UV-vis absorbance measurements were also used to study the film assembly, and linear film growth was observed. All the results indicate that the uniform multilayer can be obtained on the poly(ethylenimine)- (PEI-) coated substrate surface. The kinetics of the adsorption of DNA on PDDA surface was also studied by the real-time BIAcore technique; the observed rate constant was calculated using a Langmuir model (k(obs) = (1.28 +/- 0.08) x 10(-2) s(-1).

Preparation and properties of nanocrystalline Yb2O3

Nanocrystalline Yb2O3 of various particle sizes was prepared using sol-gel method. XRD analysis shows that the prepared nanocrystalline Yb2O3 is cubic in structure with space group Ia3. TEM photographs indicate that Yb2O3 nanoparticles are basically spherical in shape. Calculation of crystallite size indicates that the average crystallite size of Yb2O3 increases with increasing calcination temperature, but the average crystal lattice distortion rate decreases with increasing calcination temperature and crystallite size. This result shows that the smaller the crystallite size, the bigger the crystal lattice distortion, and the worse crystal growth. Solubility test of Yb2O3 in nitric acid shows that the surface activity of Yb2O3 increases with decreasing crystallite size. Fourier Transform Infrared Spectrometer (FTIR) spectra reveal that nanocrystalline Yb2O3 has higher surface activity; than that of ordinary Yb2O3. Absorbance intensity of Yb-O bond of nanocrystalline Yb2O3 is weaker than that of ordinary Yb2O3, and the absorbance of Yb-O bond of nanocrystalline Yb2O3 is small blue-shifted.

Simultaneous spectrophotometric determination of trace iron (III) and aluminum (III) with hybrid linear analysis

Hybrid linear analysis (HLA) was applied to resolution of overlapping spectra of Fe3+-salicylfluorone and Al3+-salicylfluorone complexes and simultaneous spectrophotometric determination of Fe3+ and Al3+. The absorbance matrix of 7 standard mixtures at 41 measuring points ranged from the wavelength of 550 nm to 630 nm was used for calibration. To avoid the effect of interaction between the two components on the determination, the column vector of K matrix obtained from the standard mixtures with least squares was used as the pure spectrum of component. The recoveries of the two elements for the analysis of the synthetic samples were 93.3% similar to 107.5% in the range of the concentration ratio of Fe3+:Al3+ = 10:1 to 1:8. Comparing with the partial least squares (PIS) model, the HLA method was simple, accuracy and precise.

Synthesis and properties of optically active poly(amide-imide)s containing axially dissymmetric 1,1 '-binaphthyl moieties

Novel optically active aromatic poly(amide-imide)s (PAIs) containing 1,1'-binaphthyl-2,2'-diyl units in the main chain were prepared by polycondensation reactions of newly synthesized dianhydride, 2,2'-bis(3,4-dicarboxylzenzamido)-1,1'-binaphthyl dianhydride[(S)-BN-DADA and (+/-)-BNDADA], with diamines, The properties of the resulted PAIs were fully characterized by a combination of investigations on inherent viscosity, thermal properties(DSC and TGA), specific rotation, CD and UV-Vis absorbance. These PAIs showed good solubilities, thermal properties and optical stabilities. Interesting UV-Vis absorption behavior of films casted from these PAIs was observed and analyzed.

Study of molecular orientation in Langmuir-Blodgett films by FTIR

The structure information of orientation and packing of molecular chains can be obtained from infrared transmission and reflection-absorbance (RA) spectra. In the present paper, on the basis of Umemura et al., their FORTRAN program of minicomputer was developed and can be run on 486 personal computer. By comparison of infrared transmission and RA intensities, surface enhancement factors and molecular orientation angle were calculated using the above program, and the influence of complex refractive index, angle of incidence, and thickness of LB film were discussed. These results are consistent with that of Umemura et al.

CRYSTAL-STRUCTURE AND THERMODYNAMIC PARAMETERS OF NYLON-1010

WAXD, SAXS, FTIR, DSC and density techniques have been used to investigate the crystal structure, crystal density rho(c), amorphous density rho(a), equilibrium heat of fusion DELTAH(m)degrees and equilibrium melting temperature T(m)degrees. By extrapolating the straight lines in the FTIR absorbance against density plot to zero intensity, rho(c) and rho(a) were estimated to be 1.098 and 1.003 g/cm3 respectively. The rho(c) obtained was too low in value. From X-ray diffraction patterns of uniaxially oriented fibres, the crystal structure of Nylon-1010 was determined. The Nylon-1010 crystallized in the triclinic system, with lattice dimensions: a = 4.9 angstrom, b = 5.4 angstrom, c = 27.8 angstrom, alpha = 49-degrees, beta = 77-degrees, gamma = 63.5-degrees. The unit cell contained one monomeric unit, the space group was P1BAR, and the correct value of rho(c) was 1.135 g/cm3. The degree of crystallinity of the polymer was determined as about 60% (at RT) using Ruland's method. SAXS has been used to investigate the crystalline lamellar thickness, long period, transition zone, the specific inner surface and the electron density difference between the crystalline and amorphous regions for Nylon-1010. The analysis of data was based upon a one-dimensional electron-density correlation function. DELTAH(m)degrees was estimated to be 244.0 J/g by extrapolation of DELTAH(m)degrees in the plot of heat of fusion against specific volume of semicrystalline specimens to the completely crystalline condition (V(sp)c = 1/rho(c)). Owing to the ease of recrystallization of melt-crystallized Nylon-1010 specimens, the well-known Hoffman's T(m)-T(c) method failed in determining T(m)degrees and a Kamide double extrapolation method was adopted. The T(m)degrees value so obtained was 487 K.

STRUCTURE OF MESOMORPHIC FORM OF ISOTACTIC POLYPROPYLENE

The structure of quenched isotactic polypropylene (iPP) films, including samples etched with fuming nitric acid (FNA), has been studied by infrared (IR) spectra, wide-angle x-ray diffraction (WAXD), small-angle x-ray scattering (SAXS), and differential scanning calorimetry (DSC) measurements. The changes of IR, SAXS, DSC, and WAXD results induced by annealing for etched samples have been compared with those for unetched ones. The IR absorbance spectrum of the quenched iPP etched by FNA did not change. In addition, the SAXS intensity did not increase when these samples were annealed, indicating that the total (IR) crystallinity (i.e., the content of chain segments in the helical conformations) of the etched samples does not increase. However, WAXD patterns of the samples changed in a manner similar to those of the unetched one, from the original two blurred diffraction peaks to the sharp crystal patterns of alpha-form iPP, suggesting that the mesomorphic (or liquid crystal-like) phase has reorganized to alpha-form crystals. It is concluded that the change of WAXD of quenched iPP films during annealing results mainly from transformation of order in the mesomorphic phase, rather than only from an increase of crystal size. In other words, mesomorphic-form iPP is not constituted by any known crystals (such as alpha or beta crystals) in small sizes; its WAXD pattern reflects truly the degree of order in the mesomorphic phase.

INVESTIGATION OF ELECTRIC DICHROISM OF CETYLPYRIDINIUM BROMIDE BY SPECTROELECTROCHEMISTRY WITH A LONG OPTICAL-PATH LENGTH THIN-LAYER CELL

In this paper, the electric dichroism of cetylpyridinium bromide (CPB) has been found and studied by spectroelectrochemistry with a long optical path length thin-layer cell (LOPTLC) for the first time. The CPB molecule with a long carbon chain and a polar pyridinium ring is anisotropic in molecular configuration or in polarizability. In the electric field of a thin-layer cell, the CPB molecule reorientates along the direction of the electric field and exhibits electric dichroism, which results in the increase of absorbance of CPB in the UV-vis range. By use of in situ measurement of spectroelectrochemistry, the order parameters of long molecular axis (S = 0.845) and short molecular axis (D = 0.155) and the angle between the long axis direction of the CPB molecule and the direction normal to the electrode surface (theta = 18-degrees 44') have been determined. These data were used to describe the state of arrangement of the molecules in the solution. The reorientation of CPB molecules is the result of the interaction between the anisotropic molecules and electric field. The effects of the concentration of CPB and of the applied electric field on the electric dichroism have been investigated.

SPECTROELECTROCHEMISTRY WITH CYLINDRICAL CARBON-FIBER MICROELECTRODES

Transmittance spectroelectrochemistry can be performed using a group of cylindrical microelectrodes. A dependence of absorbance on electrolytic charge during the potential step was derived. The rate constant of catalytic reaction of the ferrocyanide-ascorbic acid system was determined using single potential step-open circuit relaxation chronoabsorptometry. This is the first report that the reaction can still be considered as a pseudo-first-order reaction when the concentration of ascorbic acid is close to and even slightly lower than the concentration of ferrocyanide. The determined rate constant is in agreement with the reported value. The reason is that the diffusion of ascorbic acid toward electrode surface is contractive and the diffusion of the electrogenerated ferricyanide from the electrode surface to the bulk of solution is expansive.

THE REVERSIBLE ELECTRON-TRANSFER REACTION OF MYOGLOBIN AT BRILLIANT CRESYL BLUE MODIFIED PLATINUM GAUZE ELECTRODE

The electrochemical behavior of myoglobin at a Brilliant Cresyl Blue (BCB) modified platinum gauze electrode and spiral pt wire in the BCB solution in optically transparent thin layer cell base been investigated by using cyclic potential-absorbance method and double potential step chronoabsorptometry. The results reveal a reversible electron transfer resection of myoglobin. Exhaustive reductive and oxidative electrolyses are achieved at the modified platinum surface in 20 and 100s respectively. The formal h...

A potent anti-oxidant property: fluorescent recombinant alpha-phycocyanin of Spirulina

To express and product a fluorescent antioxidant holo-alpha-phycocyanin (PC) of Spirulina platensis (Sp) with His-tag (rHHPC; recombinant holo-alpha-phycocyaninof Spirulina platensis with His-tag) in 5-l bench scale. A vector harbouring two cassettes was constructed: cpcA along with cpcE-cpcF in one cassette; ho1-pcyA in the other cassette. Lyases CpcE/F of Synechocystis sp. PCC6803 (S6) could catalyse the 82 site Cys in apo-alpha-PC of Sp linking with bilin chromophores, and rHHPC was biosynthesized in Escherichia coli BL21. The constant feeding mode was adopted, and transformant reached the biomass of rHHPC up to 0.55 g l(-1) broth in 5-litre bench scale. rHHPC was purified by Ni2+ affinity column conveniently. The absorbance and the fluorescence emission spectra of rHHPC had lambda(max) at 621 and 650 nm, respectively. The IC50 values of rHHPC were 277.5 +/- 25.8 mu g ml(-1) against hydroxyl radicals and 20.8 +/- 2.2 mu g ml(-1) against peroxyl radicals. Combinational biosynthesis of rHHPC was feasible, and the constant feeding mode was adopted to produce good yields of rHHPC. Fluorescent rHHPC with several unique qualitative and quantitative features was effective on scavenging hydroxyl and peroxyl radicals. A potent antioxidant rHHPC was co-expressed, produced and characterized for nutritional and pharmacological values, which would help to develop phycobiliproteins' applications in their fluorescent and biological activities.

Photosynthetic parameters of sexually different parts of Porphyra katadai var. hemiphylla (Bangiales, Rhodophyta) during dehydration and re-hydration

Physiological data from extreme habitat organisms during stresses are vital information for comprehending their survival. The intertidal seaweeds are exposed to a combination of environmental stresses, the most influential one being regular dehydration and re-hydration. Porphyra katadai var. hemiphylla is a unique intertidal macroalga species with two longitudinally separated, color distinct, sexually different parts. In this study, the photosynthetic performance of both PSI and PSII of the two sexually different parts of P. katadai thalli during dehydration and re-hydration was investigated. Under low-grade dehydration the variation of photosystems of male and female parts of P. katadai were similar. However, after the absolute water content reached 42%, the PSI of the female parts was nearly shut down while that of the male parts still coordinated well and worked properly with PSII. Furthermore, after re-hydration with a better conditioned PSI, the dehydrated male parts were able to restore photosynthesis within 1 h, while the female parts did not. It is concluded that in P. katadai the susceptibility of photosynthesis to dehydration depends on the accommodative ability of PSI. The relatively lower content of phycobiliprotein in male parts may be the cause for a stronger PSI after severe dehydration.

One-step chromatography method for efficient separation and purification of R-phycoerythrin from Polysiphonia urceolata

Phycoerythrins have been widely used in food, cosmetics., immunodiagnostics and analytical reagents. An efficient one-step chromatography method for purification of R-phycoerythrins from Polysiphonia urceolata was described in this paper. Pure R-phycoerythrin was obtained with an absorbance ratio A(565)/A(280) of 5.6 and a high recovery yield of 67-33%, using a DEAE-Sepharose Fast Flow chromatography with a gradient elution of pH, alternative to common gradient elution of ionic strength. The absorption spectrum of R-phycoerythrin was characterized with three absorbance maxima at 565, 539 and 498 mum, respectively and the fluorescence emission spectrum at room temperature was measured to be 580nm. The results of native-PAGE. and SDS-PAGE showed no contamination by other proteins in the phycoerythrin solution. which suggests an efficient method for the separation and purification of R-phycoerythrins from Polysiphonia urceolata. (C) 2004 Elsevier B.V. All rights reserved.

Study of a new derivatizing reagent that improves the analysis of amino acids by HPLC with fluorescence detection: application to hydrolyzed rape bee pollen

A simple and sensitive method for evaluating the chemical compositions of protein amino acids, including cystine (Cys)(2) and tryptophane (Try) has been developed, based on the use of a sensitive labeling reagent 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl chloroformate (BCEC-Cl) along with fluorescence detection. The chromophore of the 1,2-benzo-3,4-dihydrocarbazole-ethyl chloroformate (BCEOC-Cl) molecule was replaced with the 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl functional group, yielding the sensitive fluorescence molecule BCEC-Cl. The new reagent BCEC-Cl could then be substituted for labeling reagents commonly used in amino acid derivatization. The BCEC-amino acid derivatives exhibited very high detection sensitivities, particularly in the cases of (Cys)(2) and Try, which cannot be determined using traditional labeling reagents such as 9-fluorenyl methylchloroformate (FMOC-Cl) and ortho-phthaldialdehyde (OPA). The fluorescence detection intensities for the BCEC derivatives were compared to those obtained when using FMOC-Cl and BCEOC-Cl as labeling reagents. The ratios I (BCEC)/I (BCEOC) = 1.17-3.57, I (BCEC)/I (FMOC) = 1.13-8.21, and UVBCEC/UVBCEOC = 1.67-4.90 (where I is the fluorescence intensity and UV is the ultraviolet absorbance). Derivative separation was optimized on a Hypersil BDS C-18 column. The detection limits calculated from 1.0 pmol injections, at a signal-to-noise ratio of 3, ranged from 7.2 fmol for Try to 8.4 fmol for (Cys)(2). Excellent linear responses were observed, with coefficients of > 0.9994. When coupled with high-performance liquid chromatography, the method established here allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids including (Cys)(2) and Try from bee-collected pollen (bee pollen) samples.

Photosynthesis of Saussurea superba and Gentiana straminea is not reduced after long-term enhancement of UV-B radiation

Experiments were conducted in an alpine Kobresia humilis meadow near Haibei Alpine Meadow Ecosystem Research Station (37degrees29'-37degrees45'N, 101degrees12'-101degrees33'E; altitude 3200 m). Effects of enhanced ultraviolet-B (UV-B) radiation on photosynthesis of the alpine plants of Saussurea superba and Gentiana straminea were investigated. Both species were exposed to a UV-B-BE density at 15.80 kJ m(-2) per day, simulating nearly 14% ozone (O-3) reduction during the plant growing season. Neither photosynthetic CO2 uptake rate nor photosynthetic O-2 evolution rate were decreased after a long period of enhanced UV-B radiation treatment. On the contrary, there was a tendency to increase of both parameters in both species. The photosynthetic pigments were also increased, when expressed on a leaf area basis. UV-B absorbing compounds, detected by the absorbance values at 300 mm, had a tendency to increase in both species after enhanced UV-B radiation. After long-term exposure of plants to enhanced UV-B radiation, leaf morphology was also affected. Leaf thickness in both S. superba and G. straminea were increased significantly (P < 0.001). This supports our hypothesis that the increase of leaf thickness in both species after long-term exposure of enhanced UV-B radiation could compensate for the photodestruction of photosynthetic pigments when light passes through the leaf. Therefore, photosynthesis is not reduced in either species when expressed on leaf area basis. (C) 2003 Elsevier B.V. All rights reserved.