In situ EPR and UV-vis spectroelectrochemistry of hole-transporting organic substrates

A newly developed in situ electron paramagnetic resonance (EPR)/ultraviolet-visible (UV-vis) spectroelectrochemical cell equipped with a laminated indium-tin oxide (ITO) working electrode was used in the investigation of various organic substrates which are potential hole-transporting materials. The experiment demonstrated the possibility of using such a technique for examining redox behavior of conducting polymers (polypyrrole, PPy), oligomers (thiophene dimmer and quarterthiophene) and bis-anilines (N,N,N',N'-tetraphenylbenzidine, TPB). All investigated structures formed stable paramagnetic intermediates in the first oxidation step characterised with UV-vis spectra in the region 400-600 nm. In the second oxidation step EPR-silent di-cationic structures are formed with broad vis bands in the region 600-1000 nm. The measurement of the reference UV-vis spectra direct in the EPR cavity was possible using a specially-constructed non-contacted ITO plate in the spectroelectrochemical cell in the case of polypyrrole.     

Controlled adsorption of cellulase onto pretreated corncob by pH adjustment

The effective recycling of cellulase requires an in-depth understanding of cellulase adsorption and desorption. In the present study, we examined the adsorption behaviors and stabilities of cellulase at different pH values. Acidic pH (<4.8) was found to favor adsorption, whereas neutral and alkaline pH (especially pH 7 and 10) favored desorption. The influence of pH on cellulase activity was temperature dependent. Under mild conditions (e.g., pH 7 and 25 °C), the effect of pH on cellulase activity was reversible, and the cellulase activity can return to almost 100% by adjusting the pH value to 4.8. However, under severe conditions (e.g. pH 10 and 50 °C), irreversible inactivation may take place. We also explored the roles of pH and temperature in cellulase adsorption kinetics and isotherms. At pH 4.8, temperature had no remarkable effect on the adsorption capacity of the cellulases onto substrate. However, at pH 7 and 10, high temperatures lead to more cellulase desorption. Only at pH 4.8 does cellulase adsorption well fit (R ² > 0.96) the pseudo-first-order kinetic and Langmuir adsorption isotherm (R ² > 0.99) models.     

In situ electroacoustic monitoring of polyelectrolyte adsorption onto protein-coated oil droplets

The purpose of this study was to compare the ability of electroacoustic (EA) and microelectrophoresis (ME) techniques for monitoring the adsorption of an anionic polysaccharide onto the surfaces of oppositely charged protein-coated oil droplets. The zeta-potential values determined by the EA technique were in excellent agreement with those determined by the ME technique. Both techniques were able to monitor the adsorption of pectin onto the surfaces of beta-lactoglobulin-coated droplets as a function of pectin concentration and pH. The major advantage of the EA technique was that it could be carried out in situ without having to dilute the emulsions, so that the equilibrium between adsorbed and non-adsorbed polyelectrolyte was not disturbed by dilution. Nevertheless, the good agreement between the zeta-potential values determined by the EA and ME techniques suggested that emulsion dilution did not cause an appreciable change in polysaccharide partitioning for the system used in this study. In summary, the EA technique appears to be a powerful means of monitoring polyelectrolyte adsorption in concentrated colloidal dispersions.     

Comparison between the growth of gold particles onto MgO and amorphous carbon substrates by in situ electrical conductance measurements

The sheet conductance of gold condensates on MgO anda-C is expressed in terms of granulometric quantities. This expression enables us to follow the evolution of metal repartition on its substrate during the gold evaporation. The difference between the growth modes of these gold layers on MgO and ona-C is explained by the predominance of respectively nucleation and coalescence phenomena     

Bovine serum albumin adsorption onto colloidal Al2O3 particles: a new model based on zeta potential and UV-vis measurements

We investigated the adsorption of bovine serum albumin (BSA) on colloidal Al2O3 particles in an aqueous environment. Changes in the zeta potential of the Al2O3 particles upon the adsorption of BSA were measured using an electro-acoustic technique. The mass of protein adsorbed was determined by using UV-vis spectroscopy. The change of the isoelectric point of the Al2O3 powder-protein suspension was found to be a function of adsorbed protein mass. It was shown that approximately one monolayer of BSA was needed to fully mask the surface and to compromise the charge of Al2O3. From titration experiments it follows that about 30-36% of the negatively charged groups of the protein form bonds with the protonated and charged Al2O3 surface. On the basis of our observations we introduced a new adsorption model for BSA on Al2O3 particles.     

Determination of trace phosphorus in zirconium-niobium alloy and Zircaloy by UV-vis spectrophotometry

A spectrophotometric method has been developed for the determination of traces of phosphorus in zirconium based alloys (Zr-2.5Nb and Zircaloy). It is achieved by selective fluoride complexation controlled by boric acid. The samples were dissolved in HF and fluoro-complexes of the matrices were formed by maintaining the concentration of HF while the excess HF was controlled by boric acid. After the formation of phosphomolybdate, extracted into n-butyl acetate, ion-associated with crystal violet and the absorbance was measured at 582 nm. The results obtained by this procedure were in close agreement with the certified reference material (CRM) values and further these values were compared with the values determined by Glow Discharge-Quadrupole Mass Spectrometry (GD-QMS). The potential interferences like fluoride, silicon, arsenic(V), niobium, titanium, tantalum, etc., were tolerable to large level. LOD (3 s) was found to be 0.055 mg kg(-1) with a precision (R.S.D.) of 2-3% and molar absorptivity was 2.7x10(5) L mol(-1) cm(-1).     

Spectroscopic and thermodynamic characterization of the adsorption of plasma proteins onto cellulosic substrates

The sorption of the plasma proteins human serum albumin (HSA) and human fibrinogen (FIB) onto hemodialytic cellulosic substrates was investigated by the surface sensitive ATR-FTIR-spectroscopy. By means of this method we monitored the protein sorption kinetics onto acetylated and unmodified cellulose (AKZO-NOBEL). Furthermore, secondary structure alterations of the adsorbed proteins as well as changes of the composition in sorbed layers consisting of two proteins were detected. These findings were compared with results of the zeta potential and contact angle measurements on comparable sorption experiments.     

Study of the adsorption of a hydrophobic peptide onto carbon surfaces by capacitance measurements

The adsorption of a hydrophobic peptide (β-CN (193–209)) onto glassy carbon and a carbon support of membrane was studied by double-layer capacitance measurements using electrochemical impedance spectroscopy (SIE). The kinetics of adsorption was investigated by recording the changes that occurred in the double-layer capacitance after adding the peptide. The change in capacitance was interpreted in terms of the number of close-contact areas between the peptide and the surface. A two-consecutive reaction model was used to describe peptide adsorption. The first step was attributed to the adsorption reaction itself and the second to a change in the conformation of the adsorbed peptide molecules. The corresponding theoretical equation of the variation of capacitance with time fits our results. Moreover, it allowed determination of the time constants for both reactions and three double-layer capacitances: the bare surface and the surfaces covered with monolayers of the peptide in states 1 and 2. For glassy carbon, the activation energies are 4.7 and 3.5 kJ mol⁻¹ for the first and second step of the reaction and the reaction orders are 0.64 and 0.35, respectively. These values are different for each step. This confirms the model of two separate reactions to describe adsorption. The first step comprises two elementary mechanisms. The first may correspond to the adsorption of the peptide onto the surface. The second may be consistent with a modification of the adsorbed molecules induced by the adsorption of other molecules over them. The second step of the process requires the contribution of peptides of the solution for it to occur. The changes in the double-layer capacitance depend on the peptide bulk concentration. This suggests that the peptide adsorbs in a different conformation depending on its bulk concentration. Peptide polymerisation could be responsible for this phenomenon.     

Fibrinogen adsorption on mica studied by AFM and in situ streaming potential measurements

Adsorption of fibrinogen from aqueous solutions on mica was studied using AFM and in situ streaming potential measurements. In the first stage, bulk physicochemical properties of fibrinogen and the mica substrate were characterized for various ionic strength and pH. The zeta potential and number of uncompensated (electrokinetic) charges on the protein surfaces were determined from microelectrophoretic measurements. Analogously, using streaming potential measurements, the electrokinetic charge density of mica was determined for pH range 3-10 and the NaCl background electrolyte concentration of 10(-3) and 10(-2) M. Next, the kinetics of fibrinogen adsorption at pH 3.5 and 7.4 in the diffusion cell was studied using a direct AFM determination of the number of molecules per unit area of the mica substrate. Then, streaming potential measurements were performed to determine the apparent zeta potential of fibrinogen-covered mica for different pH and ionic strength in terms of its surface concentration. A quantitative interpretation of these streaming potential measurements was achieved in terms of the theoretical model postulating a side-on adsorption of fibrinogen molecules as discrete particles. On the basis of these results, the maximum coverage of fibrinogen Θ close to 0.29 was predicted, in accordance with previous theoretical predictions. It was also suggested that anomalous adsorption for pH 7.4, where fibrinogen and the mica substrate were both negatively charged, can be explained in terms of a heterogeneous charge distribution on fibrinogen molecules. It was estimated that the positive charge was 12 e (for NaCl concentration of 10(-2) M and pH 7.4) compared with the net charge of fibrinogen at this pH, equal to -21 e. Results obtained in this work proved that the coverage of fibrinogen can be quantitatively determined using the streaming potential method, especially for Θ < 0.2, where other experimental methods become less accurate.     

Ultra-sensitive determination of cadmium in rice and water by UV-vis spectrophotometry after single drop microextraction

In this work, a new method based on single drop microextraction (SDME) preconcentration using tetrachloromethane (CCl(4)) as extraction solvent was proposed for the spectrophotometric determination of cadmium in rice and water samples. The influence factors relevant to SDME, such as type and volume of extractant, stirring rate and time, dithizone concentration, pH, drop volume and instrumental conditions were studied systematically. Under the optimal conditions, the limit of detection (LOD) was 0.5 ng L(-1), with sensitivity enhancement factor (EF) of 128. The different maximum absorption wavelength caused by the different extraction acidity compared with some conventional works and the enhancement effect of acetone (dilution solvent) for the spectrophotometric determination were the two key factors of the high EF and sensitivity. The proposed method was applied to the determination of rice and water samples with satisfactory analytical results. The proposed method was simple, rapid, cost-efficient and sensitive.     

In situ FT-IR and UV-vis spectroscopy of the low-temperature NO disproportionation mediated by solid state manganese(II) porphyrinates

The heterogeneous reaction between NO gas and sublimed layers of manganese(II) porphyrinato complexes Mn(Por) (Por = TPP (tetraphenylporphyrinato dianion), TMP (tetramesitylporphyrinato dianion), or TPP(d20) (perdeuterated tetraphenylporphyrinato dianion)) has been monitored by IR and optical spectroscopy over the temperature range of 77 K to room temperature. These manganese porphyrins promote NO disproportionation to NO2 species and N2O, and the reaction proceeds via several distinct stages. At 90 K, the principal species observed spectrally are the nitric oxide dimer, cis-ONNO, two manganese nitrosyls, the simple NO adduct Mn(Por)(NO), and another intermediate (1) that is apparently critical to the disproportionation mechanism. This key intermediate is formed prior to N2O evolution, and proposals regarding its likely structure are offered. When the system is warmed to 130 K, the disproportionation products, N2O and the O-coordinated nitrito complex Mn(Por)(NO)(ONO) (2), are formed. IR spectral changes show that, upon further warming to 200 K, 2 isomerizes into the N-bonded nitro linkage isomer Mn(Por)(NO)(NO2) (3). After it is warmed to room temperature, the latter species loses NO and converts to the known 5-coordinate nitrito complex Mn(Por)(ONO) (4).     

Probing protein adsorption onto mercaptoundecanoic acid stabilized gold nanoparticles and surfaces by quartz crystal microbalance and zeta-potential measurements

The adsorption characteristics of three proteins [bovine serum albumin (BSA), myoglobin (Mb), and cytochrome c (CytC)] onto self-assembled monolayers of mercaptoundecanoic acid (MUA) on both gold nanoparticles (AuNP) and gold surfaces (Au) are described. The combination of quartz crystal microbalance measurements with dissipation (QCM-D) and pH titrations of the zeta-potential provide information on layer structure, surface coverage, and potential. All three proteins formed adsorption layers consisting of an irreversibly adsorbed fraction and a reversibly adsorbed fraction. BSA showed the highest affinity for the MUA/Au, forming an irreversibly adsorbed rigid monolayer with a side-down orientation and packing close to that expected in the jamming limit. In addition, BSA showed a large change in the adsorbed mass due to reversibly bound protein. The data indicate that the irreversibly adsorbed fraction of CytC is a monolayer structure, whereas the irreversibly adsorbed Mb is present in form of a bilayer. The observation of stable BSA complexes on MUA/AuNPs at the isoelectric point by zeta-potential measurements demonstrates that BSA can sterically stabilize MUA/AuNP. On the other hand, MUA/AuNP coated with either Mb or CytC formed a reversible flocculated state at the isoelectric point. The colloidal stability differences may be correlated with weaker binding in the reversibly bound overlayer in the case of Mb and CytC as compared to BSA.     

In situ control of cellular growth and migration on substrates using microelectrodes

We describe an electrochemical method to direct the growth and migration of mammalian cells on a substrate during cultivation in situ. Exposing the albumin-coated substrate to an oxidizing agent, hypobromous acid, electrochemically generated at the tip of the scanning microelectrode, locally switched the substrate from cytophobic to cell-adhesive. This transformation generated the formation of cellular micropatterns. Since the concentration of the oxidizing agent required for the surface processing did not cause significant damage to the cell cultures, we were able to direct in situ cellular proliferation and migration by drawing adhesive micropatterns over the preexisting cellular pattern.     

In situ measurements of nanotube dimensions in suspensions by depolarized dynamic light scattering

We show that the dimensions of carbon nanotubes (CNTs) in suspension can be characterized by depolarized dynamic light scattering. Taking advantages of this in situ technique, we investigate in detail the influence of sonication procedures on the length and diameter of CNTs in surfactant solutions. Sonication power is shown to be particularly efficient at unbundling nanotubes, whereas a long sonication time at low power can be sufficient to cut the bundles with limited unbundling. We finally demonstrate the influence of CNT dimensions on the electrical properties of CNT fibers. Slightly varying the sonication conditions, and thereby the suspended nanotube dimensions, can affect the fibers conductivity by almost 2 orders of magnitude.     

In situ recording of particle network formation in liquids by ion conductivity measurements

The formation of fractal silica networks from a colloidal initial state was followed in situ by ion conductivity measurements. The underlying effect is a high interfacial lithium ion conductivity arising when silica particles are brought into contact with Li salt-containing liquid electrolytes. The experimental results were modeled using Monte Carlo simulations and tested using confocal fluorescence laser microscopy and ζ-potential measurements.     

采用实时直接分析质谱法原位快速鉴别茶叶

采用近年来发展迅速的常温常压离子化技术——实时直接分析质谱法,建立了对茶叶中主要成分如茶氨酸、咖啡碱等的快速测定方法,通过特征的质谱信号离子,实现了对不同茶叶的快速鉴别。实时直接分析质谱法在大气压下进行,无需对茶叶进行任何的样品处理,大大缩短了分析时间,实现了原位、快速、准确且高通量的检测。     

In situ small-angle neutron scattering and rheological measurements of shear-induced gelation

The microscopic structure of shear-induced gels for a mixed solution of 2-hydroxyethyl cellulose and nanometer-size spherical droplets has been investigated by in situ small-angle neutron scattering (SANS) with a Couette geometry as a function of shear rate gamma. With increasing gamma, the viscosity increased rapidly at gamma approximately 4.0 s(-1), followed by a shear thinning. After cessation of shear, the system exhibited an extraordinarily large steady viscosity. This phenomenon was observed as a shear-induced sol-gel transition. Real-time SANS measurements showed an increase in the scattering intensity exclusively at low scattering angle region. However, neither orientation of polymer chains nor droplet deformation was detected and the SANS patterns remained isotropic irrespective of gamma. It took about a few days for the gel to recover its original sol state. A possible mechanism of gelation is proposed from the viewpoint of shear-induced percolation transition.     

Comparative study on the determination of cephalexin in its dosage forms by spectrophotometry and HPLC with UV-vis detection

This paper discusses the spectrophotometric determination of cephalexin as the intact cephalexin or as its acid-induced degradation product. Cephalexin can be determined in the range 1 × 10^–5–18 × 10^–5 M with relative standard deviations of 5-1%. The limits of quantitation and detection were 10^–5 and 0.3 × 10^–5 M, respectively. These procedures were compared with reversed-phase HPLC determination. No interference was observed in the presence of common pharmaceutical adjuvants. The H-point standard additions method was applied in order to correct for the possible presence of the cephalexin precursor, 7-aminocephalosporanic acid; this improves the selectivity of the UV-vis spectrophotometric method.