Determination of Arsenic and Mercury in Chinese Medicinal Herbs by Atomic Fluorescence Spectrometry with Closed‐Vessel Microwave Digestion

Abstract

A simple method was developed for the determination of trace arsenic and mercury in Chinese medicinal herbs. The samples were digested in closed‐Teflon vessels in a microwave oven, and followed with hydride generation atomic fluorescence spectrometric measurements. The experimental conditions for the digestion were carefully optimized using an orthogonal design. The accuracy of the method was validated by recovery experiments, and the analytical results for arsenic in seven medicinal herbs (Codonopsis pilosula, Radix angelicae sinensis, Aconitum carmichaeli debx, crude aconite root, giant typhonium rhizome, Rhizoma typhonii, and Radix aconiti lateralis preparata) were found to agree well with those by inductively coupled plasma atomic emission spectrometry (ICP‐AES). The linear dynamic range of the calibration curve was in the range of 0.1–400 ng/mL for arsenic, and the correlation coefficient was better than 0.999. The limit of detection was 0.1 ng/mL for arsenic. For mercury, the determination was accomplished through mercury cold vapor generation in the same instrumental system. The linear dynamic range was 0.03–250 ng/mL, with a limit of detection of 0.03 ng/mL for mercury. This was a rapid, convenient, precise, and cost‐effective method.     

Relationship of Processing Conditions to Structure and Properties in PMDA‐ODA Polyimide

A combined wide angle X‐ray diffraction (WAXD)/small‐angle X‐ray scattering (SAXS)/scanning electron microscopy (SEM)/density study of structure and morphology was carried out for a large series of pyromellitic dianhydride‐oxydianiline (PMDA‐ODA) polyimide (PI) samples processed using different powder metallurgy techniques. Using a combined DSC/creep rate spectroscopy (CRS)/long‐term creep resistance (LTCR) approach, their molecular dynamics, thermal and elastic properties, and creep resistance in the temperature range from 20 to 470°C were also studied. Both a choice of the method of formation of fine PI particles and the order of applying high pressure relative to high temperature to form the monolithic samples led to the observation of significant property differences. Relationships between the processing conditions, structure, and properties were determined. As a result, the conditions for optimizing certain PMDA‐ODA polyimide properties, especially creep resistance and elastic properties at extreme temperatures, were determined.     

Characterization of Crystalline Phase‐Transformations in Theophylline by Time‐Domain Terahertz Spectroscopy

Time‐domain terahertz (THz) spectroscopy has been used to characterize polymorphic transformations in polycrystalline theophylline, a widely used pharmaceutical compound. On transformation, different intermolecular bonding arrangements arise owing to changes in the lattice structure of the molecular crystal, leading to distinct THz spectral signatures. Temperature‐dependent THz absorption measurements in anhydrous theophylline confirm that the observed vibrational modes originate from phonons within the crystal structure.     

Application of Synchrotron X‐Ray Microbeam Spectroscopy to the Determination of Metal Distribution and Speciation in Biological Tissues

Abstract

Resolving the distribution and speciation of metal(loid)s within biological environmental samples is essential for understanding bioavailability, trophic transfer, and environmental risk. We used synchrotron x‐ray microspectroscopy to analyze a range of samples that had been exposed to metal(loid) contamination. Microprobe x‐ray fluorescence elemental mapping (µSXRF) of decomposing rhizosphere microcosms consisting of Ni‐ and U‐contaminated soil planted with wheat (Triticum aestivum) showed the change in Ni and U distribution over a 27‐day period, with a progressive movement of U into decaying tissue. µSXRF maps showed the micrometer‐scale distribution of Ca, Mn, Fe, Ni, and U in roots of willow (Salix nigra L.) growing on a former radiological settling pond, with U located outside of the epidermis and Ni inside the cortex. X‐ray computed tomography (CMT) of woody tissue of this same affected willow showed that small points of high Ni fluorescence observed previously are actually a Ni‐rich substance contained within an individual xylem vessel. µSXRF and x‐ray absorption near‐edge spectroscopy (XANES) linked the elevated Se concentrations in sediments of a coal fly ash settling pond with oral deformities of bullfrog tadpoles (Rana catesbeiana). Se distribution was localized within the deformed mouthparts, and with an oxidation state of Se (?II) consistent with organo‐Se compounds, it suggests oral deformities are caused by incorporation of Se into proteins. The range of tissues analyzed in this study highlight the applicability of synchrotron X‐ray microspectroscopic techniques to biological tissues and the study of metal(loid) bioavailability.     

Modification of Absorption of a Bulk Material by Photonic Crystals

We show theoretically that it is possible to modify absorption of a bulk absorbing material by inserting another non-absorbing dielectric slab periodically to form one-dimensional photonic crystals.It is found that,for frequencies within photonic bandgaps,absorption is always suppressed.For frequencies located at photonic bands,absorption can be suppressed or enhanced,which depends on the relative values of the real refractive index of the absorbing and non-absorbing dielectric layers.     

Determination of Toxic Elements in Muscle Tissues of Five Fish Species Using Ultrasound‐Assisted Pseudodigestion by Electrothermal Atomic Absorption Spectrophotometry: Optimization Study

A simple and rapid method is described for the determination of As, Cd, and Pb in muscle tissue of five freshwater fish species by ultrasound‐assisted pseudodigestion (USD). A Plackett‐Burman experimental design was used as a multivariate strategy for the evaluation of the effects of varying several variables at once. The variables such as sonication time (ST), sample mass of muscle tissues (SM), temperature of ultrasonic bath (T), nitric acid (A1), and mixture of acid and oxidant (A2) have been studied. From these studies, some variables showed significant effect on % recovery, and they were further optimized by a 2³+star central composite design, which involved 16 experiments. Optimum values of the variables were selected for the development of USD to determine the contents of As, Cd, and Pb in muscle tissue of five fish species, used as bioindicators for Lake Manchar (Sindh, Pakistan) to know whether consumption of these fishes threatens human health. The determination of three toxic elements under study was carried out by electrothermal atomic absorption spectrometry (ETAAS). The accuracy of the optimized procedure was evaluated by analysis of certified reference materials DORM‐2 (Dogfish Muscle Certified Reference Material for Trace Elements) and by comparison with conventional wet acid digestion methodology. No significant differences were observed for p=0.05 when comparing the values obtained by the proposed USD method and conventional digestion method (CDM) (paired t‐test). The average relative standard deviation of the USD method varied between 4.05%, 7.53%, and 4.55% for As, Cd, and Pb, respectively (n=10).     

The Investigation of Miscibility in Blends of ENR/AO‐80 by DMA and FT‐IR

A hindered phenol 3,9‐bis[1,1‐dimethyl‐2{β‐(3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl) propionyloxy}ethyl]‐2,4,8,10‐tetraoxaspiro[5,5]‐undecane (AO‐80) was solution blended with epoxidized natural rubber (ENR). The miscibility behavior and hydrogen bonding of the blend were investigated by dynamic mechanical analysis (DMA) and Fourier‐transform infrared spectroscopy (FT‐IR). Only one glass transition due to the inter‐hydrogen bond between hydroxyls of AO‐80 and oxirane rings of ENR was observed by DMA, which indicates the ENR/AO‐80 system is miscible. Furthermore, a negative Tg‐composition deviation was obtained in terms of the Gorden‐Taylor equation. In order to illustrate the interaction between AO‐80 and ENR, FT‐IR was used to study the hydrogen bond interaction between the hydroxyl of AO‐80 and the oxirane ring of ENR at various temperatures and compositions. Finally, a possible dispersion state of AO‐80 in the ENR matrix was proposed to illustrate the phenomena obtained by DMA and FT‐IR.     

Interpretation of Viscosity Behavior of a Polyelectrolyte in a Salt‐Free Polar Solvent by Ion‐Association

Abstract

On the basis of three hypothesis: (1) ion association according to the mass action law, (2) no interchain association due to the same sort of charges on the chains, and (3) chain expansion owing to intrachain Coulombic repulsive force, a theoretical equation was derived to describe the viscosity behavior of a polyelectrolyte in a salt‐free polar solvent. The resulting equation fits well with experimental viscosity behavior of a polyelectrolyte solution in polar solvents. With some approximations, the equation leads to the Fuoss empirical equation. The effects of molecular weight, the average distance of two neighboring ionizable groups along the polymer chain, and the nature of the solvent on the polyelectrolyte conformation are discussed.     

Fluorescence Quenching of UVITEX‐OB by Aniline in Alcohols and Alkanes

Fluorescence quenching of UVITEX‐OB [2,5‐thiophenediylbis(5‐tert‐butyl‐1,3‐benzoxazole)] by aniline in different polar and nonpolar solvents was examined at room temperature by steady‐state fluorescence measurements. Positive deviations from the nonlinear Stern–Volmer plots were observed in most of the solvents indicating the extent of quenching to be large. The quencher concentration dependence data were analyzed using ground‐state complex and sphere of action static quenching models in order to interpret the results. The magnitudes of the quenching rate parameters suggest that a sphere of action static quenching model is expected to describe the data most accurately. Also, the results are suggestive of both static and dynamic quenching processes being responsible for the observed positive deviation in the Stern–Volmer plot. Experimental results are described by an equation derived using the finite sink approximation model, which allows the evaluation of diffusion‐limited interaction and the estimation of encounter distance and mutual diffusion coefficient independently.     

Spectrophotometric Determination of Ammonia in Estuarine Waters by Hybrid Reagent‐Injection Gas‐Diffusion Flow Analysis

Abstract

A flow‐injection gas‐diffusion technique is described for the online determination of ammonia in estuarine waters covering a salinity range of S=0 to 36. The flow analysis system, which is a hybrid of reagent injection and conventional sample‐injection flow systems, avoids the need for a rotary injection valve. Whereas gas‐diffusion techniques have been widely applied in conventional sample‐injection flow analysis, reagent‐injection flow analysis involving gas diffusion has been little used because it is susceptible to interference from dissolved gaseous species such as carbon dioxide coexisting with ammonia in the sample. This source of interference has been overcome by online adjustment of sample to pH 8.4 prior to the injection of the base that initiates gas diffusion of ammonia. The pore sizes of hydrophobic membranes used in gas diffusion were characterized by a bubble‐point test prior to use in the flow analysis system. These showed wide variation in pore size, and grading and careful selection was necessary in order to obtain reliable gas diffusion measurements of ammonia. The proposed flow‐injection system can be operated in a continuous flow mode, at a sample throughput of 135 measurements hr^?1 with a typical limit of detection (LOD) of 9 µg N L^?1, or in stopped‐flow mode at 60 measurements hr^?1 with a LOD of 3 µg N L^?1. The technique was validated using water samples containing a wide range of dissolved carbon dioxide concentrations, salinity, and pH. Excellent agreement (r=0.999) was observed between results obtained using the reagent‐injection system and an approved reference method.     

Conditions for Obtaining Stimulated Radiation in Thin‐Film Organic Electroluminescent Structures

This paper analyzes the possibilities of obtaining induced radiation in singlelayer organic electroluminescent structures on the basis of the proposed model of luminophor molecule excitation by hot electrons emitted from the cathode as a result of the tunnel effect. Numerical calculations of the kinetic, spectral, and energy characteristics of radiation in the regime of singlepass superluminescence and in the presence of positive feedback have been made. It has been concluded that, in principle, it is possible to obtain in such systems induced radiation at actually attainable values of the applied electricfield strength, and the conditions for this have been analyzed.     

Analysis of hyperfine structure of Rare‐Earth Ions in Single Crystals by Electron Paramagnetic Resonance Spectroscopy

Electron paramagnetic spectroscopy of rare‐earth ions in single crystals is an interesting tool to analyze the hyperfine structure of the ground state of the rare‐earth. This can be useful for coherent spectroscopy and quantum information applications where the hyperfine structure of the electronic levels is used. Moreover, in some cases, the electron paramagnetic resonance hyperfine structure of interacting rare‐earth ions allows us to retrieve the isotropic exchange interaction between the two interacting ions. We illustrate these points with the hyperfine structure of Yb³⁺ ions in vanadate crystals, the hyperfine structure of Er³⁺ ions in Y₂SiO₅, and the hyperfine structure of Yb³⁺ pairs in CsCdBr₃.     

Modelling and Optimization for Deposition of SiOxNy Films by Radio-Frequency Reactive Sputtering

SiOxNy films are deposited by reactive sputtering from a Si target in Ar/O2/N2 atmospheres. In order to achieve the control of film composition and to keep a high deposition rate at the same time, a new sputtering model based on Berg＇s work is provided for the condition of double reactive gases. Analysis based on this model shows that the deposition process can easily enter the target-poisoning mode when the preset gas flow （N2 in this work） is too high, and the film composition will change from nitrogen-rich to SiO2-like with the increase of oxygen supply while keeping the N2 supply constant. The modelling results are confirmed in the deposition process of SiOxNy. Target self-bias voltages during sputtering are measured to characterize the different sputtering modes. FTIR-spectra and dielectric measurements are used to testify the model prediction of composition. Finally, an optimized sputtering condition is selected with the O2/N2 flow ratio varying from 0 to I and N2 supply fixed at I sccm. Average deposition rate of 17nm/min is obtained under this selected condition, which has suggested the model validity and potential for industry applications.     

Existence Conditions of Collision Sheath in the Tokamak Scrape-off Layer

In controlled nuclear fusion devices like tokamaks, plasma particles are confined by closed magnetic flux surfaces. Outside the last closed flux surface (LCFS), plasma is in direct contact with a solid wall in the scrape-off layer (SOL). Due to the different     

Kinetics of Photogel Formation in Anthracene‐Containing Copolymers in the Presence of Singlet‐Excitation Energy Acceptors

We suggest a technique to control the rate of photocrosslinking fluorescent polymers by introducing a consumable acceptor of the energy of singlet excitation. We have constructed a model of the processes occurring in a layer of a photocrosslinking anthracenecontaining copolymer with the addition of the acceptor which is spent in the reaction of photooxidation by oxygen of the air and the algorithm for calculating the curves of gel formation in the presence of the acceptor. Comparison of the experimental kinetics of the depletion of the acceptor and accumulation of a gel in a layer with the data of model calculations has proved their good agreement. The possibility of increasing the contrast coefficient of the characteristic curve of negative photoresists on the basis of fluorescent photocrosslinked polymers with the aid of singlet excitation energy acceptors is demonstrated.     

Photodegradation Studies by Laser‐Induced Fluorescence of the Reaction Product of 1,2‐Indanedione And Glycine

Photodegradation of the reaction product of 1,2‐indanedione with glycine in methanol at room temperature has been studied using laser-induced fluorescence. Samples were liquid solution and developed fingerprints on papers. Continuous laser excitation of fresh solution of 1,2‐indanedione–glycine dissolved in methanol shows that the emission peak at 564 nm reached a quite stable low level after almost 1 hr of continuous excitation. For latent fingerprints on papers developed with 1,2‐indanedione dissolved in methanol solution, the luminescence peak decreases for the first week and reached a stable level for almost 2 weeks. A long‐term study is needed to reach a conclusion on the stability of the samples (liquid and developed fingerprints) at room temperature conditions.     

Optimization of High-Order Harmonic by Genetic Algorithm for the Chirp and Phase of Few-Cycle Pulses

The brightness of a particular harmonic order is optimized for the chirp and initial phase of the laser pulse by genetic algorithm. The influences of the chirp and initial phase of the excitation pulse on the harmonic spectra are discussed in terms of the semi-classical model including the propagation effects. The results indicate that the harmonic intensity and cutoff have strong dependence on the chirp of the laser pulse, but slightly on its initial phase. The high-order harmonics can be enhanced by the optimal laser pulse and its cutoff can be tuned by optimization of the chirp and initial phase of the laser pulse.     

Spectral‐Luminescent Properties of 1,1‐Dioctadecyl‐3,3,3'3'‐Tetramethylindodicarbocyanineperchlorate in Binary Solutions

On the basis of investigation of the absorption and luminescence spectra of 1,1dioctadecyl3,3,3'3'tetramethylindodicarbocyanineperchlorate (D307) molecules and their nonamphiphilic analog in binary solutions of dimethylformamide and water of different composition, a mechanism underlying the quenching luminescence of the D307 molecules has been established which is related to the formation of nonluminescent associates. It is shown that the formation of the micelles of sodium dodecylsulfate (SDS) in a binary solution with 99% content of water destroys the associates, the D307 molecules are captured by the micelles, and their mobility in the micelles is limited.     

Spectral‐Luminescent Properties of Oxazoles and Oxadiazoles in a Gas Phase on Excitation by Electrons

The energyloss spectra of electrons, fluorescence excitation functions, and the fluorescence spectra on excitation of the vapors of a number of oxazoles and oxadiazoles by monokinetic beams of electrons of various energies are determined. In contrast to optical absorption spectra, in the energyloss spectra of a number of studied substances a band associated with the S ₀–T ₁ singlettriplet transition is observed. The –^*type transitions are fixed up to S ₀–S ₅ on excitation of molecules by highenergy electrons, including the region of vacuum ultraviolet. The cross sections of elastic and inelastic collisions of electrons of different energies with POPOP molecules have been measured. The dependences obtained differ substantially from those calculated in the Born approximation. The cross section of elastic scattering is in a rather good correspondence with the geometric section of the molecule.