采用流变学方法研究聚酰胺酸6FDA-TFDB溶液的降解行为

合成了一种聚酰胺酸6FDA-TFDB溶液,利用流变仪研究其在不同影响因素(如:温度、升温速率、溶剂含水量等)下的流变行为,发现聚酰胺酸溶液的降解在高温区和低温区存在不同的行为.通过Andrade公式获得不同条件下聚酰胺酸溶液的黏流活化能,并比较其差异,同时对溶剂水含量在不同温度区域下对聚酰胺酸降解速率的影响也进行了深入的分析,从而建立一种半定量比较不同条件下聚酰胺酸溶液降解速率的方法.     

Instrumental multielement activation analysis of soil samples

Soil samples from a waste water cleaning facility in Berlin, Germany, have been analyzed using several activation analysis methods. 43 elements have been determined by instrumental high energy photon activation analysis (PAA), instrumental thermal neutron activation analysis (NAA) and 14 MeV neutron activation analysis (fNAA). Conventional gamma ray spectroscopy and low energy photon spectroscopy (LEPS) have been applied for product activity measurement. It has turned out that these methods in combination offer a wide spectrum of analytical information.     

Analysis of high-purity material—A comparison of photon activation analysis with other instrumental methods

Photon activation analysis (PAA) has been a well-established analytical method for about two decades. In this paper, its particular features are outlined in comparison with other modern instrumental techniques, especially radioanalytical methods, e.g. activation analysis with thermal or fast neutrons (NAA) or charged particles (CPA). Emphasis is placed upon the determination of trace components of high-purity material; iron, copper and lead matrix were selected as examples. In PAA, both instrumental and radiochemical procedures were applied. The results are presented in comparison with those obtained by other laboratories using a large variety of different techniques.     

Interaction of a poly(acrylic acid) oligomer with dimyristoylphosphatidylcholine bilayers

We studied the influence of 5 kDa poly(acrylic acid) (PAA) on the phase state, thermal properties, and lateral diffusion in bilayered systems of dimyristoylphosphatidylcholine (DMPC) using (31)P NMR spectroscopy, differential scanning calorimetry (DSC), (1)H NMR with a pulsed field gradient, and (1)H nuclear Overhauser enhancement spectroscopy (NOESY). The presence of PAA does not change the lamellar structure of the system. (1)H MAS NOESY cross-peaks observed for the interaction between lipid headgroups and polyion protons demonstrated only surface PAA-biomembrane interaction. Small concentrations of PAA (up to ～4 mol %) lead to the appearance of a new lateral phase with a higher main transition temperature, a lower cooperativity, and a lower enthalpy of transition. Higher concentrations lead to the disappearance of measurable thermal effects. The lateral diffusion coefficient of DMPC and the apparent activation energy of diffusion gradually decreased at PAA concentrations up to around 4 mol %. The observed effects were explained by the formation of at least two types of PAA-DMPC lateral complexes as has been described earlier (Fujiwara, M.; Grubbs, R. H.; Baldeschwieler, J. D. J. Colloid Interface Sci., 1997, 185, 210). The first one is characterized by a stoichiometry of around 28 lipids per polymer, which corresponds to the adsorption of the entire PAA molecule onto the membrane. Lipid molecules of the complex are exchanged with the "pure" lipid bilayer, with the lifetime of the complex being less than 0.1 s. The second type of DMPC-PAA complex is characterized by a stoichiometry of 6 to 7 lipids per polymer and contains PAA molecules that are only partially adsorbed onto the membrane. A decrease in the DMPC diffusion coefficient and activation energy for diffusion in the presence of PAA was explained by the formation of a new cooperative unit for diffusion, which contains the PAA molecule and several molecules of lipids.     

Web-based spectrum analysis software for photon activation analysis

Photon activation analysis (PAA) includes extensive data evaluation that is sensitive to error. In order to save time and minimize human error, a new computer program—photon activation analysis system (PAAS)—was designed, built and implemented using the SQL language and Asp.net technology to analyze PAA data. Given peak information from PAA spectra and aided by a photonuclear data library, the program identifies the product isotopes, recognizes the possible nuclear reactions, and evaluates the concentration of target elements. Uncertainties of concentrations are estimated using standard error propagation techniques. The program can be accessed conveniently anywhere the internet is available and gives a fast and reliable determination of the trace elemental content of samples. Furthermore, this program also allow one to search its database for the information of general photonuclear reactions (e.g. energy lines, line intensities, target and product nuclides, photonuclear reactions, cross sections, natural abundance, etc.) and estimating the activity even before the activation begins. By switching the nuclide libraries, the program could also be expanded to neutron activation analysis and charged particle activation analysis (CPAA) without any difficulty. This program can be a versatile tool for the daily use of the nuclear and radiochemistry laboratories that conduct activation analysis.     

Properties of TiO2-polyacrylic acid dispersions with potential for molecular recognition

Titanium dioxide (TiO₂)/polyacrylic acid (PAA) (TiO₂/PAA) particles were formed by mixing PAA and an acidic solution of TiO₂ nanoparticles in dimethylformamide (DMF) followed by heat treatment. TEM and particle analysis showed that the resulting particles had a narrow size distribution. The colloid was very stable and aggregation was not observed over a wide pH range (3–9) or at high salt concentration. The residual carboxylic acid of PAA could be modified via EDC/NHS activation to form an amide bond with a protein. An antibody was attached to the hybrid nanoparticle and specific binding to antigen was monitored by surface plasmon resonance. The results suggest that TiO₂/PAA nanoparticles are candidates as the base component of a photocatalytic system with potential for substrate selectivity.     

Possibilities of low-level determination of silicon in biological materials by activation analysis

The capabilities of neutron and photon activation analysis (NAA and PAA, respectively) for low-level determination of silicon in biological materials have been examined. Sensitivities of a variety of modes of NAA and PAA with radiochemical separation have been evaluated. Results are presented for silicon in reference materials CSRM 12-2-03 Lucerne, Bowen's Kale, NIST SRM-1571 Orchard Leaves, and NIST SRM-1515 Apple Leaves. The results were obtained by employing the 29Si(n,p)29Al reaction with fast reactor neutrons and the radiochemical procedure developed for aluminium separation. Possibilities of further improvement of the silicon determination limit down to the microg g(-1) level by employing NAA and PAA with radiochemical separation are outlined.     

A provenance study of coffee by photon activation analysis

Photon activation analysis (PAA) is a multi-elemental radioanalytical technique in trace elements analysis with high accuracy and precision. Researchers at the Idaho accelerator center performed PAA analysis on coffee samples from several locations around the world as an initial step in assessing the relationship between trace elements in illicit drugs and the soils in which they were grown. The preliminary results show coffees from different locations have different concentrations of trace elements. In the three cases where we have soil samples, the matrices of elements in the coffee samples are closely related to the matrices of the elements of the local soil samples. The majority of trace elemental content is similar to that of the local soil sample in which the coffee is planted. It may be that coffee assimilates numerous elements from the soil where it is grown in similar ratios as is found in the soil. Thus, it is conceivable that the elemental content could serve as “fingerprint” to trace the origins of the coffee. To verify our analytical results we applied X-ray fluorescence (XRF) methods as well. Our PAA results are consistent with XRF experimental data. The future of tracing the origin of illicit drugs with the PAA technique is promising.     

Surface-grafted poly(acrylic acid) brushes as a precursor layer for biosensing applications: effect of graft density and swellability on the detection efficiency

Carboxyl groups along poly(acrylic acid) (PAA) brushes attached to the surface of a gold-coated substrate served as the precursor moieties for the covalent immobilization of amino-functionalized biotin or bovine serum albumin (BSA) to form a sensing probe for streptavidin (SA) or anti-BSA detection, respectively. Surface-grafted PAA brushes were obtained by acid hydrolysis of poly(tert-butyl acrylate) brushes, formerly prepared by surface-initiated atom transfer radical polymerization of tert-butyl acrylate. As determined by surface plasmon resonance, the PAA brushes immobilized with functionalized biotin or BSA probes not only showed good binding with the designated target analytes but also maintained a high resistance to nonspecific protein adsorption, especially those PAA brushes with a high surface graft density. Although the probe binding capacity can be raised as a function of the graft density of the PAA brushes or the amount of carboxyl groups along the PAA chains, the accessibility of the target analyte to the immobilized probe was limited at the high graft density of the PAA brushes. The effect was far more apparent for the BSA-anti-BSA probe-analyte pair than for the much smaller biotin-SA probe-analyte pair. The impact of the swellability of the PAA brushes, as tailored by the degree of carboxyl group activation, on both the sensing probe immobilization and analyte detection was also addressed. This investigation demonstrated that PAA brushes having a defined graft density have a promising potential as a precursor layer for biosensing applications.     

Possibilities of low-level determination of silicon in biological materials by activation analysis

The capabilities of neutron and photon activation analysis (NAA and PAA, respectively) for low-level determination of silicon in biological materials have been examined. Sensitivities of a variety of modes of NAA and PAA with radiochemical separation have been evaluated. Results are presented for silicon in reference materials CSRM 12–2-03 Lucerne, Bowen’s Kale, NIST SRM-1571 Orchard Leaves, and NIST SRM-1515 Apple Leaves. The results were obtained by employing the ²⁹Si(n,p)²⁹Al reaction with fast reactor neutrons and the radiochemical procedure developed for aluminium separation. Possibilities of further improvement of the silicon determination limit down to the μg g^–1 level by employing NAA and PAA with radiochemical separation are outlined.     

Determination of chromium,iron and copper in niobium by radiochemical proton activation analysis

Chromium, iron and copper were determined in niobium by radiochemical proton activation analysis (PAA). The main steps of the technique involved the irradiation of the samples with 13 MeV protons, the post-irradiation decontamination of the sample surface, a two-step separation procedure based on anion exchange from HF and HCl medium, and counting the separated indicator radionuclides with a well-type NaI detector. For a 5-hr irradiation, limits of detection for chromium, iron, and copper were 0.2, 5.0, and 15 ppb respectively. The results obtained by this technique are compared with data obtained by radiochemical neutron activation analysis (NAA) and atomic absorption spectrometry (AAS).     

Purification, biochemical characterization, and bioactive properties of a lectin purified from the seeds of white tepary bean (phaseolus acutifolius variety latifolius)

The present work shows the characterization of Phaseolus acutifolius variety latifolius, on which little research has been published, and provides detailed information on the corresponding lectin. This protein was purified from a semi-domesticated line of white tepary beans from Sonora, Mexico, by precipitation of the aqueous extract with ammonium sulfate, followed by affinity chromatography on an immobilized fetuin matrix. MALDI TOF analysis of Phaseolus acutifolius agglutinin (PAA) showed that this lectin is composed of monomers with molecular weights ranging between 28 and 31 kDa. At high salt concentrations, PAA forms a dimer of 63 kDa, but at low salt concentrations, the subunits form a tetramer. Analysis of PAA on 2D-PAGE showed that there are mainly three types of subunits with isoelectric points of 4.2, 4.4, and 4.5. The partial sequence obtained by LC/MS/MS of tryptic fragments from the PAA subunits showed 90-100% identity with subunits from genus Phaseolus lectins in previous reports. The tepary bean lectin showed lower hemagglutination activity than Phaseolus vulgaris hemagglutinin (PHA-E) toward trypsinized human A and O type erythrocytes. The hemagglutination activity was inhibited by N-glycans from glycoproteins. Affinity chromatography with the immobilized PAA showed a high affinity to glycopeptides from thyroglobulin, which also has N-glycans with a high content of N-acetylglucosamine. PAA showed less mitogenic activity toward human lymphocytes than PHA-L and Con A. The cytotoxicity of PAA was determined by employing three clones of the 3T3 cell line, demonstrating variability among the clones as follows: T4 (DI?? 51.5 μg/mL); J20 (DI?? 275 μg/mL), and N5 (DI?? 72.5 μg/mL).     

Principles,methodologies, and applications of photon activation analysis: a review

This review describes the basic principles of photon activation analysis (PAA) and gives an extensive overview of its numerous applications. Uses of PAA for environmental, biological, geological, archeological, and forensic samples are reviewed. Both scientific and industrial applications of PAA are covered. Potential future uses of PAA are addressed.     

Comparison of the role of photon and neutron activation analyses for elemental characterization of geological,biological and environmental materials

The potential of photon activation analysis (PAA) for multielement trace analysis can hardly compare with that of neutron activation analysis (NAA). However, PAA appears superior over NAA for the determination of a number of elements, namely C, N, O, F, Mg, Si, Ca, Ti, Ni, Sr, Y, Zr, Nb, Sn, Tl and Pb in geological, environmental and biological materials. Most of these and other elements can be determined using nondestructive, instrumental PAA (IPAA), especially in geological materials. The possibilities of IPAA for multielement analysis using photoexitation and other photonuclear reactions are reviewed and compared with those of instrumental NAA (INAA), namely for geological materials. The need for and usefulness of radiochemical PAA (RPAA) procedures are also discussed.     

The Influence of the Cathodic Pretreatment on the Electrochemical Detection of Dopamine by Poly(1‐aminoanthracene) Modified Electrode

In this study we demonstrated the influence of the cathodic pretreatment of poly(1‐aminoanthracene) (PAA) electropolymerized on a platinum electrode for determination of dopamine (DA). The DA electrochemical response was obtained after a cathodic pretreatment of the PAA electrode which consisted of applying a potential of ?0.7 V (vs. Ag/AgCl) for 3 s before each measurement. The pretreatment of the electrode changed the PAA electrocatalytic properties so that the electrode began to present electrochemical response to DA without interference of ascorbic acid (AA). The anodic peak currents determined by differential pulse voltammetry using pretreated PAA showed a linear dependence on the DA concentration from 0.56 to 100 µM with a detection limit of 0.13 µM and a correlation coefficient of 0.9986. The electrode exhibits a relative standard deviation of 1.2 % for ten successive measurements of a 0.5 mM DA solution. The analysis by scanning electron microscopy and atomic force microscopy show a homogeneous and nanostructured film with globular structures with diameter of about 20 nm. The analytical results obtained for DA determination at a pretreated PAA electrode in pharmaceutical formulation sample were in good agreement with those obtained by a comparative procedure at a 95 % confidence level. PAA electrode after the pretreatment showed electrochemical responses to DA with excellent selectivity, sensitivity, and high stability without interference of AA.     

Thermal decomposition of acrylamide from polyacrylamide

Ion-attachment mass spectrometry with a temperature-programed direct probe allows the detection of intact pyrolysis products. It, therefore, offers the opportunity to monitor directly thermal byproducts on a real-time basis and potentially to detect thermally unstable products. With this technique, we investigated the thermal decomposition of polyacrylamide (PAA). Pyrolysis of PAA at around 450?°C produces many products (e.g., amides, imides, nitriles, ketones, aldehydes, and acrylamide oligomers). Acrylamide, which is a possible carcinogen, is produced abundantly in various industries, and, therefore, continues to be a cause for concern. We also investigated the kinetics of the thermal decomposition of PAA, and observed that the degradation of acrylamide obeys Arrhenius kinetics, which allowed us to correlate the rate constant with the absolute temperature and the activation energy. The activation energy of thermal decomposition was calculated from selected ion-monitoring curves of acrylamide.     

Trace element determination in soft tissues of marine bivalves by activation analysis

Trace elements in soft tissues of marine bivalves were determined by neutron activation analysis (NAA) and photon activation analysis (PAA). Elemental levels of Ag, As, Br, Co, Cu, Fe, I, Mn, Ni, Rb, Se, and Zn in the organs of giant ezoscallos, rock oysters, and giant crams were obtained. The metal-bound proteins were extracted from the mantles and hepatopancreases of rock oysters. By irradiating the fraction obtained by HPLC gel chromatography, we found the possibility for the existence of an Ag bound protein in the mantles.     

Design and synthesis of optically transparent calcium‐incorporated polymer complexes

Transparent thin films of calcium‐ion‐incorporated polymer composites were synthesized with calcium carbonate (CaCO₃) and polymers such as poly(acrylic acid) (PAA), poly(ethylene glycol) (PEG), and methylcellulose. The homogeneous distribution of Ca²⁺ in the composite films was observed because of the high concentration of COO^? groups along the PAA backbone for the complexation of Ca²⁺ ions. The optical transparency of the composites depends on the weight percentages of the three polymers and the molar concentration of CaCO₃ in the composites. Maximum transparency was obtained for a composite film with a PAA/CaCO₃ ratio of 9:1. The results indicated that methylcellulose improved the film‐forming capabilities and that PEG improved the transparency of the composites. All polymer complexes were characterized with X‐ray diffraction, fourier transfer infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, dynamic mechanical analysis, and optical transparency measurements. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4459–4465, 2004     

Comparison of photon activation analysis with other modern analytical methods as tools for the solution of actual analytical problems

A 35 MeV linear electron accelerator is used to investigate how far photon activation analysis can be used within the broad spectrum of analytical methods applied in BAM. The irradiation facilities are described. Examples are given for the application of PAA in the analysis of oxygen in metals and compared with conventional heat extraction and other nuclear analytical methods. It is further shown that PAA is a very useful tool for the analysis of traces of noble metals in Cu compared with other methods. Finally the possibilities of PAA in the field of multielement analysis are demonstrated taking ancient roman potsherds and bronze as examples. The results are compared with those of XRF and AAS. It is concluded that PAA is a valuable tool in the analysis of light elements with at least partly unique possibilities, that it can serve as an independent method for the certification of Reference Materials in many cases and that PAA can be very useful applied for multielement analysis.     

Inteferences in neutron and photon activation analysis

The effect of following interferences was quantitatively assessed in terms of interference factor by irradiating samples together with highly pure reagents at two reactor sites of diferent neutron spectra and fluxes for neutron activation analysis (NAA) and an electron LINAC for photon activation analysis (PAA). The interfering reactions studied are 91) fast neutron-induced reactions, (2) uranium fission (3) (n,γ) reactions of other target elements in NAA, and (4) reactions induced by secondary neutrons in PAA. Corrections for these interferences were successfully applied to the activation analysis of some geological reference rock samples and biological samples.