Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Time-resolved chemiluminescence technique for the microdetermination of proteins based on their complexation with copper(II).

Based on the complexation between proteins and Cu(II) coupled with the time-resolved chemiluminescence (CL) technique, a highly sensitive and quantitative assay for measuring proteins in solution is described. The complexes of proteins with Cu(II) have a strongly catalytic effect on the luminol-H2O2 CL reaction. Because the CL emission produced by the complexes is much more long-lived than that by Cu(II), the CL signals originating from proteins can be easily identified and measured with a time-resolved technique. On this basis, bovine albumin fraction V (BAF V) can be quantitatively determined in the range of 0.01 - 5.0 microg/ml with a detection limit of 5.8 ng/ml. The results show that the proposed assay exhibits a small variation in the response values for the same amount of different proteins, as compared to the Lowry as well as Bradford assays. The CL assay has also been studied for the detection of immobilized proteins.     

Determination of polymeric aluminum in soil extracted with a modified anion-exchange resin as a solid-phase adsorbent by ICP-AES.

In the present work, a new method was established by applying solid-phase extraction (SPE) to preconcentrate and separate polymeric aluminum (Al) and using ICP-AES to determine the polymeric Al, the total monomeric Al, and the total Al in soil extracts, respectively. A modified resin was prepared with impregnated 8-hydroxyquinoline-5-sulfoxinate (HQS) on the anion-exchange resin. It has good recognition ability for Al fractions, compared to the commonly used cation ion-exchange resin, which has a better ability to adsorb cations and a weak ability to recognize detailed Al species. The optimum conditions for Al fractionation sorption, elution and separation and the interference of foreign ions were studied with the prepared resin by continuous column and batch procedures. Monomeric Al was bound to Pyrocathecol Violet (PCV) at pH 6.2, whereas the polymeric Al species did not react with PCV for at least 15 min. Because a stable complex of Al-PCV was not absorbed on the HQS modified resin, the polymeric Al could be preconcentrated on-line by the HQS-modified resin. The adsorbed polymeric Al was eluted with 3 mL of 3 mol L(-1) of HCl, and then detected by ICP-AES. The method has been applied to directly determine polymeric Al in soil extracts with high selectivity as well as a high preconcentration factor. It gives a limit of detection of 0.6 ng mL(-1) with a relative standard deviation of less than 5.7% (n = 5, 0.24 microg mL(-1) Al).     

Resonance-stabilized phenoxy-like radicals formed by NO-mediated mono-nitration of coumarins containing a hydroxy group

Stable aminoxyls and an iminoxyl were observed by spin trapping and EPR techniques during the nitration of coumarins containing a hydroxy group by nitric oxide. The trapped free radicals are deduced to be the resonance stabilized phenoxy-like radicals. The mechanisms for the nitrations are suggested.     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 2004     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Concentrations of hazardous heavy metals in environmental samples collected in Xiamen, China, as determined by vapor generation non-dispersive atomic fluorescence spectrometry.

Non-dispersive atomic fluorescence spectrometry (NDAFS) coupled with vapor generation (VG) sample introduction was applied to the determination of the concentrations of hazardous heavy metals, such as arsenic, cadmium, lead and mercury, in seawater, soils and total airborne particulate matter (PM) collected around the Xiamen area in China. Almost 100% sample introduction efficiency was achieved by using thiourea and ascorbic acid for the pre-reduction of As(V) to As(III), K3Fe(CN)6 and tartaric acid for pre-oxidation of Pb(II) to Pb(IV), and masking the interferences arising from the co-existing transition metals to As, Cd, Hg and Pb during their vapor generation process. Moreover, a novel sample pretreatment device was developed to avoid the loss of mercury, lead, cadmium and arsenic during sample pretreatment. With such methods, the detection limit (DL) of arsenic, cadmium, lead and mercury was down to 0.08, 0.03, 0.05, 0.01 ng mL(-1) (3sigma), respectively. The relative standard deviations (RSD, n = 11) for arsenic, cadmium, lead and mercury at 10 ng mL(-1) were 0.9%, 1.6%, 1.3% and 2.0%, respectively. The concentrations of hazardous heavy metals in the environmental samples collected in Xiamen, China are in the range from 0.02 +/- 0.001 ng mL(-1) in seawater to 15.3 +/- 0.2 microg g(-1) in soils. Besides flame/GF-AAS and ICP-AES/MS, VG-NDAFS should be another choice for the determination of hazardous heavy metals in environmental samples.     

光纤光栅选频掺Yb3+双包层光纤激光器

利用相位掩模法 ,在D形内包层掺Yb3 双包层光纤一端直接写制出Bragg光栅 ,用作双包层光纤激光器的输出腔镜 .试验得到了线宽为 0 196nm ,波长为 10 5 8 2nm ,最高输出功率为 5 70mW的稳定激光输出 ,解决了激光器中模式竞争造成的输出不稳定现象 .从速率方程出发 ,对激光器的输出功率与抽运功率、光栅反射率的关系以及最佳光纤长度进行了理论分析 ,结果与实验符合很好     

Optimality Conditions and Geometric Properties of a Linear Multilevel Programming Problem with Dominated Objective Functions

In this paper, a model of a linear multilevel programming problem with dominated objective functions (LMPPD(l)) is proposed, where multiple reactions of the lower levels do not lead to any uncertainty in the upper-level decision making. Under the assumption that the constrained set is nonempty and bounded, a necessary optimality condition is obtained. Two types of geometric properties of the solution sets are studied. It is demonstrated that the feasible set of LMPPD(l) is neither necessarily composed of faces of the constrained set nor necessarily connected. These properties are different from the existing theoretical results for linear multilevel programming problems.     

Spectra Analysis of a Novel Ti-Doped LiAlO2 Single Crystal

LiAlO2 single crvstals doped with Ti at concentration 0.2at.% are grown by the Czochralskl technique with dimensions φ42×55mm. Ti ions in the crystal are quadrivalence proven by comparing the absorption and fluorescence spectra of pure LiAlO2 and Ti： LiAlO2. After air and Li-rich atmosphere annealing, the absorption peaks in the range of 600-800nm disappear. We conclude that 682 and 756nm absorption peaks are attributed to the VLi and Vo absorptions, respectively： The peaks at 716nm and 798nm may stem from the VLi^＋ and absorptions. The colour-centre model can be applied to explain the experimental phenomena. Ti^4＋-doping produces more lithium vacancies in the LiAlO2 crystal. The intensities of [LiO4] and the associated bonds remain unchanged, which improves the anti-hydrolyzation and thermal stability of LiAlO2 crystals.