Voltage dependence of bilayer membrane capacitance

The change in capacitance of cholesterol-hexadecyltrimethylammonium bilayer membranes upon application of relatively high dc and ac potentials was measured as a function of frequency. Capacitance increases proportional to the square of voltage were observed (0.5–1% for 100 mV dc). The amplitude of the ac component of the capacitance variation decreased with frequency until a break frequency was reached, above which the capacitance response was constant at a value about two orders of magnitude lower than the dc response. By comparison with the elastic response of the membrane and border, it was concluded the capacitance response at higher frequency was due to bilayer thickness decrease with voltage (electrostriction) while the lower frequency response was associated with a bilayer area increase. Agreement was obtained between the measured electrostriction and that calculated from membrane elasticity. Area increases with voltage calculated assuming border shrinkage as a result of an increase in contact angle were in order of magnitude agreement with the observed dc response. The effects of lenses and bowed membranes are discussed.     

定量SEC法同时测定短链共聚物的组成和分子量

由于端基对整体高分子链光学性质的贡献，短链高分子的折光指数增量有明显的分子量依赖性．从整体高分子链折光指数增量依从各结构组成单元折光指数增量的重量分数加和律，指示同一高分子链改变端基后，如分别测定它们的折光指数增量。由其差值可以同时获得链干的分子量和折光指数增量，对共聚物言，从链干的折光指数增量又可进而估定共聚物的组成．这一原则特别适用于具有显著端基效应的短链高分子．本工作用定量尺寸排除色谱方法测量具有不同端基的环氧乙烷－环氧丙烷共聚物苯溶液的折光指数增量，以考验此原则，获得了满意结果．     

Direct Spectrochemical Analysis of Solids: A Method for Characterization of Sediments

Techniques for the direct analysis of powdered samples provide an advantageous alternative to methods using wet digestion in sample preparation. The direct spectrochemical methods based on electrothermal vaporization (ETV-ICP-OES, solid-ETV-AAS, etc.) show a great similarity to the classical method of dc arc excitation, used in spectrography. Owing to this, the classical dc arc spectrographical method was used in parallel with ETV methods in the direct solid sampling analysis of river and basin sediments. The calibration procedure is the major difficulty of all techniques applied to direct solid sample analysis because of a lack of suitable reference materials. Consequently, it was necessary to verify the application of model calibration samples, preferentially using the simple dc arc OES system and both spectrographic and spectrometric evaluation. The performance parameters of the methods mentioned are compared with those published for the ETV-ICP-OES and SS-ETV-AAS methods.     

激光小角光散射测定多嵌段共聚物分子量

聚对苯二甲酸乙二醇醋(PET)-聚己内酯(PCL)是一种新的热塑弹性体。由于PET与PCL相容性较好,PET硬段含量可以在很宽的范围内变化,为全面研究热塑弹性体的结构与性能之间的关系提供了便利的条件。     

State-selected imaging of HCCO radical photodissociation dynamics

We present a dc sliced ion imaging study of HCCO radical photodissociation to CH and CO at 230 nm. The measurements were made using a two-color reduced Doppler probe strategy. The CO rotational distribution was consistent with a Boltzmann distribution at 3500 K. Using the dc slice ion imaging approach, we obtained CO images for various rotational levels of CO (v=0). The results are largely consistent with earlier work, albeit with a significant 0.9 eV peak seen previously in the translational energy distributions absent in our state-selected imaging study.     

Identification of the adsorption sites of molecular oxygen on Si(111) using XPS

Most of the oxygen adsorb dissociatively on Si, however there is also a significant amount of metastable molecular oxygen chemisorbed on Si. The adsorption site/configuration of these molecular oxygen species is still a controversial subject. New XPS results for oxygen adsorption on Si(111) 7×7 (150K) are presented. They reveal four distinct oxygen components; one of the metastable components has never been reported before. We tentatively identify them as: i) stable oxide (Si-O-Si bridges)(˜532 eV), ii) diffusing oxygen atom (˜533 eV) in silicon oxide and iii) metastable molecular oxygen species (˜527.6 eV and ˜530.6 eV). The latter have been attributed to peroxy radical which is defined as a diatomic oxygen bonded to a single Si adatom. Our results allow us to distinguish the two main configurations of peroxy radical: paul-para and grif. Both of them possess a lifetime of ˜ 180 min.     

Polymerization of 1,2,4,5-tetramethylbenzene (durene) in direct-current discharge

Polymer films possessing dielectric properties were prepared from 1,2,4,5-tetramethylbenzene (durene) at the cathode in a dc discharge. The chemical structure of the films was studied by IR and UV spectroscopy. It was shown that the polymer synthesized from durene in a dc discharge contains basically polyene structures produced via the opening of aromatic rings.     

Frequency tuning of long-wavelength VCSELs

Tuning properties of long-wavelength VCSELs have been studied experimentally, for the first time to our knowledge. Injection current and temperature tuning rates of two VCSELs operating near 1,512 and 1,577 nm have been measured using a Fabry-Perot etalon with free spectral range 0.056 cm(-1). A 100-Hz saw-tooth modulation with depths of modulation of approximately 10% or less was superimposed on a direct injection current (dc bias) to tune lasers in narrow spectral intervals (0.3-1.2 cm(-1)) around a central frequency set by the dc bias. The lasers have been found to be capable of being tuned faster at higher levels of dc bias. The enhancement factors were up to approximately 2 and approximately 3 for the 1,512- and 1,577-nm lasers, respectively, as compared with their tuning rates measured at the levels of the dc bias close to the threshold of lasing. A linear dependence between injection current tuning rates and the levels of dc bias has been observed. Temperature tuning coefficients have been proved to be independent of the laser heat sink temperature and of the dc bias. Frequency tuning curves were approximated with a second-order polynomial. The frequencies of more than 40 absorption lines of CO, CO(2), H(2)O and NH(3) known from spectral databases were compared with the calculated frequencies. The accuracy of the approximation was found to be within 0.2 cm(-1) for spectral intervals up to 38 cm(-1). The dependence of current tuning rates of the VCSELs on dc bias was shown to be taken into account for accurate analysis of absorption line profiles. The results obtained can be used for precise spectroscopic measurements with long-wavelength VCSELs.     

Quadrupole mass filters with octopole fields

The performance of quadrupole mass filters with added octopole fields in the range 2.0-4.0% has been investigated. The added fields are much greater than those normally added to conventional rod sets by mechanical tolerances or construction errors. Quadrupole rod sets with added octopole fields were constructed with round rods by making one pair of rods greater in diameter than the other pair. For positive ions, resolution at half height of only about 200 is possible if the negative direct current (dc) output of the quadrupole power supply is connected to the smaller rods. If the positive dc output of the quadrupole power supply is connected to the smaller rods, the resolution improves dramatically; a resolution at half height of 5800 has been observed with a rod set with 2.6% added octopole field. For negative ions the best resolution is obtained with the polarity of the dc reversed, i.e. with the negative dc applied to the smaller rods. These findings are unexpected in view of the literature that argues that to obtain high mass resolution with quadrupole mass filters, higher order multipoles must be kept as small as possible. Numerical simulations of peak shapes agree qualitatively with experiments. Simulation of the boundaries of the first stability region for positive ions shows that when the positive dc is applied to the smaller rods, the addition of a 2.0% octopole field causes the boundaries to shift slightly but the boundaries are well defined, and the tip of the stability region remains sharp. When the positive dc is applied to the larger rods, the boundaries of the stability region move out and become diffuse. For instruments that require a rod set that can be used both as a linear trap and a mass filter, these rod sets may offer improved trap performance while still being capable of providing conventional mass analysis.     

Electrical properties of carbon black‐filled polymer composites

This work deals with the dielectric properties of conductive composite materials, which consist of thermoplastic polypropylene (PP) matrix filled with carbon black (CB). The CB concentration was systematically varied in a wide range. Our main interest is focused on the investigation of electrical conductivity mechanism and related percolation phenomena in these materials. To study the electrical and dielectric properties of composites we used broadband ac dielectric relaxation spectroscopy (DRS) techniques in a wide temperature range. By measurements of complex dielectric permittivity, ϵ*, the dependence of ac conductivity, σ_ac, and dc conductivity, σ_dc, on the frequency, the temperature and the concentration of the conductive filler was investigated. The behavior of this system is described by means of percolation theory. The percolation threshold, P_C, value was calculated to be 6.2 wt.% CB. Both, dielectric constant and dc conductivity follow power‐law behavior, yielding values for the critical exponents, which are in good agreement with the theoretical ones. Indications for tunneling effect in the charge carriers transport through the composites are presented. The temperature dependence of dc conductivity gives evidence for the presence of positive temperature coefficient (PTC) effect.     

Characterization of a serial array of miniature cylindrical ion trap mass analyzers

Two small (5 mm internal radius) cylindrical ion traps (CITs) are arranged in series and operated using a single ion source, detector and radio frequency (rf) trapping signal. Ions are trapped in the first CIT and later transferred to the second by applying a direct current (dc) pulse to the endcap electrode of the first trap. This process is facilitated if a second, appropriately timed, retarding dc pulse is applied to the exit endcap electrode of the second trap. Mesh endcaps are used for the CITs to increase the number of ionizing electrons entering the trap and to maximize the transfer efficiency and detected signal. The transfer efficiency is dependent on the amplitude of the dc potential applied to eject the ions from the first trap, the amplitude of the dc potential applied to retain the ions in the second trap, and the period during which the retarding potential is applied. The amplitude and phase of the rf also affect the transfer process. Ions that readily dissociate upon collision have low transfer efficiencies; more stable ions can be transferred with up to 50% efficiency. Copyright 1999 John Wiley & Sons, Ltd.     

The origin of DC electrical conduction and dielectric relaxation in pristine and doped poly(3‐hexylthiophene) films

We present here the evidence for the origin of dc electrical conduction and dielectric relaxation in pristine and doped poly(3‐hexylthiophene) (P3HT) films. P3HT has been synthesized and purified to obtain pristine P3HT polymer films. P3HT films are chemically doped to make conducting P3HT films with different conductivity level. Temperature (77–350 K) dependent dc conductivity (σ_dc) and dielectric constant (ε′(ω)) measurements on pristine and doped P3HT films have been conducted to evaluate dc and ac electrical conduction parameters. The relaxation frequency (f_R) and static dielectric constant (ε₀) have been estimated from dielectric constant measurements. A correlation between dc electrical conduction and dielectric relaxation data indicates that both dc and ac electrical conductions originate from the same hopping process in this system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1047–1053, 2010     

固相反应中扩散动力学方程的新探讨

通过对г~NHCTJINHT方程中把э~c/э~r作为产物层增厚速率的基础作出分析,对由扩散控制的固相反应中扩散浓度与时间的关系作了进一步探讨, 提出产物层增厚速率应建立在Fick第二定律的基础上, 并导出了新的扩散动力学方程。     

Analytical properties of the amidoxime group: Part VI. Electroanalytical behaviour of ethanediamidoxime

The electroanalytical behaviour of ethanediamidoxime (EDA) has been studied at 0.1 mol l^?1 ionic strength and several pH values (1.75–8.62), using several techniques (dc and DP polarography, chronocoulometry, dc and DP cyclic voltammetry). EDA undergoes an irreversible diffusion-controlled reduction in the entire pH range considered. The best conditions for identification and determination of EDA with the techniques mentioned are also studied.     

Surface-induced dissociation of molecular ions in a quadrupole ion trap mass spectrometer

A method is reported by which surface-induced dissociation is used to activate ions stored in a quadrupole ion trap mass spectrometer. The method employs a short (< 5 μs), fast-rising (< 20-ns rise time), high voltage direct current (dc) pulse, which is applied to the endcaps of a standard Paul-type quadrupole ion trap. This is in contrast to the application of an alternating current (ac) signal normally used to resonantly excite and dissociate ions in the trap. The effect of the dc pulse is to cause the ions rapidly to become unstable in the radial direction and subsequently to collide with the ring electrode. Sufficient internal energy is acquired in this collision to cause high energy fragmentations of relatively intractable molecular ions such as pyrene and benzene. The dissociations of limonene are used to demonstrate that high energy demand processes increase in relative importance in the dc pulse experiment compared with the usual resonance excitation method used to cause activation. The fragments are scanned out of the ion trap using the conventional mass-selective instability scan mode. Simulations of ion motion in the trap provide evidence that surface collisions occur at kinetic energies in the range of tens to several hundred electronvolts. The experiments also demonstrate that production of fragment ions is sensitive to the phase of the main radiofrequency drive voltage at the point when the dc is initiated.     

Self-assembled linear bundles of single wall carbon nanotubes and their alignment and deposition as a film in a dc field

A one-step process of solubilization of single wall carbon nanotubes (SWCNT) in an organic solvent has enabled us to polarize them asymmetrically in a dc electric field. Quaternary ammonium ion-capped SWCNTs readily suspend in organic solvents; under the influence of a dc electric field, they assemble as stretched bundles anchored on the positive electrode. At low dc applied field (approximately 40 V), all of the SWCNTs from the suspension are deposited on the electrode, thus providing a simple methodology to design robust SWCNT films. At higher applied voltages (>100 V), the SWCNT bundles stretch out into the solution and orient themselves perpendicular to the electrode surface. The alignment of these bundles is responsive to the ON-OFF cycles of the applied electric field. The possibility of modulating the alignment of SWCNT in an electric field opens new ways to achieve electrical contacts in nano- to micro-devices.     

Supramolecular architectures and magnetic properties of coordination polymers based on pyrazinedicarboxylato ligands showing embedded water clusters

The synthesis, crystal structure, and magnetic behavior of nine transition-metal complexes based on pyrazine-2,5-dicarboxylato (pz25dc) and pyrazine-2,3-dicarboxylato (pz23dc) ligands are reported. The pz25dc ligand displays a bis-bidentate coordination mode, with the carboxylate groups almost coplanar with the pyrazine ring, to afford polymeric 1-D chains [Mn(1), Fe(2), Zn(3), and Cu(4 and 5)] and discrete dimeric entities [Mn(6)] when the 1,10-phenanthroline (phen) blocking ligand is used to avoid further polymerization. The nonplanar pz23dc ligand chelates to a unique copper center, while it bridges another one or two metal centers via the remaining carboxylate group, leading to 1-D polymeric chains (7), ladder chains (8), and sheets (9). The crystal packing of the metal-organic frameworks of compounds 4-9 generates voids which are occupied by assembled water molecules. The different water cluster patterns (tapes, four-membered discrete rings, and chains for compounds 6, 8, and 9, respectively) and their role in the cohesiveness of supramolecular architectures are analyzed. Thermogravimetric and variable-temperature X-ray powder diffraction studies have revealed the occurrence of reversible dehydration processes in compounds 6, 8, and 9. Furthermore, the magnetic behavior of these compounds has been studied in order to analyze the capability of the pyrazine ring to transmit magnetic interactions.     

Large amplitude Fourier transformed ac voltammetry at a rotating disc electrode: a versatile technique for covering Levich and flow rate insensitive regimes in a single experiment

The theory for large amplitude Fourier transformed ac voltammetry at a rotating disc electrode is described. Resolution of time domain data into dc and ac harmonic components reveals that the mass transport for the dc component is controlled by convective-diffusion, while the background free higher order harmonic components are flow rate insensitive and mainly governed by linear diffusion. Thus, remarkable versatility is available; Levich behaviour of the dc component limiting current provides diffusion coefficient values and access to higher harmonics allows fast electrode kinetics to be probed. Two series of experiments (dc and ac voltammetry) have been required to extract these parameters; here large amplitude ac voltammetry with RDE methodology is used to demonstrate that kinetics and diffusion coefficient information can be extracted from a single experiment. To demonstrate the power of this approach, theoretical and experimental comparisons of data obtained for the reversible [Ru(NH(3))(6)](3+/2+) and quasi-reversible [Fe(CN)(6)](3-/4-) electron transfer processes are presented over a wide range of electrode rotation rates and with different concentrations and electrode materials. Excellent agreement of experimental and simulated data is achieved, which allows parameters such as electron transfer rate, diffusion coefficient, uncompensated resistance and others to be determined using a strategically applied approach that takes into account the different levels of sensitivity of each parameter to the dc or the ac harmonic.     

Creation of Polymerizable Species in Plasma Polymerization

Plasma polymerization of trimethylsilane (TMS) was carried out and investigated in a direct current (dc) glow discharge. The formation of TMS plasma glow was carefully examined with optical photography as compared with an Ar dc glow discharge. It was found that there exists a significant difference in the nature of glow and how the glow is created in TMS glow discharge, which polymerizes or causes deposition, and that of monatomic gas such as Ar, which does not polymerize or deposit. In dc Ar discharge, the negative glow, which is the most luminous zone in the discharge, develops in a distinctive distance away from the cathode surface, and the cathode remains in the dark space. In a strong contrast to this situation, in TMS dc discharge, the primary glow that is termed as cathode-glow in this paper appears at cathode surface, while a much weaker negative glow as a secondary glow was observed at the similar location to where the Ar negative glow appears. The deposition results of plasma polymers and gas phase composition data of TMS in a closed reactor acquired by ellipsometry and residual gas analyzer (RGA) measurements clearly indicated that the cathode-glow in TMS glow discharge is mainly associated with chemically reactive species that would polymerize or form deposition, but the negative glow is related to species from simple gases that would not polymerize or deposit. Based on the glow location with respect to the cathode, it was deduced that the cathode-glow is due to photon emitting species created by molecular dissociation of the monomer that is caused by low energy electrons emanating from the cathode surface. The negative glow is due to the ionization and the formation of excited neutrals of fragmented atoms caused by high-energy electrons. Polymerizable species that would cause deposition of material (plasma polymers) are created mainly by the fragmentation of monomer molecules by low energy electrons, but not by electron-impact ionization of the monomer.