Quartz Oscillator Study of Monolayer 4He and 3He - 4He Mixture Films Adsorbed on Solid H2

The superfluid transition in submonolayer and monolayer ⁴ He films and ³ He - ⁴ He mixture films on solid H ₂ has been studied using a quartz crystal microbalance technique. Kosterlitz-Thouless (KT) transitions were observed in submonolayer ⁴ He films with density greater than 0.062 ± 0.002 Å ^–2 . We determine a binding energy of ⁴ He to 0.241 Å ^–2 H ₂ of –15.7 K in the. presence of 1 monolayer of ⁴ He. At several ⁴ He coverages, a range of submonolayer ³ He coverages was studied (n ₃ 0.0567 Å ^–2 ). With each increase in the ³ He coverage, the KT transition temperature decreased. For the higher coverage mixture films studied (n ₄ 0.0726 Å ^–2 ) we observed an apparent second decoupling of the film from the quartz oscillator frequency in addition to the KT transition. We have studied the. coverage dependence of this new feature.     

基于QCM-D的天然多糖材料的蛋白吸附研究

采用QCM-D和AFM等技术研究比较了海藻酸钙和壳聚糖两种天然多糖材料经旋转成膜后的表面形貌、亲疏水性、水合过程及蛋白吸附和解吸行为.结果发现,海藻酸钙相比壳聚糖具有更好的亲水性,在生理环境中的水合过程达到平衡较快,且水合程度较高,这也影响材料的蛋白吸附性能.白蛋白吸附和洗脱实验表明,水舍程度较高的海藻酸钙初始吸附蛋白量较少,但海藻酸钙吸附的蛋白量在PBS洗脱后反而较大.而蛋白层|△D/△F|值在洗脱后减小,表明残留的蛋白层发生一定程度的构象变化,结构相对致密,其粘弹性变小.用3种动力学模型拟合蛋白吸附动力学过程发现Langmuir模型拟合度较高,且壳聚糖薄膜的蛋白吸附过程比海藻酸钙具有更小的速率常数k,达到吸附平衡较缓慢.     

Heat capacity study of4He desorbing from H2-plated graphite

We report measurements of the surface binding energy of⁴He adsorbed on 1.45, 2.15, or 3.15 layers of hydrogen plating graphite. The heat capacity of partial monolayer coverages of helium was measured using adiabatic heat pulse calorimetry from 0.2 to 9 K. Desorption of low surface density⁴He films was indicated above 2 K by a broad peak in the heat capacity. A model was developed to calculate the specific heat of an ideal gas in two dimensions as it desorbs into an ideal gas in three dimensions. This model was used to obtain the binding energies from our experimental data. The binding energies per atom are –39, –25.8, and –22 ± 0.5 K, respectively, for the three hydrogen platings. The 2-d compressibility of the partial solid second layer of H₂ in the 1.45 layer H₂ coverage was calculated from an increase in its melting temperature with increase of⁴He 2-d pressure.     

Quartz crystal microbalance study of volume changes and modulus shift in electrochemically switched polypyrrole

The performance of conducting polymers as actuators is determined by a complicated series of molecular processes that occur as a result of oxidation and reduction of the polymer. In particular, the amount of actuation strain generated for a given voltage stimulus is determined by the number and type of ions (and solvent) that enter and leave the polymer and changes in the mechanical properties (particularly elastic modulus) of the polymer. In this paper, we present the effects of cyclic voltammetry on the shear modulus and volume of polypyrrole in two different electrolytes: propylene carbonate and an ionic liquid. An electrochemical quartz crystal microbalance has been used to study simultaneous volume and modulus changes occurring during redox cycling of polypyrrole. The results demonstrate that the modulus generally increases due to oxidation of the polymer, although initial oxidation from the fully reduced state first produces a decrease in modulus followed by a larger increase. The modulus shift and volume changes were smaller in the ionic liquid electrolyte, probably because of the absence of solvent. Comparison of the results obtained in the two electrolytes suggest that interchain interactions dominate in the determination of modulus, so that modulus is higher in the oxidised state even when the polymer is swollen with counterions and solvent.     

Quartz crystal microbalance study of DNA immobilization and hybridization for nucleic Acid sensor development

The immobilization of two 30-mer oligonucleotides, one biotinylated (biotin-DNA) and the other having a mercaptohexyl group at the 5'-phosphate end (BS1-SH), onto modified gold surfaces has been examined using a quartz crystal microbalance (QCM). Both single-layer and multilayer DNA films were prepared. The single-layer films of biotin-DNA were constructed by binding to a precursor layer of avidin, which had been attached to the QCM either covalently using a water-soluble carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) or via electrostatic interaction with poly(allylamine hydrochloride) (PAH). Single-layer films of BS1-SH were also formed on PAH via the electrostatic attraction between the amine groups on PAH and the negatively charged phosphate backbone of DNA. Multilayer films of DNA were fabricated by the successive deposition of avidin and poly(styrenesulfonate) (PSS), up to a total of nine avidin/PSS layers, followed by DNA adsorption. DNA immobilization and hybridization of the immobilized DNAs was monitored in situ from QCM frequency changes. Hybridization was induced by exposure of the DNA-containing films to complementary DNA in solution. Equal frequency changes were observed for the DNA immobilization and hybridization steps for the single-layer films, indicating a DNA probe-to-hybridized DNA target ratio of 1:1. The multilayer DNA films also exhibited DNA hybridization, with a greater quantity of DNA hybridized compared with the single-layer films. The multilayer films provide a novel means for the fabrication of DNA-based thin films with increased capacity for nucleic acid detection.     

Quartz Crystal Microbalance Study of Superfluid 4He Films on Gold and Porous Gold Surfaces

The superfluid transition in sub-rnonolayer ⁴He films was studied using quartz crystal microbalance (QCM). We recently improved the QCM technique by replacing the conventional gold electrodes with porous gold, thus increasing the surface area and therefore sensitivity by 40 times. Simugtaneous measurements were taken for QCMs with flat and porous gold electrodes contained within the same copper cell. For both QCMs the superfluid transition temperature was found to be proportional to the ⁴He film thickness. The superfluid transition temperature at each film coverage was greater for porous gold than for flat gold electrodes.     

Quartz Microbalance Study of Thick 4He Film Near the Superfluid Transition

We present the resugts of a quartz microbalance measurement of a ～440 Å thick ⁴He film adsorbed on Au. This measurement confirms the resugt of an earlier capacitance measurement that showed a dip in the film thickness just below Ta due to the critical Casimir force. The magnitude of the dip in the two measurements agrees within 15% . In addition to the dip, we see a signal due to the onset of superfluidity in the film. An apparent peak in the film thickness, not observed previously, is also found coinciding closely with the bulk T _λ. This extra feature may be due to a sound resonance in the cell associated with the bulk fluid.     

Determination of the thermodynamic phases of4He adsorbed on H2 plated graphite

Thermodynamic measurements have been used to investigate the surface phases of monolayer⁴He adsorbed on graphite plated with 1.45, 2.15, and 3.15 layers of H₂. In each case the⁴He preferentially adsorbed on the lower completed layer. In this paper we report the measurements of⁴He on the 1.45 layer H₂ graphite plating. For this plating the⁴He goes into a condensed phase below 0.87 K. The high temperature-low density film entropy has been calculated.     

Quartz crystal microbalance detection of glutathione-protected nanoclusters using antibody recognition

A quartz crystal microbalance (QCM) immunosensor was developed for the quantitative detection of glutathione-protected nanoclusters. Advantages intrinsic to QCM were employed to make it an attractive alternative to other immunosensing techniques. We have addressed challenges in the area of QCM mass sensing through experimental correlation between damping resistance and frequency change for a reliable mass measurement. Electrode functionalization was optimized with the use of protein A to immobilize and present polyclonal IgG for antigen binding. This method was developed for the detection of glutathione (antigen)-protected clusters of nanometer size with high surface area and thiolate valency. Quantitation of glutathione-nanocluster binding to immobilized polyclonal antibody provides equilibrium constants (K(a) = (3.6 +/- 0.2) x 10(5) M(-1)) and kinetic rate constants (k(f) = (5.4 +/- 0.7) x 10(1) M(-1) s(-1) and k(r) = (1.5 +/- 0.4) x10(-4) s(-1)) comparable to literature reports. These observations further imply that immunoreactive nanoparticles have potential in medical diagnostics and materials assembly.     

Quartz crystal microbalance studies of polymer gels and solutions in liquid environments

Spreading of liquids and soft solids on a rigid surface in a surrounding liquid medium is investigated by utilizing the lateral sensitivity of the quartz crystal microbalance (QCM). While the QCM has been used extensively to study systems with spatial variations in the direction normal to the crystal's electrodes, few studies have exploited the QCM's ability to sense changes in loading in the plane of the electrodes. We propose equations to describe the predicted response of the QCM to a generalized viscoelastic material spreading at the QCM surface at the expense of the surrounding liquid medium. Several experimental examples are given in order to support the validity of the proposed equations, including situations where the spreading material is a Newtonian liquid, a viscoelastic liquid, or one of two viscoelastic solids. The first viscoelastic solid is a physically cross-linked gel based on a styrene/ethylene-butene/styrene triblock copolymer in mineral oil, and the second is a cross-linked poly(ethylene glycol) hydrogel.     

Vortex Diffusivity and Core Diameter of 2D Superfluid in 4He Films on Gold and H2 Substrates

The two-dimensional (2D) ⁴He fluid films show the Kosterlitz-Thouless (KT) transition where pairing and unpairing of the 2D vortices play an important role. However, the vortex properties (the diffusion constant D, the core diameter a ₀) have not been precisely obtained for various conditions. Here, we accurately determined the parameter D/a ₀ ² by the high frequency dependence of the superfluid onset up to 180 MHz for the submonolayer ⁴He fluid films adsorbed on gold and H₂ (3.3 layers) preplated on gold, respectively. The superfluid onset coverage changes from 1.6 (gold) to 0.5 layers (H₂), which clearly indicates the large difference of the adsorption potential. The parameter D/a ₀ ² , on the other hand, has the same value for the coverages with the same KT temperature T _KT. This suggests that the vortex diffusions on both substrates have the largest value D～?/m in the quantum limit. The core diameter a ₀ was estimated to be the same magnitude as the de Broglie wavelength at T _KT between 0.1 and 0.9 K.     

Path integral Monte Carlo simulations of thin4He films on a H2 surface

The adsorption of ⁴ He films for coverages from1/4 to3 monolayers ona H₂ surface at low temperatures is studied with Path Integral Monte Carlo. We calculate the binding energy per ⁴ He atom to the substrate, density profiles of ⁴ He and H₂, zero point motion of ⁴ He and H₂, and the superfluid density of ⁴ He.     

Path integral monte carlo simulations of thin4He films on a H2 surface

Atomatically thin⁴He films of up to three monolayers on molecular hydrogen (1,1,1) surfaces are studied at T = 0.5 K, using path integral Monte Carlo. We compute the binding energy of⁴He to the H₂ substrate as a function of⁴He coverage and obtain evidence of the prewetting transition. Density profiles perpendicular to the⁴He-H₂ interface are obtained, as well as the zero point motion and effective mass of⁴He parallel to the substrate surface. The superfluid density of⁴He vs. coverage is calculated, and the intermediate scattering function is computed, from which we estimate the speed of third sound. Finally, we calculate the vorticity-vorticity correlation function.     

Hysteresis,Switching and Anomalous Behaviour of a Quartz Tuning Fork in Superfluid 4He

We have been studying the behaviour of commercial quartz tuning forks immersed in superfluid ⁴He and driven at resonance. For one of the forks we have observed hysteresis and switching between linear and non-linear damping regimes at temperatures below 10 mK. We associate linear damping with pure potential flow around the prongs of the fork, and non-linear damping with the production of vortex lines in a turbulent regime. At appropriate prong velocities, we have observed metastability of both the linear and the turbulent flow states, and a region of intermittency where the flow switched back and forth between each state. For the same fork, we have also observed anomalous behaviour in the linear regime, with large excursions in both damping, resonant frequency, and the tip velocity as a function of driving force.     

Quartz crystal microbalance and spectroscopy measurements for acid doping in polyaniline films

Abstract

We investigated the doping of thin polyaniline (PANI) films, prepared by the chemical oxidation of aniline, with different acids. The initial step in the investigation is the preparation of PANI films from aqueous hydrochloric acid solution. This is followed by dedoping with ammonia to obtain a PANI base, which is subsequently doped with strong acids (e.g. hydrochloric, sulfuric, phosphoric and trichloroacetic acids) and with a weak acid (acetic acid). The dopant weight fraction (w), which is connected with the gain of mass during the doping of PANI, was determined in situ using a quartz crystal microbalance (QCM). The behavior of PANI upon doping with different anions derived from strong acids indicates that both proton and the anion uptake into the polymer chains occur sharply, rapidly, completely, and reversibly. However the uptake in the case in acetic acid is characterized by slow diffusion. The doping was studied at different concentrations of acetic acid. A second cycle of dedoping–redoping was also performed. The kinetics of the doping reaction is dominated by Fickian diffusion kinetics. The diffusion coefficients (D) of the dopant ions into the PANI chains were determined using the QCM and by UV–Vis absorption spectroscopy in the range of (0.076–1.64)× 10^?15 cm² s^?1. It was found that D in the second cycle of doping is larger than that evaluated from the first cycle of doping for high concentrations of acetic acid. D for the diffusion and for the dopant ion expulsion from the PANI chains was also determined during the redoping process. It was found that D for acetic acid ions in the doping process is larger than that calculated for the dedoping process.     

Vibrating Quartz Crystal Studies of Wall-Film Superfluidity in Liquid 3He/4He Mixtures Near the Tricritical Concentration

We are using a thin quartz crystal immersed in the liquid, vibrating in shear modes at 24.8 and 94.0 MHz, to investigate the onset and growth of superfluidity in a thin film at the crystal surface in liquid ³He/⁴He mixtures having ³He mole fractions x near the tricritical value x=0.675. A parallel-plate capacitor in the cell monitors the phase-separation transition. Preliminary measurements of frequency shifts at x=0. 644 and x=0.705 show a relatively abrupt onset of wall-film superfluidity in the bulk normal region of the phase diagram at temperatures in good agreement with earlier studies of wall-film superfluidity by other methods.     

Adsorption of 4He N and 4He N 3He Clusters on Cesium

The ground-state properties of helium clusters ⁴He _N and ⁴He _N ³He, for N≤ 40, adsorbed on the surface of cesium are studied using variational and diffusion Monte Carlo calculations. Binding properties are determined using two different Cs–He interaction potentials. For the smallest clusters, self-binding on a Cs surface is stronger than in two or three dimensions. For N > 10 self-binding in three dimensions is stronger than on Cs for both types of Cs–He interaction potential considered. The obtained binding energies and structure are compared to results of recent density functional calculations. The emergence of edge states of ³He atom, localized along the contact line of ⁴He cluster with a cesium surface, is studied. First indication that ³He atom prefers to be close to the contact line appears already for the ⁴He₃ ³He cluster.     

Quartz crystal microbalance sensor for organic vapor detection based on molecularly imprinted polymers

Molecularly imprinted polymers on quartz crystal microbalances (QCM) are examined for their ability to detect vapors of small organic molecules with greater sensitivity and selectivity than the traditional amorphous polymer coatings. Hydroquinone and phenol serve as noncovalently bound templates that generate shape-selective cavities in a poly(acrylic) or poly(methacrylic) polymer matrix. The imprinted polymers are immobilized on the piezoelectric crystal surface via a precoated poly(isobutylene) layer. The behavior of the imprinted polymer films is characterized by the dynamic and steady-state response of the QCM frequency to pulses of organic vapors in dry air. The apparent partition coefficients are determined for imprinted and nonimprinted polymers prepared by two synthetic methods and for varying mole ratios of template to monomer. The hydroquinone-imprinted polymers and, to a lesser extent, the phenol-imprinted polymers exhibit greater sensitivity and higher selectivity than the nonimprinted polymers toward organic vapors that are structurally related to the templates. These results indicate that molecularly imprinted polymers are promising for the development of selective piezoelectric sensors for organic vapor detection.     

Spreading of superfluid4He on MgF2

We have investigated the spreading of superfluid⁴He on top of a polished fused silica plate which is coated by a thin layer of MgF₂. Our interferometric experiments indicate that a superfluid⁴He film of about 100 nm thickness is not able to spread uniformly over a nearly horizontal substrate, and hence these films cannot be governed by the Van der Waals forces only. Even in the stationary state, we observe nonzero (1 – 20 mrad) contact angles which display hysteresis, spatial variation, and strong history dependence.