Revisit the classical theories of the conductance of unassociated electrolytes. Is there reality in relaxation?

The experimental results of the ionic conductance of the electrolytic solution can be explained without the use of relaxation until almost 2M concentration of the NaCl solution within 97% agreement with two parameters: the hydrated ion radii for cations and anions. No other fitting parameters were introduced, and no ion association was assumed. The theory is based on a newly introduced electrochemical potential that incorporates the interaction between ions and fluctuations in electrolyte concentration in the nanosized region. It was found that the concept of local chemical potential, fluctuation in the nanosized area, and symmetry of the system are closely related to the Boltzmann distribution of ions. Extending the concept of a local chemical potential to the case of an external field, the derived ionic mobility automatically includes the effect of electrophoresis. The so-called electrophoretic retardation was found to be equivalent to the shielding effect of the external field. Relaxation bears a minor effect and may contribute to the ion transport of electrolytic solution at most 3%, if exists.

Contribution of adenosine to the increase in skeletal muscle blood flow caused by manual acupuncture in rats.

BACKGROUND AND AIM: Adenosine is believed to play an important role in local acupuncture analgesia. The aim of this study was to investigate the contribution of adenosine to the increase in skeletal muscle blood flow (MBF) caused by manual acupuncture (MA). METHODS: Thirty-two male Sprague-Dawley rats (310-360 g) were anaesthetised and divided into four equal groups (n=8 each): Saline, Saline+MA, Theophylline, and Theophylline+MA. In the two MA groups, the sparrow-pecking MA technique was applied at 30 repetitions per min for 1 min to a depth of 15-18 mm using a stainless steel acupuncture needle (0.20×40 mm). The stimulus point was located on the right tibialis anterior (TA) muscle 7-8 mm below the knee. Animals in the two theophylline groups were intra-arterially injected with 8-(p-sulphophenyl) theophylline, a non-selective adenosine receptor antagonist, at a dose of 30 mg/kg before MA. Animals in the two saline groups received control saline. Fluorescent microspheres (15 µm in diameter, yellow-green fluorescent) were used for MBF measurement in all four groups. RESULTS: MA of the TA muscle significantly increased MBF (Saline+MA vs Saline: p=0.001; Saline+MA vs Theophylline: p=0.008). Pre-treatment with theophylline appeared to inhibit this increase (Theophylline vs Theophylline+MA; p=1.000). MBF in the Theophylline+MA group was 43% lower than in the Saline+MA group, although this was not significantly different (p=0.104). CONCLUSIONS: The results suggest that adenosine leads to an increase in MBF caused by MA. Adenosine may play a role in acupuncture analgesia by washing out algesic substances. Further studies are needed in order to elucidate the precise mechanism.

Contributions of nitric oxide and prostaglandins to the local increase in muscle blood flow following manual acupuncture in rats.

OBJECTIVE: To investigate the contributions of nitric oxide (NO) and prostaglandins (PGs) to the increase in local muscle blood flow (MBF) observed following manual acupuncture (MA). METHODS: Male Sprague-Dawley rats (n=112; 250-310 g) were injected intraperitoneally with a non-selective NO synthase inhibitor (NG-nitro-L-arginine methyl ester hydrochloride: L-NAME; 10, 50 or 500 mg/kg), a non-selective cyclo-oxygenase inhibitor (indomethacin; 10, 50 or 500 mg/kg), a combination of L-NAME and indomethacin (500 mg/kg each) or saline only under urethane anaesthesia (1.2 g/kg). We used the sparrow pecking technique for 1 min with a stainless steel acupuncture needle (0.20×30 mm) as the acupuncture stimulation method. The stimulus point was on the right tibialis anterior muscle. (51)Chromium-labelled microspheres were used for MBF measurement. RESULTS: MA increased MBF in the saline-injected group (p<0.001). This increase was partially inhibited by L-NAME in a dose-dependent manner (p>0.05, p<0.05 and p<0.001 for 10, 50 and 500 mg/kg, respectively). On the other hand, indomethacin did not suppress the increase (p>0.05 each for 10, 50 and 500 mg/kg). No significant difference was observed between the inhibitory effects of combined administration of L-NAME and indomethacin and single administration of L-NAME (p>0.05). CONCLUSIONS: These results suggest that NO is a major factor in the MA-induced increase in MBF, while PGs do not contribute significantly to this increase. As complete inhibition was not achieved by administration of L-NAME±indomethacin, it appears that non-NO and non-PG vasodilators are additionally involved.

Measurement of the index of refraction of µm crystals by a confocal laser microscope--potential application for the refractive index mapping of µm scale.

A conventional laser microscope can be used to derive the index of refractivity by the ratio of geometrical height of the transparent platelet to the apparent height of the normal incident light for very small crystals in the wide size range. We demonstrate that the simple method is effective for the samples from 100 µm to 16 µm in size using alkali halide crystals as a model system. The method is also applied for the surface fractured micro-crystals and an inclined crystal with microscopic size regime. Furthermore, we present two-dimensional refractive index mapping as well as two-dimensional height profile for the mixture of three alkali halides, KCl, KI, and NaCl, all are µm in size.

Participation of calcitonin gene related peptide released via axon reflex in the local increase in muscle blood flow following manual acupuncture.

OBJECTIVE: The purpose of this study was to determine how calcitonin gene related peptide (CGRP) via axon reflex participates in increasing local muscle blood flow (MBF) following manual acupuncture (MA). METHODS: Male Sprague-Dawley rats (N=56, 270-350 g) were used. We examined (1) the effects of MA on MBF in the tibialis anterior (TA) muscle in normal rats; (2) the effects of MA on MBF in the TA injected with saline or hCGRP8-37 (low: 2×10(-4) mol/litre; high: 2×10(-3) mol/litre), a competitive CGRP receptor antagonist, in rats; and (3) the effects of MA on MBF in the TA in capsaicin-treated rats. The capsaicin-treated rats were injected with capsaicin dissolved in an ethanol solution within 24 h after birth (50 mg/kg subcutaneously). MA was applied to the right TA for 1 min. (51)Cr-labelled microspheres (15 µm in diameter) were used to measure MBF. RESULTS: MA significantly increased MBF without changing arterial blood pressure in normal rats (p<0.05). MA also significantly increased MBF in saline-injected, low hCGRP8-37-injected and high hCGRP8-37-injected rats (p<0.001, 005 and 0.05, respectively). The increases in low and high hCGRP8-37-injected rats were lower than those in saline-injected rats, but the difference was not significant. However, MA did not significantly increase MBF in capsaicin-treated rats (p=0.38). CONCLUSIONS: We obtained conflicting results, suggesting that the participation of CGRP released via axon reflex may be limited to a local increase in MBF following MA.

Functional noble metal nanoparticle superlattices grown at interfaces.

Nanoparticle crystals or superlattices (SLs) are three dimensional arrangements of nanoparticles in the micrometre regime. In SLs, the particles are periodically arranged in a coherent long range order and hence they show collective properties. Various spectroscopic, scattering and imaging techniques have been used to understand the structure of self-assembled SLs. Extensive interest in particle SLs is due to the collective properties of the building blocks, which help us to understand the evolution in properties of organized structures. Controlling the assembly of such organized solids may open up new opportunities for fundamental studies as well as for engineering advanced materials with useful attributes. This review presents our efforts in creating SLs of noble metal nanoparticles and studies performed with those materials.

Organic mediator-induced structural transformation in superlattices of monolayer-protected gold nanoparticles.

N-acetylglutathione (NAG)-protected gold nanoparticles self-assemble into three-dimensional (3D) face-centered cubic (fcc)-type superlattices at an air/water interface under highly acidic conditions. To prepare the well-defined superlattices, 1month's incubation is at least necessary since the size growth of the as-prepared nanoparticles is essential. Addition of 4-pyridinecarboxyic acid (PyC), a bifunctional hydrogen-bonding mediator, promotes the formation of the superlattices, which are created for about 2weeks' storage. Interestingly, PyC-induced nanoparticle superlattices are in a body-centered tetragonal (bct) structure. The fcc-to-bct phase transformation would be due to stronger interaction between NAG and PyC than that between NAG molecules on the gold nanoparticle surfaces.

Temperature dependence on the charge transport behaviour of 3-D superlattice crystals of mercaptosuccinic acid-protected gold nanoparticles.

The electric charge transport behavior of a random assembly of three-dimensional superlattice crystals (having different core sizes) of mercaptosuccinic acid-protected gold nanoparticles showed a unique behavior of metallic-like nature at low temperatures and semiconductor nature at high temperatures in addition to a reversible transition feature in the hopping region.

Charge transport behavior of N-(2-Mercaptopropionyl glycine)-protected gold clusters with temperature.

N-(2-Mercaptopropionyl glycine)-passivated gold clusters (Au-MPG) represent a unique networked system of monolayer-protected clusters (MPCs) due to inter- and/or intramolecular hydrogen bonding between the MPC units thanks to the terminal carboxylic acid groups of the monolayers. We have investigated the size-dependent electric charge transport in well-dried thin films of Au-MPG MPCs by a four-probe methodology as a function of temperature. The MPCs display a novel behavior of metallic-like-to-semiconductor crossover with increase of temperature. The MPCs having average cluster core sizes of approximately 1.6, approximately 3, and approximately 4 nm displayed a metallic-like nature (a linear increase of resistance of the films with increase of temperature) at low temperatures ( approximately 20-60 K), which crosses over to semiconductor behavior (decrease of resistance with increase of temperature) at high temperatures.

Organic styryl dye nanoparticles: synthesis and unique spectroscopic properties.

We report the synthesis and unique spectroscopic properties of organic styryl dye nanoparticles. Aqueous-phase ion association between a cationic styryl dye 2-(4-(dimethylamino)styryl)-1-ethylpyridinium (DASPE), possessing both electron donor and acceptor groups in its molecule, and tetraphenylborate (TPB) or tetrakis(4-fluorophenyl)borate (TFPB) anion, in the presence of poly(vinylpyrrolidone), produces the ion-based dye (DASPE) nanoparticles of approximately 30-100 nm in diameter. Absorption spectra of the DASPE nanoparticles show a large bathochromic shift in comparison with that of the dye monomer in water. Quantum chemical calculations demonstrate that ion-pair formation brings about a large internal rotation around a single bond in DASPE, and this internal twisting as well as local polarity of the counteranion have a strong influence on the red shift of the optical spectra. Furthermore, nanoparticle formation results in enhanced fluorescence of DASPE: more than a 20-fold enhancement in the fluorescence quantum yield as compared to that of the dye monomer in water, giving a new methodology for the synthesis of fluorescent organic nanoparticles. The observed fluorescence would come from an intramolecular charge-transfer (ICT) excited state stabilized by the matrix of TPB or TFPB, and the enhancement is due to both the high rotational resistance for the single bond in DASPE and the matrix polarity effect that can suppress the nonradiative processes.

Investigation of charge transport in mercaptosuccinic acid-passivated gold clusters.

Investigation of electric charge transport in well-dried thin films of mercaptosuccinic acid-protected gold clusters having different cluster core sizes by a four-probe methodology revealed a novel behavior of metalliclike to semiconductor crossover with an increase in temperature. The systems were found comprising of minor metallic and major insulating networks. At low temperatures, the monolayer-protected clusters (MPCs) were found to show a metalliclike nature with a linear increase in resistivity with an increase in temperature. The temperature coefficient of resistivity decreases and approaches that of bulk gold with an increase in the size of the cluster cores of the MPCs. This behavior was correlated with the phonon softening mechanism to the electron scattering and was explained by a simple model with a spherical layer lattice vibration. High temperature region was marked by a sharp decrease in resistivity due to thermally activated nearest neighbor electron hopping process, which follows either Arrhenius or Abeles activation models. We believe that this is the first report showing a maximum in the resistivity of any MPC with temperature as also describing the effect of phonon softening on temperature coefficient of resistivity from charge transport measurements.

Chiral functionalization of optically inactive monolayer-protected silver nanoclusters by chiral ligand-exchange reactions.

We report the ligand-exchange reaction between the optically inactive racemic penicillamine monolayer on a silver nanocluster surface and enantiopure D- or L-penicillamine dissolved in solution. Emergence of the identical band positions in the gel electrophoresis separation assures the presence of size-invariant silver nanoclusters (1.05 and 1.30 nm in core diameter) during the ligand-exchange reaction and allows us to further examine the optical/chiroptical properties of these nanoclusters. Consequently, chiral functionalization of the achiral silver nanoclusters has been demonstrated, yielding large Cotton effects in metal-based electronic transitions with an almost mirror-image relationship between the enantiomeric compounds. The ligand-exchange experiments as well as the normal syntheses of the silver nanoclusters revealed that their absorption profiles and anisotropy factors were strongly dependent on the enantiomeric purity (or enantiomeric excess) of surface chiral penicillamine, so that (several-fold) larger chiroptical responses of the silver nanoclusters as compared to those of the analogous gold clusters with a comparable size could be induced by the metal core deformation or rearrangement along with a universally influential vicinal contribution from the chiral ligand field.

Effect of organic solvents on J aggregation of pseudoisocyanine dye at mica/water interfaces: morphological transition from three-dimension to two-dimension.

Morphological and spectroscopic properties of pseudoisocyanine (PIC) J aggregates produced at mica/solution interfaces have been characterized by absorption/fluorescence spectroscopy, fluorescence microscopy, and atomic force microscopy. Addition of organic solvents (1-propanol (PrOH) or 1,4-dioxane (Dox)) into aqueous solutions of the PIC dye induced a transition of the morphology of the interfacial J aggregates. The characteristic feature of this transition is the thickness (or height) change of the aggregate domain layers from three-dimensions to two-dimensions: The domain area of the J aggregates was dependent on the amount of the organic cosolvent, while the domain thickness was dependent on the type of the cosolvent. In pure aqueous solution, the J aggregates at the mica/water interface had a three-dimensional structure with the height of approximately 3 nm (multilayer structure). In mixed solvents of PrOH/water or Dox/water (5 or 10 vol%), the interfacial aggregates became a bilayer or monolayer structure, respectively, assuming that PIC molecules are adsorbed on their molecular plane perpendicular to the mica surface. Meanwhile, optical properties (band width and peak position) of the J band were invariant upon addition of the organic cosolvents, suggesting that molecular packing in the J aggregates is essentially unchanged. These results revealed that spectroscopic properties of the interfacial PIC J aggregates were determined only by the lateral (two-dimensional) interaction within the adsorbed monolayer of PIC molecules on mica, and interlayer interaction in the multilayered J aggregate was consequently small.

Quantitative analysis of the relation between soft tissue stiffness palpated from the body surface and tissue hemodynamics in the human forearm.

We investigated the quantitative relation between soft tissue stiffness palpated from the body surface and hemodynamics in the human forearm. We examined the relation between pressures and blood flow in both the main artery and vein measured by magnetic resonance imaging (MRI), the cross-sectional area of forearm measured by MRI and soft tissue stiffness. Six male volunteers participated. Two tourniquet pressures, 120 mmHg and 230 mmHg, were used to induce an occlusion of the proximal portion of the upper arm. Measurements were made at the mid-belly of the brachioradial muscle. The venous outflow ceased at tourniquet pressures of 120 and 230 mmHg. The arterial flow was interrupted at 230 mmHg. Larger increases of the cross-sectional area and soft tissue stiffness were found at 120 mmHg than at 230 mmHg. The increase of the cross-sectional area of muscle was larger than that of the surrounding connective tissue during occlusion. We propose that low-pressure compression occludes venous outflow without restricting arterial inflow and induces an increase of the cross-sectional area that reflects the intramuscular pressure; and changes in this pressure caused by fluid accumulation should be the major factor for change in stiffness.

Chemometric and microscopic analyses for the size growth of monolayer-protected gold nanoparticles during their superlattice formation.

Superlattices of gold nanoparticles have been produced at an air/solution interface under a highly acidic condition. The nanoparticle surface is protected by N-acetylglutathione (NAG). During the course of the superlattice formation, size growth of nanoparticles was observed: The superlattices were composed of nanoparticles of 6.6 nm in core diameter, whereas the as-prepared nanoparticles had the core diameter of 1.4 nm. The growth kinetics was pursued by the time evolution of the UV-vis absorption spectra for the sample solution. The change in the absorption spectral profiles was so small that we conducted principal-component analysis (PCA), which is known as a chemometric technique to resolve (or extract) spectra of minute chemical species submerged in the original spectra. Scanning transmission electron microscopy (STEM) corroborated the PCA results, yielding a successful explanation of the growth scheme of the NAG-protected gold nanoparticles.

Electrolyte-induced mesoscopic aggregation of thiacarbocyanine dye in aqueous solution: counterion size specificity.

Countercation size specificity is presented for the electrolyte-induced aggregation of 3,3'-disulfopropyl-5,5'-dichloro-9-methyl thiacarbocyanine (TCC) dye in aqueous solution. Addition of electrolytes having a small monovalent cation (Na+, NH4+, or Cs+) induced pure H aggregates of TCC, whereas J aggregates were preferentially promoted by electrolytes with a large monovalent cation ([N(CH3)4]+ or [N(C2H5)4]+). The electrolyte-induced H aggregate (HS aggregate) differed spectroscopically from that spontaneously self-assembled in aqueous solution. Mesoscopic structure of the HS aggregates was revealed via polarized-light microscopy and atomic force microscopy; a rodlike morphology of 50-70 nm wide and tens to hundreds of micrometers long with very strong negative birefringence. A simple structural model based on semiempirical molecular orbital calculations can explain the aggregation behaviors: The anionic TCC monomer shows a considerable planar geometry between two benzothiazole end groups when it involves a sodium cation, which favors the H-type molecular arrangements in a face-to-face orientation. On the other hand, the TCC dye has a twisted conformation when it implicates a large tetramethylammonium cation, resulting in the formation of the J aggregates.

Self-assembly of acridine orange dye at a mica/solution interface: formation of nanostripe supramolecular architectures.

Optical waveguide spectroscopy and atomic force microscopy (AFM) have been used to characterize the supramolecular architectures of acridine orange (AO) dye self-assembled at a mica/aqueous solution interface. Under the saturated adsorption conditions, optical waveguide spectroscopy revealed that the dye formed H-type aggregates at the interface. In situ AFM visualized interesting morphology of the dye aggregates showing nanosized meandering stripes with the width of approximately 1.5 nm (or brightness periodicity of approximately 3 nm). Electrostatic adsorption of the dye cations onto a mica surface as well as the intermolecular pi-pi stacking brought about the ordered nanostructures. We propose an interfacial aggregation model that shows a meandering staircase structure with the intermolecular slip angle of 60 degrees. According to the model, the AO molecule occupies a surface area of about 1.0 nm2.

Surface charge driven size evolution during the formation of self-assembled nanostructures from discrete hydrophilic silver nanoparticles.

We investigate the spontaneous evolution of mercaptosuccinic acid-capped silver nanoparticles (MSA-Ag) of size 2.5 ± 1.0 nm during the formation of assembled nanostructures at the air/water interface. In the phase transfer approach induced by the cationic surfactant cetyltrimethylammonium bromide (CTAB), the fusion among MSA-Ag nanoparticles is notably accelerated owing to the formation of a CTA-MSA bilayer on the particle surface. Provided that the size-selective separation is carried out in advance for these polydisperse MSA-Ag nanoparticles, either a unitary or a binary orderly superlattice composed of evolved nanoparticles is obtained at the air/water interface. For self-corrective equilibrium growth by adjusting the pH value of the bulk solution through the diffusion of HCl vapor, a competition is found between the superlattice formation and the size growth. The possible size evolution mechanism of each method is proposed. This work also shows that controllable evolution is a useful approach to prepare nanostructures with structural diversity.

Highly ordered superlattices from polydisperse Ag nanoparticles: a comparative study of fractionation and self-correction.

We have examined two different routes to construct highly ordered two- or three-dimensional (2D or 3D) superlattice structures from hydrophilic polydisperse mercaptosuccinic acid (MSA)-modified Ag nanoparticles of the average size of 2.5 nm. First, polydisperse particles were fractionized by the polyacrylamide gel electrophoresis (PAGE) method. Due to the size-dependent migration under the electric field, the particles were isolated into a series of gel bands and each band contained particles with significantly narrow size distribution. Subsequent to phase transfer into chloroform by cationic surfactant, long-range 2D superlattices were simultaneously formed on the substrate upon evaporation of chloroform. Second, 3D superlattices were directly grown at an air-water interface from the polydisperse bulk dispersion by diffusion of HCl vapor without any pretreatment for the size narrowing. The influence of diffusion rate of HCl was also studied. The achievement of 3D superlattices via this route was ascribed as a long-time self-correction process. Furthermore, it was revealed that the superlattice structures obtained by the above two procedures exhibited distinct features though the starting material was the same MSA-Ag nanoparticles. The surface distance of core between component particles, the orientation of particles inside the superlattice, and the process of superlattice formation were comprehensively studied. We confirmed that each growth process depended on a corresponding self-assembly mechanism.