Quartz crystal microbalance (QCM) in high-pressure carbon dioxide (CO2): experimental aspects of QCM theory and CO2 adsorption

The quartz crystal microbalance (QCM) technique has been developed into a powerful tool for the study of solid-fluid interfaces. This study focuses on the applications of QCM in high-pressure carbon dioxide (CO2) systems. Frequency responses of six QCM crystals with different electrode materials (silver or gold) and roughness values were determined in helium, nitrogen, and carbon dioxide at 35-40 degrees C and at elevated pressures up to 3200 psi. The goal is to experimentally examine the applicability of the traditional QCM theory in high-pressure systems and determine the adsorption of CO2 on the metal surfaces. A new QCM calculation approach was formulated to consider the surface roughness contribution to the frequency shift. It was found that the frequency-roughness correlation factor, Cr, in the new model was critical to the accurate calculation of mass changes on the crystal surface. Experiments and calculations demonstrated that the adsorption (or condensation) of gaseous and supercritical CO2 onto the silver and gold surfaces was as high as 3.6 microg cm(-2) at 40 degrees C when the CO2 densities are lower than 0.85 g cm(-3). The utilization of QCM crystals with different roughness in determining the adsorption of CO2 is also discussed.     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.     

ESI‐MS/MS of expanded porphyrins: a look into their structure and aromaticity

Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.     

Investigating the vortex melting phenomenon in BSCCO crystals using magneto-optical imaging technique

Using a novel differential magneto-optical imaging technique we investigate the phenomenon of vortex lattice melting in crystals of Bi₂Sr₂CaCu₂O₈ (BSCCO). The images of melting reveal complex patterns in the formation and evolution of the vortex solid-liquid interface with varying field (H)/temperature (T). We believe that the complex melting patterns are due to a random distribution of material disorder/inhomogeneities across the sample, which create fluctuations in the local melting temperature or field value. To study the fluctuations in the local melting temperature/field, we have constructed maps of the melting landscape T _m(H, r), viz., the melting temperature (T _m) at a given location (r) in the sample at a given field (H). A study of these melting landscapes reveals an unexpected feature: the melting landscape is not fixed, but changes rather dramatically with varying field and temperature along the melting line. It is concluded that the changes in both the scale and shape of the landscape result from the competing contributions of different types of quenched disorder which have opposite effects on the local melting transition.     

Energy dependence of multiplicity in proton-nucleus collisions and models of multiparticle production

This is a continuation of our earlier investigation (Gurtuet al 1974Phys. Lett. 50 B 391) on multiparticle production in proton-nucleus collisions based on an exposure of emulsion stack to 200 GeV/c beam at the NAL. It is found that the ratioR _em = 〈n _s〉/〈n _ch〉, where 〈n _ch〉 is the charged particle multiplicity in pp-collisions, increases slowly from about 1 at 10 GeV/c to 1·6 at 68 GeV/c and attains a constant value of 1·71 ± 0·04 in the region 200 to 8000 GeV/c. Furthermore,R _em = 1·71 implies an effectiveA-dependence ofR _A =A ^0.18,i.e., a very weak dependence. Predictions ofR _em on various models are discussed and compared with the emulsion data. Data seem to favour models of hadron-nucleon collisions in which production of particles takes place through adouble step mechanism,e.g., diffractive excitation, hydrodynamical and energy flux cascade as opposed to models which envisage instantaneous production.     

Tri-partite complex for axonal transport drug delivery achieves pharmacological effect

Background

Targeted delivery of pharmaceutical agents into selected populations of CNS (Central Nervous System) neurons is an extremely compelling goal. Currently, systemic methods are generally used for delivery of pain medications, anti-virals for treatment of dermatomal infections, anti-spasmodics, and neuroprotectants. Systemic side effects or undesirable effects on parts of the CNS that are not involved in the pathology limit efficacy and limit clinical utility for many classes of pharmaceuticals. Axonal transport from the periphery offers a possible selective route, but there has been little progress towards design of agents that can accomplish targeted delivery via this intraneural route. To achieve this goal, we developed a tripartite molecular construction concept involving an axonal transport facilitator molecule, a polymer linker, and a large number of drug molecules conjugated to the linker, then sought to evaluate its neurobiology and pharmacological behavior.

Results

We developed chemical synthesis methodologies for assembling these tripartite complexes using a variety of axonal transport facilitators including nerve growth factor, wheat germ agglutinin, and synthetic facilitators derived from phage display work. Loading of up to 100 drug molecules per complex was achieved. Conjugation methods were used that allowed the drugs to be released in active form inside the cell body after transport. Intramuscular and intradermal injection proved effective for introducing pharmacologically effective doses into selected populations of CNS neurons. Pharmacological efficacy with gabapentin in a paw withdrawal latency model revealed a ten fold increase in half life and a 300 fold decrease in necessary dose relative to systemic administration for gabapentin when the drug was delivered by axonal transport using the tripartite vehicle.

Conclusion

Specific targeting of selected subpopulations of CNS neurons for drug delivery by axonal transport holds great promise. The data shown here provide a basic framework for the intraneural pharmacology of this tripartite complex. The pharmacologically efficacious drug delivery demonstrated here verify the fundamental feasibility of using axonal transport for targeted drug delivery.     

Accuracy of the multipole expansion applied to a sphere in a creeping flow parallel to a wall

An example system is studied to discuss precision of the multipoleexpansion, applied to determine forces exerted on particlesby a viscous low-Reynolds-number fluid flow. A single spherein an ambient flow (pure shear, quadratic, and modulated shear)parallel to a close plane wall is considered. Forces and torquesexerted by the ambient flow on a motionless sphere are evaluated.Their precision is determined and related to a multipole orderof the truncation. Similar analysis is performed for a movingsphere with no ambient flow and for a freely moving sphere.Relative motion of the sphere with respect to the wall givesrise to strong lubrication interactions. It is analysed howthese interactions affect accuracy of the pure multipole expansion,and what are the smallest distances where it becomes insufficient.An alternative precise method is applied, in which lubricationexpressions are subtracted from the hydrodynamic forces andtorques, and the residue is evaluated as a fast-convergent seriesof inverse powers of the distance between the sphere centreand the wall. The accuracy of this procedure is carefully analysed.     

Examination of glass transitions in CO(2)-processed, peracetylated sugars using sum frequency generation spectroscopy

The present study utilizes vibrational sum frequency generation (SFG) spectroscopy to study changes in the surface crystallinity of various peracetylated sugars, a class of materials that have a high affinity for carbon dioxide (CO(2)). Studies of the solid-air interface of acetylated beta-cyclodextrin (Ac-beta-CD) and sucrose octaacetate (SOA) show that diffuse reflectance SFG spectroscopy is sensitive to changes in crystallinity from processing with either heat or solvation in CO(2), due to the loss of signal after glassification occurs. beta-d-Glucose pentaacetate (Ac-beta-GLC) was used as a control for this experiment due to the fact that it does not undergo a crystalline phase transition, regardless of processing conditions. The crystalline to amorpohous transitions of these bulk materials were verified using differential scanning calorimetry (DSC) as a function of thermal and CO(2) processing. In addition, preliminary results suggest that the SFG technique is sensitive in detecting the degree of crystallinity at the interface as a result of incomplete processing and presents new opportunities for the examination and detection of surface crystallinity changes.