A search for interstellar gas-phase CO2 gas: Solid state abundance ratios

We present searches for gas-phase CO2 features in the ISO-SWS infrared spectra of four deeply embedded massive young stars, which all show strong solid CO2 absorption. The abundance of gas-phase CO2 is at most 2. 10(-7) with respect to H-2, and is less than 5% of that in the solid phase. This is in strong contrast to CO, which is a factor of 10-100 more abundant in the gas than in solid form in these objects. The gas/solid state ratios of CO2, CO and H2O are discussed in terms of the physical and chemical state of the clouds.

Spray Congealed Lipid Microparticles with High Protein Loading: Preparation and Solid State Characterization

The spray-congealing technique, a solvent-free drug encapsulation process, was successfully employed to obtain lipid-based particulate systems with high (10–20% w/w) protein loading. Bovine serum albumin (BSA) was utilised as model protein and three low melting lipids (glyceryl palmitostearate, trimirystin and tristearin) were employed as carriers. BSA-loaded lipid microparticles were characterised in terms of particle size, morphology and drug loading. The results showed that the microparticles exhibited a spherical shape, mean diameter in the range 150–300 µm and an encapsulation efficiency higher than 90%. Possible changes in the protein structure as a result of the manufacturing process was then investigated for the first time using UV spectrophotometry in fourth derivative mode and FT-Raman spectroscopy. The results suggested that the structural integrity of the protein was maintained within the particles. Thermal analysis indicated that the effect of protein on the thermal properties of the carriers could be detected. Spray-congealing could thus be considered a suitable technique to produce highly BSA-loaded microparticles preserving the structure of the protein.

Solid-state sodium-selective sensors based on screen-printed Ag/AgCl reference electrodes

The potentiometric and AC impedance characteristics of all solid-state sodium-selective electrodes based on planar screen-printed Ag/AgCl electrodes are described. Two solid-state designs have been investigated. The first was based on the deposition of a sodium-selective PVC membrane directly on top of a screen-printed Ag/AgCl electrode, The second design included a NaCl doped hydrogel layer, between the PVC and Ag\AgCl layers. The hydrogel provides a mechanism to relieve any blockage to charge transfer occurring when PVC membranes are used directly on top of Ag/AgCl and also improves adhesion between the two layers. Results suggest the electrodes display Fast ion exchange kinetics, low noise and drift. The performance compares favorably to that of a conventional ion-selective electrode with internal filling solution.

Pinning down the solid-state polymorphism of the ionic liquid [bmim][PF6]

The solid-state polymorphism of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], has been investigated via low-temperature and high-pressure crystallisation experiments. The samples have been characterised by single-crystal X-ray diffraction, optical microscopy and Raman spectroscopy. The solid-state phase behaviour of the compound is confirmed and clarified with respect to previous phase diagrams. The structures of the previously reported gamma-form, which essentially exhibits a G'T cation conformation, as well as those of the elusive beta- and alpha-forms, are reported. Crystals of the beta-phase are twinned and the structure is heavily disordered; the cation conformation in this form is predominantly TT, though significant contributions from other less frequently encountered conformers are also observed at low temperature and high pressure. The cation conformation in the alpha-form is GT; the presence of the G'T conformer at 193 K in this phase can be eliminated on cooling to 100 K. Whilst X-ray structural data are overall in good agreement with previous interpretations based on Raman and NMR studies, they also reveal a more subtle interplay of intermolecular interactions, which give rise to a wider range of conformers than previously considered.

Homologous size-extension of hybrid vanadate capsules – solid state structures, solution stability and surface deposition

The dimensions and cavity sizes of the molecular capsules with the general formula [V₁₀O₁₈L₄]¹⁰⁻ can be controlled modularly through the nature of the bifunctional, rigid organophosphonate ligands L¹ and L² (L¹ = bis(4-phosphonatophenyl)ethyne and L² = bis(4-phosphonatophenyl)butadiyne); the solution stability of the molecular entities as demonstrated by ESI-MS studies permits their assembly on the Au(111) surface on a sub-monolayer scale giving rise to a 2D supramolecular structure that is comparable to the packing arrangements of the capsules in the crystal structures.

Polymorphism in Sulfadimidine/4-Aminosalicylic Acid Cocrystals: Solid-State Characterization and Physicochemical Properties

Polymorphism of crystalline drugs is a common phenomenon. However, the number of reported polymorphic cocrystals is very limited. In this work, the synthesis and solid-state characterization of a polymorphic cocrystal composed of sulfadimidine (SD) and 4-aminosalicylic acid (4-ASA) is reported for the first time. By liquid-assisted milling, the SD:4-ASA 1:1 form I cocrystal, the structure of which has been previously reported, was formed. By spray drying, a new polymorphic form (form II) of the SD:4-ASA 1:1 cocrystal was discovered which could also be obtained by solvent evaporation from ethanol and acetone. Structure determination of the form II cocrystal was calculated using high-resolution X-ray powder diffraction. The solubility of the SD:4-ASA 1:1 cocrystal was dependent on the pH and predicted by a model established for a two amphoteric component cocrystal. The form I cocrystal was found to be thermodynamically more stable in aqueous solution than form II, which showed transformation to form I. Dissolution studies revealed that the dissolution rate of SD from both cocrystals was enhanced when compared with a physical equimolar mixture and pure SD.

Electrochemical promotion of catalysis using solid-state proton-conducting membranes

A solid-state electrochemical reactor with ceramic proton-conducting membrane has been used to study the effect of electrochemically induced hydrogen spillover on the catalytic activity of platinum during ethylene oxidation. Suitable proton-conducting electrolyte membranes (Gd-doped BaPrO ₃ (BPG) and Y-doped BaZrO₃ (BZY)) were fabricated. These materials were chosen because of their protonic conductivity in the operational temperature region of the reaction (400-700 °C). The BZY-based electrochemical cell was used to investigate the open-circuit voltage (OCV) dependence on H₂ partial pressure with comparison being made to the theoretical OCV as predicted by the Nernst equation. Furthermore, the BZY pellets were used to study the effect of proton transfer of the catalytic activity of platinum during ethylene oxidation. The reaction was found to exhibit electrochemical promotion at 400 °C and to be electrophilic in nature, i.e. proton addition to the platinum surface resulted in an increase in reaction rate. At higher temperatures, the rate was not affected, within experimental error, by proton addition or removal. Under similar conditions, AC impedance showed that there was a large overall cell resistance at 400 °C with significantly decreased resistance at higher temperatures. It is possible that there could be a relationship between large cell resistances and the onset of electrochemical promotion in this system but there is, as yet, no conclusive evidence for this. © 2003 Elsevier B.V. All rights reserved.

Solid-state NMR and powder XRD studies of the structure of SAPO-40 upon hydration-dehydration cycles

It is well known that after the removal of the template many porous aluminophosphates and related materials are very sensitive to water.' Depending on the type of structure, reversible or irreversible phase transitions, loss of crystallinity and changes in the coordination of some framework A1 upon rehydration are observed. For example, solid-state NMR shows that the rehydration of SAPO-5 leads to the formation of octahedral Al. Subsequent dehydration restores the initial tetrahedral coordination of Al. Template-free SAPO-37 becomes totally amorphous to X-rays after exposure to water and stays so after subsequent thermal treatment^.,,^ In contrast, Barthomeuf and co-workers have shown recently, that, on hydration, template-free SAPO-34, an analogue of chabasite, shows the opening of some Si-0-A1 bonds, the effect being reversible upon dehydrati~n.T~h e hydrated distorted structure was found to be stable for months with no further modifications and the ordered material could be regenerated by removal of water. Here we wish to report that the structure of template-free SAPO-40 undergoes a similar reversible modification.

Disposable solid state probe for optical screening of chlorpromazine

We are presenting a simple, low-cost and rapid solid-state optical probe for screening chlorpromazine (CPZ) in aquacultures. The method exploits the colourimetric reaction between CPZ and Fe(III) ion that occurs at a solid/liquid interface, the solid layer consisting of ferric iron entrapped in a layer of plasticized PVC. If solutions containing CPZ are dropped onto such a layer, a colour change occurs from light yellow to dark pink or even light blue, depending on the concentration of CPZ. Visual inspection enables the concentration of CPZ to be estimated. The resulting colouration was also monitored by digital image collection for a more accurate quantification. The three coordinates of the hue, saturation and lightness system were obtained by standard image processing along with mathematical data treatment. The parameters affecting colour were assessed and optimized. Studies were conducted by visible spectrophotometry and digital image acquisition, respectively. The response of the optimized probe towards the concentration of CPZ was tested for several mathematical transformations of the colour coordinates, and a linear relation was found for the sum of hue and luminosity. The limit of detection is 50 μM (corresponding to about 16 μg per mL). The probe enables quick screening for CPZ in real water samples with prior sample treatment.

Polytypism and Silicon carbide : a solid state nuclear magnetic resonance study

A survey of predominantly industrial silicon carbide has been carried out using Magic Angle Spinning nuclear magnetic resonance (MAS nmr); a solid state technique. Three silicon carbide polytypes were studied; 3C, 6H, and 15R. The 13C and 29 Si MAS nmr spectra of the bulk SiC sample was identified on the basis of silicon (carbon) site type in the d iff ere n t pol Y t Y pes • Out to 5.00 A fro mac en t r a lsi 1 i con (0 r carbon) atom four types of sites were characterized using symmetry based calculations. This method of polytype analysis was also considered, in the prelminary stages, for applications with other polytypic material; CdBr 2 , CdI 2 , and PbI 2 " In an attempt to understand the minor components of silicon carbide, such as its surface, some samples were hydrofluoric acid washed and heated to extreme temperatures. Basically, an HF removable species which absorbs at -110 ppm (Si0 2 ) in the 29 Si MAS nmr spectrum is found in silicon carbide after heating. Other unidentified peaks observed at short recycle delays in some 29 Si MAS nmr spectra are considered to be impurities that may be within the lattice. These components comprise less than 5% of the observable silicon. A Tl study was carried out for 29 Si nuclei in a 3C ii polytype sample, using the Driven Equilibrium Single-Pulse Observation of T1 (DESPOT) technique. It appears as though there are a number of nuclei that have the same chemical shift but different T1 relaxation times. The T1 values range from 30 seconds to 11 minutes. Caution has to be kept when interpreting these results because this is the first time that DESPOT has been used for solid samples and it is not likely in full working order. MAS nmr indicates that the 13C and 29 Si ~sotropic chemical shifts of silicon carbide appear to have a reciprocal type of relationship_ Single crystal nmr analysis of a 6H sample is accordance with this finding when only the resultant isotropic shift is considered. However, single crystal nmr also shows that the actual response of the silicon and carbon nuclear environment to the applied magnetic field at various angles is not at all reciprocal. Such results show that much more single crystal nmr work is required to determine the actual behavior of the local magnetic environment of the SiC nuclei.

Raman spectra of polymethyl methacrylate optical fibres excited by a 532 nm diode pumped solid state laser

Polymethyl methacrylate (PMMA) optical fibres are fabricated by a preform drawing process. The Raman spectra of PMMA fibres are recorded using a diode pumped solid state laser emitting at 532 nm and a CCD-spectrograph in the 400–3800 cm−1 range. The variation of the Raman intensity with the length of the optical fibre is studied. Investigations are carried out on the variation of FWHM of the Raman peak at 2957 cm−1 with the length of the optical fibre and pump power. The differential scattering cross section and gain coefficient of the Raman peak at 2957 cm−1 in PMMA are calculated in relation to that of toluene.

Raman spectra of polymethyl methacrylate optical fibres excited by a 532 nm diode pumped solid state laser

Polymethyl methacrylate (PMMA) optical fibres are fabricated by a preform drawing process. The Raman spectra of PMMA fibres are recorded using a diode pumped solid state laser emitting at 532 nm and a CCD-spectrograph in the 400–3800 cm−1 range. The variation of the Raman intensity with the length of the optical fibre is studied. Investigations are carried out on the variation of FWHM of the Raman peak at 2957 cm−1 with the length of the optical fibre and pump power. The differential scattering cross section and gain coefficient of the Raman peak at 2957 cm−1 in PMMA are calculated in relation to that of toluene

Sulfated titania mediated regioselective nitration of phenol in solid state

Titania, sulfated titania and chromium loaded sulfated titania were prepared by sol–gel method and characterized using different technique. Phenol is nitrated regioselectively by nitric acid using chromium loaded sulfated titania catalysts. A remarkable ortho selectivity is observed in solid state nitration to yield exclusively ortho-nitrophenol. Compared to the conventional process, phenol nitration over solid acid catalyst is a clean and environment friendly process. Catalytic activity well correlates with the Brönsted acid sites of these catalysts.