Residence of liquids in the infra-junctional portion of the proximal stomach in patients with gastroesophageal reflux disease

Patients with gastroesophageal reflux disease may have disturbances of gastric motility, which could play a role in the pathophysiology of the disease. Recent studies have suggested that the gastric region just below the gastroesophageal junction may have a distinct physiological behavior. We determined whether patients with gastroesophageal reflux disease have abnormal residence of food in the infra-junctional portion of the stomach after ingesting a liquid nutrient meal. Fasted adult patients with reflux disease (N = 11) and healthy volunteers (N = 10) ingested a liquid meal (320 ml; 437 kcal) labeled with 99m technetium-phytate and their total gastric emptying half-time and regional emptying from the stomach infra-junctional region were determined. In 8 patients, episodes of postprandial acidic reflux to the esophagus were measured for 2 h using pH monitoring. There were no differences between reflux patients and controls regarding total gastric emptying time (median: 68 min; range: 39-123 min vs 65 min and 60-99 min, respectively; P > 0.50). Food residence in the infra-junctional area was similar for patients and controls: 23% (range: 20-30) vs 27% (range: 19-30%; P = 0.28) and emptying from this area paralleled total gastric emptying (Rs = 0.79; P = 0.04). There was no correlation between residence of food in the infra-junctional area and episodes of gastroesophageal reflux (Rs = 0.06; P = 0.88). We conclude that it is unlikely that regional motor disturbances involving the infra-junctional region of the stomach play a relevant role in the pathogenesis of acidic gastroesophageal reflux.

Phospha-adamantane ligands and phosphorous ionic liquids for palladium-catalyzed cross-coupling reactions /

New and robust methodologies have been designed for palladiumcatalyzed cross-coupling reactions involving a library of novel tertiary phosphine ligands incorporating a phospha-adamantane framework. The secondary phosphine, l,3,5,7-tetramethyl-2,4,8-trioxa-6-phospha-adamantane was converted into a small library of tertiary phosphine derivatives and the ability of these tertiary phosphaadamantanes to act as effective ligands in the palladium-catalyzed amination reaction and p-alkyl-Suzuki cross-coupling was examined. l,3,5,7-Tetramethyl-6- phenyl-2,4,8-trioxa-6-phosphaadamantane (PA-Ph) used in combination with Pd2(dba)3 CHCI3 facilitated the reaction of an array of aryl iodides, bromides and chlorides with a variety secondary and primary amines to give tertiary and secondary amines respectively in good to excellent yields. 8-(2,4-Dimethoxyphenyl)- l,3,5,7-tetramethyl-2,4,6-trioxa-8-phospha-tricyclo[3.3.1.1*3,7*]decane used in combination with Pd(0Ac)2 permitted the reaction of an array of alkyl iodides, and bromides with a variety aryl boronic acids and alkyl 9-BBN compounds in good to excellent yields. Subsequent to this work, the use of phosphorous based ionic liquids, specifically tetradecyltrihexylphosphonium chloride (THPC), in the Heck reaction provided good to excellent yields in the coupling of aryl iodides and bromides with a variety of olefins.

Thermal diffusivity measurements in organic liquids using transient thermal lens calorimetry

Thermal diffusivity measurements are carried out in certain organic liquids using the pulsed dual beam thermal lens technique. The 532 nm pulses from a frequency doubled Q-switched Nd:YAG laser are used as the heating source and an intensity stabilized He-Ne laser serves as the probe beam. Experimental determination of the characteristic time constant of the transient thermal lens signal is verified theoretically. Measured thermal diffusivity values are in excellent agreement with literature values.

Pulsed photoacoustic technique to study nonlinear processes in liquids: Results in toluene

Pulsed photoacoustic measurements have been carried out in toluene at 532 nm wavelength using a Q-switched frequency doubled Nd:YAG laser. The variation of photoacoustic signal amplitude with incident laser power indicates that at lower laser powers one photon absorption takes place at this wavelength while a clear two photon absorption occurs in this liquid at higher laser powers. The studies made here demonstrate that pulsed photoacoustic technique is simple and effective for the investigation of multiphoton processes in liquids.

Study of Laser Ablation in Liquids Using Pulsed Photoacoustic Technique

Laser ablation processes in liquid benzene, toluene and carbon disulphide have been investigated by pulsed photoacoustic technique using 532 nm radiation from a frequency doubled Q-switched Nd:YAG laser. The nature of variation of photoacoustic signal amplitude with laser energy clearly indicates that different phenomena are involved in the generation of photoacoustic effect and these are discussed in detail. Our results suggest multiphoton induced photofragmentation as the most plausible interaction process occurring during laser ablation in these liquids.

Broadband coaxial cavity resonator for complex permittivity measurements of liquids

A novel cavity perturbation technique using coaxial cavity resonators for the measurement of complex permittivity of liquids is presented. The method employs two types of resonators (Resonator I and Resonator II). Resonator I operates in the frequency range 600 MHz-7 GHz and resonator II operates in the frequency range 4 GHz-14 GHz. The introduction of the capillary tube filled with the sample liquid into the coaxial resonator causes shifts in the resonance frequency and loaded Q-factor of the resonator. The shifts in the resonance frequency and loaded Q-factor are used to determine the real and imaginary parts of the complex permittivity of the sample liquid, respectively. Using this technique, the dielectric parameters of water and nitrobenzene are measured. The results are compared with those obtained using other standard methods. The sources of errors are analyzed.

Gases, liquids and solids.

Este título se ha desarrollado específicamente para la enseñanza de la Química en el nuevo Nivel Avanzado (A2) de septiembre del año dos mil y aprobado por el OCR (uno de los tres órganos que ofrece la gama completa de las cualificaciones académicas y profesionales del Reino Unido). Está dividido en cuatro secciones:estados de la materia ; diagramas de fases ; distribución entre las fases ; ley de Raoult y destilación. El módulo se basa en el material del libro de texto Química 1, sin embargo, el material de apoyo se puede encontrar en la publicación Química 2. Al final de cada capítulo hay ejercicios con preguntas de autoevaluación para el estudio independiente. Tiene las respuestas a las preguntas de auto-evaluación, glosario, e índice .

Synthesis of multicarboxylic acid appended imidazolium ionic liquids and their application in palladium-catalyzed selective oxidation of styrene

A series of multicarboxylic acid appended imidazolium ionic liquids ( McaILs) with chloride [ Cl](-) or bromide [ Br](-) as anions have been synthesized and characterized. Deprotonation of these ionic acids gives the corresponding zwitterions. Re-protonation of the zwitterions with strong Bronsted acids gives a series of new ionic acid-adducts, many of which remained as room-temperature ionic liquids. A new catalytic system, McaIL/PdCl2 for the selective catalytic oxidation of styrene to acetophenone with hydrogen peroxide as an oxidant has been attempted. In the presence of McaILs, it is found that the quantity of palladium chloride PdCl2 used can be greatly reduced while the activity ( TOF) and selectivity towards acetophenone are enhanced sharply. It is also shown that the catalytic properties of this system could be finely tuned through the molecular design of the McaILs. The best TOF value obtained so far is 146 h(-1) with 100% conversion of styrene at 93% selectivity to acetophenone. In addition, the catalytic activity has been maintained for at least ten catalytic cycles.

Ultrasonic chemical oxidative degradations of 1,3-dialkylimidazolium ionic liquids and their mechanistic elucidations

A highly efficient process for oxidative degradation of 1,3-dialkylimidazolium ionic liquids in hydrogen peroxide/acetic acid aqueous medium assisted by ultrasonic chemical irradiation is, for the first time, described. It is shown that more than 93% of the 1,3-dialkylimidazolium cation with the corresponding Cl-, Br-, BF4- and PF6- counter-anions at a concentration of 2.5 mM can be degraded at 50 degrees C within 12 h while at 72 h the conversions approach 99%. A tentative mechanism for the degradation of these ILs is for the first time proposed through a detailed kinetic analysis of several characteristic transients and/or immediate products, which are identified during the ILs degradation using GC-MS. The results clearly indicate that three hydrogen atoms in the imidazolium ring are the first sites preferably oxidized, followed by cleavage of the alkyl groups attached to the N atoms from the ring. The nature of the alkyl chain length on the imidazolium ring and the type of counter anion do not seem to affect the degradation process. Further, selective fragmentations of C-N bonds of the imidazolium or derived ring lead to ring opening, forming degraded intermediates. It is also shown that acetoxyacetic acid and biurea are the final kinetically stable degraded products from the ILs under the degradation conditions.

The effect of vessel diameter on time dependent gas hold-up variations in highly viscous impeller agitated liquids

Time dependent gas hold-up generated in the 0.3 and 0.6 m diameter vessels using high viscosity castor oil and carboxy methyl cellulose (CMC) solution was compared on the basis of impeller speed (N) and gas velocity (V-G). Two types of hold-up were distinguished-the hold-up due to tiny bubbles (epsilon(ft)) and total hold-up (epsilon(f)), which included large and tiny bubbles. It was noted that vessel diameter (i.e. the scale of operation) significantly influences (i) the trends and the values of epsilon(f) and epsilon(ft), and (ii) the values of tau (a constant reflecting the time dependency of hold-up). The results showed that a scale independent correlation for gas hold-up of the form epsilon(f) or epsilon(ft) = A(N or P-G/V)(a) (V-G)(b), where "a" and "b" are positive constants is not appropriate for viscous liquids. This warrants further investigations into the effect of vessel diameter on gas hold-up in impeller agitated high viscosity liquids (mu or mu(a) > 0.4 Pa s). (C) 2003 Elsevier B.V. All rights reserved.

Relaxation of surface tension in the free-surface boundary layers of simple Lennard-Jones liquids

In this paper we use molecular dynamics to answer a classical question: how does the surface tension on a liquid/gas interface appear? After defining surface tension from the first principles and performing several consistency checks, we perform a dynamic experiment with a single simple liquid nanodroplet. At time zero, we remove all molecules of the interfacial layer of molecules, creating a fresh bare interface with the bulk arrangement of molecules. After that the system evolves towards equilibrium, and the expected surface tension is re-established. We found that the system relaxation consists of three distinct stages. First, the mechanical balance is quickly re-established. During this process the notion of surface tension is meaningless. In the second stage, the surface tension equilibrates, and the density profile broadens to a value which we call “intrinsic” interfacial width. During the third stage, the density profile continues to broaden due to capillary wave excitations, which does not however affect the surface tension.We have observed this scenario for monatomic Lennard-Jones (LJ) liquid as well as for binary LJ mixtures at different temperatures, monitoring a wide range of physical observables.

Relaxation of surface tension in the liquid-solid interfaces of Lennard-Jones liquids

We have established the surface tension relaxation time in the liquid-solid interfaces of Lennard-Jones (LJ) liquids by means of direct measurements in molecular dynamics (MD) simulations. The main result is that the relaxation time is found to be almost independent of the molecular structures and viscosity of the liquids (at seventy-fold change) used in our study and lies in such a range that in slow hydrodynamic motion the interfaces are expected to be at equilibrium. The implications of our results for the modelling of dynamic wetting processes and interpretation of dynamic contact angle data are discussed.

Influence of inherent structure shear stress of supercooled liquids on their shear moduli

Configurations of supercooled liquids residing in their local potential minimum (i.e. in their inherent structure, IS) were found to support a non-zero shear stress. This IS stress was attributed to the constraint to the energy minimization imposed by boundary conditions, which keep size and shape of the simulation cell fixed. In this paper we further investigate the influence of these boundary conditions on the IS stress. We investigate its importance for the computation of the low frequency shear modulus of a glass obtaining a consistent picture for the low- and high frequency shear moduli over the full temperature range. Hence, we find that the IS stress corresponds to a non-thermal contribution to the fluctuation term in the Born-Green expression. This leads to an unphysical divergence of the moduli in the low temperature limit if no proper correction for this term is applied. Furthermore, we clarify the IS stress dependence on the system size and put its origin on a more formal basis.

Ionic liquids and other liquid matrices for sensitive MALDI MS analysis

Although liquid matrix-assisted laser desorption/ionization (MALDI) has been used in mass spectrometry (MS) since the early introduction of MALDI, its substantial lack of sensitivity compared to solid (crystalline) MALDI was for a long time a major hurdle to its analytical competitiveness. In the last decade, this situation has changed with the development of new sensitive liquid matrices, which are often based on a binary matrix acid/base system. Some of these matrices were inspired by the recent progress in ionic liquid research, while others were developed from revisiting previous liquid MALDI work as well as from a combination of these two approaches. As a result, two high-performing liquid matrix classes have been developed, the ionic liquid matrices (ILMs) and the liquid support matrices (LSMs), now allowing MS measurements at a sensitivity level that is very close to the level of solid MALDI and in some cases even surpasses it. This chapter provides some basic information on a selection of highly successful representatives of these new liquid matrices and describes in detail how they are made and applied in MALDI MS analysis.