Automatic gravimetric apparatus for recording the adsorption isotherms of gases or vapours onto solids

The assembly described was built with the aim of obtaining high resolution and precision, together with automaticity. It was designed around a symmetrical commercial vacuum microbalance (Setaram), its main features being the following:(1) Controlled “residual” vacuum during outgassing of the sample.(2) Two possible procedures for the introduction of the adsorbate: either a conventional — but automated — point by point procedure (with discontinuous introduction of gas or vapour) or a continuous procedure, specially suited for high resolution work.(3) Measurement of pressure (0–1 atm) by a silica Bourdon gague (Texas Instruments) of 10^?5 accuracy.(4) Direct recording of the isotherms on a XY recorder.(5) Constant level (± 0.5 mm) cryogenic bath (liquid nitrogen or argon) of low consumption (4 liters per 15 hours).(6) Liquid thermostat for adsorption temperatures between ? 30 and + 100°C.(7) Temperature control (up to 50°C) of the whole assembly (manifolds, balance, gauges) allowing to handle condensable vapours.Several examples are given, illustrating the versatility and resolution of the systems. For instance, it allowed to detect, for the first time, a distinct substep at the top of the nitrogen/graphite and argon/graphite isotherms at 77 K. This is now explained by a sudden localization or “freezing” of the monolayer near its completion.     

Structural Variations in the Central Heterocyclic Scaffold of Tripartite 2,6-Difluorobenzamides: Influence on Their Antibacterial Activity against MDR Staphylococcus aureus

Five series of heterocyclic tripartite 2,6-difluorobenzamides, namely 1,2,3-triazoles, 1,2,4- and 1,3,4-oxadiazoles, analogs of reported model anti-staphylococcal compounds, were prepared. The purpose was to investigate the influence of the nature of the heterocyclic central scaffold on the biological activity against three strains of S. aureus, including two drug-resistant ones. Among the 15 compounds of the new collection, a 3-(4-tert-butylphenyl)-1,2,4-oxadiazole linked via a methylene group with a 2,6-difluorobenzamide moiety (II.c) exhibited a minimal inhibitory concentration between 0.5 and 1 µg/mL according to the strain. Subsequent studies on II.c demonstrated no human cytotoxicity, while targeting the bacterial divisome.     

Newtonian liquid jet impaction on a high-speed moving surface

In the railroad industry a friction modifying agent may be applied to the rail or wheel in the form of a liquid jet. In this mode of application the interaction between the high-speed liquid jet and a fast moving surface is important. Seven different Newtonian liquids with widely varying shear viscosities were tested to isolate the effect of viscosity from other fluid properties. Tests were also done on five surfaces of different roughness heights to investigate the effects of surface roughness. High-speed video imaging was employed to scrutinize the interaction between the impacting jet and the moving surface. For all surfaces, decreasing the Reynolds number reduced the incidence of splash and consequently enhanced the transfer efficiency. At the elevated Weber numbers of the testing, the Weber number had a much smaller impact on splash than the Reynolds number. The ratio of the surface velocity to the jet velocity has only a small effect on the splash, whereas increasing the roughness-height-to-jet-diameter ratio substantially decreased the splash threshold.     

High throughput qualitative analysis of polyphenols in tea samples by ultra-high pressure liquid chromatography coupled to UV and mass spectrometry detectors

The analysis of polyphenols in tea extracts is important due to their potential health benefits. Therefore, efficient and high throughput analytical methods have been developed for the separation of seven predominant polyphenols, also known as catechin derivatives, present in tea extracts. Columns packed with sub-2-μm particles operating at elevated pressure (UHPLC strategy) were selected to improve chromatographic performance. The potential of UHPLC–UV was demonstrated with baseline resolution of all standard catechins in only 30 s using a 50-mm column packed with 1.7-μm particles. When dealing with real samples such as tea extracts, however, longer columns of up to 150 mm in length were employed to enhance the separation of catechin derivatives and other constituents within the tea samples while maintaining an acceptable analysis time. Two strategies based on 2-D experiments were proposed to clearly identify catechins. Firstly, a liquid–liquid extraction procedure was added prior to the UHPLC–UV analysis to decrease the complexity of the sample. Secondly, UHPLC was coupled to ESI-MS/MS to attain sufficient sensitivity and selectivity between catechin derivatives and other constituents of tea extract. These two strategies were found extremely promising as a clear discrimination of catechins from the matrix could be attained.     

Coupling CE with atmospheric pressure photoionization MS for pharmaceutical basic compounds: optimization of operating parameters

The use of CE coupled with MS (CE-MS) has evolved as a useful tool to analyze charged species in small sample volumes. Because of its sensitivity, versatility and ease of implementation, the ESI interface is currently the method of choice to hyphenate CE to MS. An alternative can be the atmospheric pressure photoionization (APPI) source, however, numerous parameters must be optimized for its coupling to CE. After evaluation of the sheath liquid composition and the CE capillary outlet position, an experimental design methodology was assessed for optimizing other ionization source parameters, such as sheath liquid flow rate, drying gas flow rate and temperature, nebulizing gas pressure, vaporizer temperature, and capillary voltage. For this purpose, a fractional factorial design (FFD) was selected as a screening procedure to identify factors which significantly influence sensitivity and efficiency. A face-centered central composite design (CCD) was then used to predict and optimize sensitivity, taking into account the most relevant variables. Sensitivity was finally evaluated with the optimized conditions and height-to-noise ratios (H/N) around 10 were achieved for an injection of 200 ng/mL of each analyte.     

Fourier Transform Spectroscopy of the A'(1)Pi-X(1)Sigma(+) System of CaO

The A'(1)Pi-X(1)Sigma(+) near-infrared system of CaO was observed for the first time at high resolution using a Fourier transform spectrometer. The A'(1)Pi-X(1)Sigma(+) chemiluminescence was excited in a Ca + N(2)O flame produced in a Broida-type oven. More than 3000 rotational lines, classified into 19 bands involving the A'(1)Pi 0 /= 2) levels with the nearby b(3)Sigma(+) (v-2) levels has been detected. An extended set of A'(1)Pi (v = 0-3) data has been obtained which is suitable for use in a future multistate deperturbation analysis of the a(3)Pi approximately A'(1)Pi approximately b(3)Sigma(+) approximately A(1)Sigma(+) complex of excited states. The new near-infrared spectra of the A'(1)Pi-X(1)Sigma(+) transition of CaO also permits the first direct high-resolution linkage between the orange and green systems and the near-infrared bands. Copyright 2000 Academic Press.     

Internal kink instability during off-axis electron cyclotron current drive in the DIII-D tokamak

Experimental evidence is reported of an internal kink instability driven by a new mechanism: barely trapped suprathermal electrons produced by off-axis electron cyclotron heating on the DIII-D tokamak. It occurs in plasmas with an evolving safety factor profile q(r) when q(min) approaches 1. This instability is most active when ECCD is applied on the high field side of the flux surface. It has a bursting behavior with poloidal/toroidal mode number = m/n = 1/1. In positive magnetic shear plasmas, this mode becomes the fishbone instability. This observation can be qualitatively explained by the drift reversal of the barely trapped suprathermal electrons.     

Evaluation of thermally pretreated silica stationary phases under hydrophilic interaction chromatography conditions

Three novel hydrophilic interaction chromatography columns packed with bare silica 2.6 μm superficially porous particles were evaluated. These stationary phases undergo a different pretreatment temperature (400, 525, and 900°C) that might influence their kinetic performance and thermodynamic properties. In the first instance, we demonstrated that the performance of these columns was inferior to the commercial ones in the low plate count range (10 000 plates), but was more favorable for N values beyond 40 000 plates. Thanks to its high permeability and reasonable flow resistance (φ = 695), together with a minimum reduced heights equivalent to a theoretical plate value of only 2.4, the stationary phase pretreated at 400°C was particularly attractive for N > 70 000 plates with a remarkably low impedance value (E = 2488). In a second step, the impact of pretreatment temperature was evaluated using two mixtures of polar substances, namely nucleobases and derivatives, as well as nicotine and derivatives. Retentions and selectivities achieved on the tested stationary phases were appropriate, but selectivity differences were minor when modifying pretreatment temperature from 400 to 525°C. When we increased the pretreatment temperature up to 900°C, the surface chemistry was more seriously modified. Finally, the columns presented a good stability even at high temperature (70°C), especially for the phases pretreated at 400 and 525°C.     

The First Photochemical In Situ Production of Ti‐Based Nanoparticles: A SH2 Strategy Using Bis(cyclopentadienyl)titanium Dichloride (Cp2TiCl2)

Bis(cyclopentadienyl)titanium dichloride (Cp₂TiCl₂) is a high performance additive under UV light activation for both i) radical photopolymerization reactions (when added to a Type I photo­initiator such as 2,2‐dimethoxy‐2‐phenylacetophenone, the oxygen inhibition is reduced) and ii) a concomitant in situ photoinduced and oxygen mediated formation of Ti‐based nanoparticles (diameters ranging from 45 to 220 nm). The photochemical properties of Cp₂TiCl₂ are investigated by steady state photolysis and electron spin resonance, and its photoinitiation ability checked. The nanoparticles (NPs) are well characterized by transmission electron microscopy. The high reactivity of Cp₂TiCl₂ under air is ascribed to a bimolecular homolytic substitution (the S_H2 process is clearly demonstrated by density functional theory calculations and ESR experiments), which converts the peroxyls into new efficient initiating radicals. The photochemical in situ incorporation of Ti NPs has never previously been reported. The synthesis of metal nanoparticles by a S_H2 approach instead of the reduction of a metal salt appears to be a promising original method.