Influence of structural heterogeneity of nanoporous sorbent walls on hydrogen storage

Heterogeneity is an ubiquitous aspect of adsorption, often modifying substantially the observed behaviour of the adsorbate-adsorbent system. In this paper, the influence of heterogeneity is explicitly analyzed for the case of the adsorption of molecular hydrogen onto nanoporous carbon. Grand Canonical Monte Carlo simulations were used to study the mechanism of adsorption in the models of the adsorbate that include both energetic and structural modifications of graphene-based slit pores. In particular, a partial substitution of carbons by boron modifies both the symmetry of the energy landscape and the strength of hydrogen physisorption; which results in considerable increases of the amount of adsorbed gas without major modification of the mechanism of adsorption. Additional heterogeneity arises from structural modifications of the adsorbent by neutron irradiation of boron-doped samples, where the boron fission products generate additional surface area for adsorption. Simulations of adsorption in such pores show that hydrogen uptake is strongly dependent on the chemical nature of the modified pore walls.     

Novel oxidatively removable protecting groups and linkers for solid-phase synthesis of oligosaccharides

Summary Several new para-substituted benzyl- or phenyl-type protecting groups and their application to linkers for solid-phase synthesis are described.p-Acylaminobenzyl groups have higher acid stability than thep-methoxybenzyl (MPM) group, but are readily cleaved with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). Thep-azidobenzyl (Azb) group also has higher acid stability than the MPM group and can be removed much faster than the MPM group by DDQ oxidation after conversion of the azide group into the corresponding iminophosphorane. The acid stability of thep-azido-m-chlorobenzyl group (Cl-Azb) is higher than that of the Azb group. The former can be readily removed by DDQ oxidation after conversion of the azide group into the iminophosphorane. Thep-acylaminophenyl glycoside linker can be readily obtained fromp-nitrophenyl glycoside and can be readily cleaved by ammonium cerium(IV) nitrate (CAN) oxidation. This type of linker should be useful not only for the solid-phase synthesis of oligosaccharides but also for general solid-phase synthesis.     

Novel modified ultrasonication technique for the extraction of lycopene from tomatoes

Lycopene extraction was carried out via the ultrasonic assisted extraction (UAE) with response surface methodology (RSM). Sonication enhanced the efficiency of relative lycopene yield (enhancement of 26% extraction yield of lycopene in 6 replications at 40.0 min, 40.0 °C and 70.0% v/w in the presence of ultrasound), lowered the extraction temperature and shortened the total extraction time. The extraction was applied with the addition of oxygen-free nitrogen flow and change of water route during water bath sonication. The highest relative yield of lycopene obtained was 100% at 45.0 °C with total extraction time of 50.0 min (30:10:10) and ratio of solvent to freeze-dried tomato sample (v/w) of 80.0:1. Optimisation of the lycopene extraction had been performed, giving the average relative lycopene yield of 99% at 45.6 min, 47.6 °C and ratio of solvent to freeze-dried tomato sample (v/w) of 74.4:1. From the optimised model, the average yield of all-trans lycopene obtained was 5.11 ± 0.27 mg/g dry weight. The all-trans lycopene obtained from the high-performance liquid chromatography (HPLC) chromatograms was 96.81 ± 0.81% with 3.19 ± 0.81% of cis-lycopenes. The purity of total-lycopene obtained was 98.27 ± 0.52% with β-carotene constituted 1.73 ± 0.52% of the extract. The current improved, UAE of lycopene from tomatoes with the aid of RSM also enhanced the extraction yield of trans-lycopene by 75.93% compared to optimised conventional method of extraction. Hence, the current, improved UAE of lycopene promotes the extraction yield of lycopene and at the same time, minimises the degradation and isomerisation of lycopene.     

Detection of ibuprofen and ciprofloxacin by solid-phase extraction and UV/Vis spectroscopy

A simple and economic solid-phase extraction coupled with UV/Vis spectrophotometric method is described for the analysis of ibuprofen and ciprofloxacin. Following solid-phase extraction from model wastewater samples containing standard ibuprofen or ciprofloxacin, elutes were analyzed by a UV/Vis spectrophotometer at 225 nm for ibuprofen and 280 nm for ciprofloxacin. The assay was linear for both compounds with good coefficients of correlation. This method shows good recoveries for both compounds with 101.0 ± 9.8% for ibuprofen and 99.4 ± 11.8% ciprofloxacin.     

Novel method for multiturn extraction: trapping charged particles in islands of phase space

A novel method for multiturn extraction from a circular particle accelerator is presented, based on trapping particles into islands of phase space generated by nonlinear resonances. By appropriate use of sextupoles and octupoles, stable islands can be created at small amplitude in phase space. By varying the linear tune, particles can be trapped inside these islands and then transported towards higher amplitudes for extraction. Results of numerical simulations are discussed.     

Algorithm comparison for schedule optimization in MR fingerprinting

In MR Fingerprinting, the flip angles and repetition times are chosen according to a pseudorandom schedule. In previous work, we have shown that maximizing the discrimination between different tissue types by optimizing the acquisition schedule allows reductions in the number of measurements required. The ideal optimization algorithm for this application remains unknown, however. In this work we examine several different optimization algorithms to determine the one best suited for optimizing MR Fingerprinting acquisition schedules.     

Understanding diffusion in nanoporous materials

Can we predict diffusion behavior of molecules in confinement by looking at the match between the molecule and the structure of the confinement? This question has proven difficult to answer for many decades. As a case study, we use methane and a simple model of ellipsoids to arrive at a molecular picture that allows us to make a classification of pore topologies and to explain their diffusion behavior as a function of loading. Our model is surprisingly simple: regarding a structure as consisting of interconnected ellipsoids is enough to understand the full loading dependence.     

Liquid chromatography/mass spectrometric determination of trans-resveratrol in wine using a tandem solid-phase extraction method

Liquid chromatography/mass spectrometry (LC/MS) with electrospray ionization has been successfully applied to the determination of trans-resveratrol (3,5,4'-trihydroxystilbene) in wine. Of a range of analytical conditions that were tested, optimum results were obtained by the use of reversed-phase high performance liquid chromatography (HPLC) using a mixture of methanol and ammonium acetate as the mobile phase. The negative-ion spectrum of trans-resveratrol showed pseudo-molecular ion, [M - H](-), which was the most abundant ion, and low fragment ions corresponding to the losses of hydroxyl groups of the phenol nucleus. Enhanced selectivity for the separation between trans-resveratrol and endogenous wine constituents was afforded by sample purification with a tandem solid-phase extraction method. The approach permits detection at low concentration of trans-resveratrol. The combination of improved sample pretreatment and an isocratic chromatographic system in conjunction with internal standardization forms the basis of a new assay for the quantitation of trans-resveratrol in wine. Full-scan mass spectra were readily obtained from 8 ng of trans-resveratrol, while a limit of detection of 200 pg (signal-to-noise ratio 3) was attained in the selected ion monitoring mode. The application of LC/MS to the determination of trans-resveratrol in wines is demonstrated by the analysis of red wines. Copyright 1999 John Wiley & Sons, Ltd.     

Preparation and characterization of porous DVB copolymers and their applicability for adsorption (solid-phase extraction) of phenol compounds

Using DVB, three new porous copolymers in the form of microspheres were prepared, characterized and used as adsorbents for phenol and its chlorinated derivatives. As the monomers: 4,4′-bis(maleimidodiphenyl)methane (BM), 2,3-bis(2-hydroxy-3-methylacryloyloxy-propoxy)naphthalene (2,3-NAF) and 2,3-epoxypropyl methacrylate (GLY) were used. All the studied materials were synthesized under the same conditions by means of suspension copolymerization. The DVB copolymers were characterized by elemental analysis, FTIR spectroscopy, TG and DSC analyses and N₂ sorption. The off-line solid-phase extraction method (SPE) was used to estimate sorption properties of the copolymers. The results show that the newly obtained materials are mesoporous but their shape of pores and chemical structures are different. BM-DVB and GLY-DVB are characterized by slit-shaped pores and wide pore size distribution. 2,3-NAF-DVB also possesses slit pores but distribution of pore size is narrower. Of those studied BM-DVB is the most interesting material. It has good sorption properties and heat resistance.     

Aluminium pre-patterning for highly ordered nanoporous anodized alumina

A pre-patterning method of aluminium surface, in order to obtain highly ordered nanoporous anodized alumina on large areas is presented. Aluminium single crystals have been used as a substrate and a 2D hexagonally closed-packed lattice of shallow pits, with diameter of about 200 nm and period of 350 nm, has been successfully achieved by direct writing laser lithography (DWL) and wet etching. Finally, anodic oxidation of the single crystal at high cell voltage in phosphoric solution results in oxide growth with pore ordering superimposed by the pre-patterning procedure.     

Interactions in self-organized nanoporous organic crystals

This Letter reports on the structural analysis of a self-assembly material, the prototype host-guest urea-alkane nanoporous crystal. Different spectroscopic techniques, under hydrostatic pressure, reveal a totally unexpected ordered phase where ordering does not require any apparent deformation of the host. This fundamental observation raises the question of the actual interactions in other similar supramolecular or biological tubular systems.     

Cyclodextrin-functionalized magnetic graphene as solid-phase extraction absorbent coupled with flame atomic absorption spectrophotometry for determination of cadmium in water and food samples

A magnetic hydroxypropyl-β-cyclodextrin-functionalized reduced graphene oxide was synthesized and used as a magnetic solid-phase extraction adsorbent for the enrichment of cadmium from water and food samples before its determination by flame atomic absorption spectrometry. The effects of pH, amount of adsorbent, extraction time, desorption condition, and coexisting ions on the extraction efficiency were investigated and optimized. Under the optimal conditions, the limit of detection was 0.23?µg?L^?1 for water samples and 0.015?µg?g^?1 for food samples, respectively. The linear range was between 0.50 and 100.0?µg?L^?1 with a good correlation coefficient of 0.9986 in water samples, and between 0.050 and 5.0?µg?g^?1 with a correlation coefficient of 0.9975 in food samples. The method recoveries for the spiked samples were in the range of 87.5–102.4%, with the relative standard deviations ranging from 4.7% to 6.2% and enrichment factors ranging from 38 to 41, respectively. The adsorbent could be reused over 50 times without a significant change of extraction capability. The established method provides a promising environmentally friendly alternative for the determination of cadmium in complex matrix samples with no need of additional chelating reagents during the extraction process.     

An analytical theory for diffusion of fluids in crystalline nanoporous materials

An analytical theory for diffusion of fluids in zeolites and other nanoporous materials has been developed. The theory incorporates molecular level information about the nanoporous material, which is obtainable from an energy minimization and does not require molecular dynamics computer simulations. The theory is statistical mechanical in nature and assumes a lattice composed of adsorption sites. The theory yields a self-diffusion coefficient, which is a function of (i) temperature, (ii) adsorbate density, (iii) adsorbate size, (iv) adsorbate-adsorbate energetic interaction and (v) adsorbate-pore energetic interaction. The theory is generalized and is applicable to nanoporous materials with three-dimensional porous networks (e.g. faujusite) and one-dimensional porous networks (e.g. A1P0₄-5).

The theory is self-contained and incorporates no fitting parameters. The theory does not require computational effort beyond a few seconds on a standard personal computer.     

A generalized analytical theory for adsorption of fluids in nanoporous materials

An analytical theory is presented for the adsorption of fluids confined in zeolites, molecular sieves, and other nanoporous materials. The theory takes advantage of the localized adsorption sites within a zeolite and develops a statistical mechanical lattice model of adsorption. The theory is completely generalized and can be used to model the lattice of adsorption sites within any arbitrary zeolite. The theory also has the advantage of requiring very few parameters: it requires only 4 parameters to describe the adsorbent, which can be obtained from a potential energy map of the adsorbent. No molecular dynamics simulations are required for parametrization. The theory incorporates both the atomistic structure of the adsorbent and the fundamental physical mechanisms, which dictate the behaviour of fluids confined in nanoporous materials. Finally the theory has the practical advantage of computational efficiency. The theory can generate a complete isotherm in approximately 1 minute on a desktop PC (300 MHz), compared with tens of CPU hours of supercomputer or parallel cluster time necessary to perform the molecule dynamics simulations required to generate a few points of the same isotherm.     

Charge-response of magnetization in nanoporous Pd-Ni alloys

This work reports isothermal reversible variation of magnetization in nanoporous Pd-Ni alloys subjected to continuous charging and discharging of the sample in aprotic electrolyte medium. Polarizing metal surface with excess charge also finds strain in the nanoporous structure using the sample as working electrode. Therefore, it is proposed that pressure induced by strain is the key parameter for the observed reversible magnetization in the transition metal alloys.     

Pressure-induced lock-in in an aperiodic nanoporous crystal

This Letter reports on the first observation of a commensurate lock-in inside an aperiodic composite. This result is obtained by neutron diffraction, under hydrostatic pressure, in the prototype self-assembled crystal of hexadecane urea. A selective compressibility of the sublattices is a required condition together with the existence of a lock-in energy term in these supramolecular materials. This measurement, under one-dimensional confinement, opens the way for the use of continuously controlled forces to manipulate molecular properties or functions.     

Dynamics of quantum liquids in nanoporous media

We sketch our recent neutron scattering measurements of the phonon-roton (P-R) modes and Bose-Einstein condensation (BEC) of liquid ⁴He in porous media. The aim is to reveal the interdependence of BEC, well-defined P-R modes and superfluidity in helium confined to nanoscales and in disorder. In all porous media investigated to date, we observe well-defined P-R modes above T_c in the normal liquid phase, up to T_λ. Since well defined P-R modes are associated with BEC, this suggests that there is BEC above T_c in porous media. We interpret this as BEC localized to favorable regions separated by regions of normal fluid. At high pressures, p ≥25 bars, well defined P-R modes are no longer observed at lower wavevectors, Q ≤1.5 ?. At p ≈39 bars a roton is no longer observed. Work is in progress to explore whether loss of modes can be associated with a recently reported Quantum Phase Transition.     

Surface characterisation of selected sorbent materials for common hydrocarbon fuels

The need to find the most efficient material for the clean-up of oil/fuel spills both at sea and on land is of extreme importance. Generally, this requires material selection based upon the adsorption properties of selected sorbent materials such as sand, swelling clays, organo-clays and cotton fibres. These adsorption properties are a function of the surface characterisation where hydrophobic and oleophilic properties are essential. From BET analysis, the adsorption isotherm of the selected materials was Types II and IV in the IUPAC classification scheme. The main adsorption mechanism for these sorbents occurred on the external surface of the material in the pores or capillaries. ESEM studies indicate that cotton capillaries contribute significantly to the adsorption process of oil. In addition, the presence of surface wax on cotton-cellulose fibre facilitated the uptake by: (a) providing a relatively hydrophobic surface for sorption of organics; and (b) providing a low surface energy environment for the capillaries to aid in oil transport. Cotton fibre was observed to have several key properties such as hydrophobicity, good affinity for hydrocarbons, rapid adsorption on contact, and high adsorption and retention through interfibre capillaries. This research provides the basis for selection of cotton-cellulose fibres compared to common and other novel alternatives such as sand and organo-clays, respectively.     

Magnetism of palladium clusters in nanoporous carbon

To determine the electronic properties of metal-carbon clusters, palladium clusters are introduced into nanoporous carbon samples. The structural and magnetic properties of the nanocomposite thus obtained are investigated. A ferromagnetic resonance (FMR) component is observed in the electron spin resonance (ESR) spectra measured in a wide temperature range. The electron density of states (DOS) of clusters consisting of a palladium atom surrounded by carbon atoms is calculated, and it is shown that, due to the interaction between electronic terms of carbon and metal, such a cluster should exhibit magnetism. The investigation of the structures of the porous skeleton of nanoporous carbon and of palladium clusters has allowed us to reveal how carbon and palladium atoms are brought into close contact so that to give rise to the observed ferromagnetism.