Interaction of Hydrogen with MOF-5

Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals.     

Tandem mass spectrometric accurate mass performance of time-of-flight and Fourier transform ion cyclotron resonance mass spectrometry: a case study with pyridine derivatives

The interpretation of mass spectra is a key process during compound identification, and the combination of tandem mass spectrometry (MS/MS) with high-accuracy mass measurements may deliver crucial information on the identity of a compound. Obtaining accurate mass data of fragment ions in MS/MS reveals the particular problem of mass calibration when a lockmass, which is frequently used to obtain accurate masses in MS, is absent. An alternative technique is to recalibrate the MS/MS spectrum using a reference MS/MS spectrum acquired under the same conditions. We have tested and validated this approach using a hybrid quadrupole/orthogonal acceleration reflectron-type time-of-flight (TOF) mass spectrometer. The results were compared with those obtained under similar conditions on a Fourier transform ion cyclotron resonance (FT-ICR) instrument. We found that the mass accuracy observed with such an "external" recalibration on the TOF instrument in MS/MS is identical to what can be obtained on a similar instrument operating in one-dimensional MS mode using the lockmass technique. However, mass accuracy in both cases is one order of magnitude inferior to that obtained using FTMS, and also inferior to that observed using sector field MS when operated at comparable resolution. Nevertheless, for small (<200 Da) molecules, this mass accuracy was still sufficient to have the "true" elemental composition identified as the first hit in about 70% of all cases. It was possible to elucidate the fragmentation mechanism of eight azaheterocycles containing a pyridine moiety, where the accurate mass data from the TOF instrument allowed distinction between two alternative fragmentation pathways.     

Molecular control of recombination dynamics in dye-sensitized nanocrystalline TiO2 films: free energy vs distance dependence

In this paper we address the dependence of the charge recombination dynamics in dye-sensitized, nanocrystalline TiO2 films upon the properties of the sensitizer dye employed. In particular we focus upon dependence of the charge recombination kinetics upon the dye oxidation potential E0(D+/D), determined electrochemically, and the spatial separation r of the dye cation HOMO orbital from the metal oxide surface, determined by semiempirical calculations. Our studies employed a series of ruthenium bipyridyl dyes in addition to porphyrin and phthalocyanine dyes. A strong correlation is observed between the recombination dynamics and the spatial separation r, with variation in r by 3 A resulting in a more than 10-fold change in the recombination half-time t(50%). This correlation is found to be in agreement with electron tunneling theory, t(50%) proportional, variant exp(-betar) with beta = 0.95 +/- 0.2 A-1. In contrast, the recombination dynamics were found to be relatively insensitive to variations in E0D+/D), indicative of the recombination reaction lying near the peak of the Marcus free energy curve, DeltaG approximately lambda, and with lambda approximately 0.8 eV. A correlation is also observed between the recombination half-time and the temporal shape of the kinetics, with faster recombination dynamics being more dispersive (less monoexponential). Comparison with numerical Monte Carlo type simulations suggests this correlation is attributed to a shift from fast recombination dynamics primarily limited by dispersive electron transport within the metal oxide film to slower dynamics primarily limited by the interfacial electron-transfer reaction. We conclude that the primary factor controlling the charge recombination dynamics in dye-sensitized, nanocrystalline TiO2 films is the spatial separation of the dye cation from the electrode surface. In particular, we show that for the Ru(dcbpy)2NCS2 dye series, the use of X = NCS rather than X = CN results in a 2 A shift in the dye cation HOMO orbital away from the electrode surface, causing a 7-fold retardation of the recombination dynamics, resulting in the remarkably slow recombination dynamics observed for this sensitizer dye.     

Electrospray Ionization Mass Spectrometric Analysis of Aqueous Polysulfide Solutions

The speciation of polysulfides in aqueous solutions was investigated by electrospray – ion trap and electrospray – time of flight mass spectrometry. The pH dependence of the observed total dissolved polysulfides concentration followed the trend calculated based on reported thermodynamic constants. However, the observed species distributions were substantially different from those calculated based on thermodynamic coefficients derived by UV spectroscopy. Notably, large abundances of heptasulfide, octasulfide and nonasulfide species were observed throughout the pH range 6 to 11. The large molecular weight anions had not been reported before in aqueous solutions although indirect evidence had suggested their existence.     

Microbial pretreatment of biomass

Typical pretreatment requires high-energy (steam and electricity) and corrosion-resistant, high-pressure reactors. A review of the literature suggests that fungal pretreatment could potentially lower the severity requirements of acid, temperature and time. These reductions in severity are also expected to result in less biomass degradation and consequently lower inhibitor concentrations compared to conventional thermochemical pretreatment. Furthermore, potential advantages of fungal pretreatment of agricultural residues, such as corn stover, are suggested by its effectiveness in improving the cellulose digestibility of many types of forage fiber and agricultural wastes. Our preliminary tests show a three- to five-fold improvement in enzymatic cellulose digestibility of corn stover after pretreatment with Cyathus stercoreus; and a ten- to 100-fold reduction in shear force needed to obtain the same shear rate of 3.2 to 7 rev/s, respectively, after pretreatment with Phanerochaete chrysosporium.     

Sol-gel derived ceramic-carbon enzyme electrodes: Glucose oxidase as a test case

Several types of amperometric biosensors comprised of immobilized glucose oxidase in chemically-modified ceramic-carbon matrices are compared. The electrodes are comprised of several building blocks each performing a specific function. Glucose oxidase is used to catalyze the bio-oxidation of glucose; carbon powder imparts conductivity and favorable electrochemical characteristics; the Ormosil network provides rigidity and porosity; and the organic modification of the Ormosil imparts controlled surface polarity. Additionally, hydrophilic chemical modifiers are incorporated in order to control the size of the wetted, electroactive layer; high dispersion of inert metal catalysts is used to enhance hydrogen peroxide oxidation and redox mediators may be co-immobilized when oxygen independent response is desirable. The electrodes can be prepared either in the form of thick supported film, useful for disposable electrodes or as bulk-modified, disk shape electrodes, which can be used as renewable surface electrodes.     

Proteomic analysis of immunostained,laser-capture microdissected brain samples

Proteomic analysis is often performed on homogenized preparations of whole tissues, which does not provide any information about relevant biochemical changes in specific cell types. Laser-capture microdissection (LCM) is a technique that is precise enough to dissect single cells within a tissue section. Phenotypically defined cells of interest may be visualized by immunostaining prior to microdissection. Previously published immunostaining protocols adapted to LCM require the use of very high antibody titers and very short incubation times. This raises the concern that low-abundance antigens would not be detected and that antisera would be rapidly depleted. In addition, protein recovery from samples was not evaluated in most of these studies. Here, we describe an optimized immunostaining method based on immunofluorescence. By comparing two-dimensional electrophoresis (2-DE) results obtained from immunostained LCM brain tissue samples to those obtained from unstained, manually dissected samples, we demonstrated that immunofluorescent staining gave comparable protein recovery and similar resolution of protein spots on 2-DE gels. Moreover, matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry analysis of selected spots from gels derived from control and immunostained LCM samples revealed that the immunostaining process had minimal effect on protein identification. LCM of immunofluorescently labeled tissue sections is a practical and powerful method to perform proteomic studies on specifically defined cell groups.     

Spectroscopic consequences of a mixed valence excited state: quantitative treatment of a dihydrazine diradical dication

A model for the quantitative treatment of molecular systems possessing mixed valence excited states is introduced and used to explain observed spectroscopic consequences. The specific example studied in this paper is 1,4-bis(2-tert-butyl-2,3-diazabicyclo[2.2.2]oct-3-yl)-2,3,5,6-tetramethylbenzene-1,4-diyl dication. The lowest energy excited state of this molecule arises from a transition from the ground state where one positive charge is associated with each of the hydrazine units, to an excited state where both charges are associated with one of the hydrazine units, that is, a Hy-to-Hy charge transfer. The resulting excited state is a Class II mixed valence molecule. The electronic emission and absorption spectra, and resonance Raman spectra, of this molecule are reported. The lowest energy absorption band is asymmetric with a weak low-energy shoulder and an intense higher energy peak. Emission is observed at low temperature. The details of the absorption and emission spectra are calculated for the coupled surfaces by using the time-dependent theory of spectroscopy. The calculations are carried out in the diabatic basis, but the nuclear kinetic energy is explicitly included and the calculations are exact quantum calculations of the model Hamiltonian. Because the transition involves the transfer of an electron from the hydrazine on one side of the molecule to the hydrazine on the other side and vice versa, the two transitions are antiparallel and the transition dipole moments have opposite signs. Upon transformation to the adiabatic basis, the dipole moment for the transition to the highest energy adiabatic surface is nonzero, but that for the transition to the lowest surface changes sign at the origin. The energy separation between the two components of the absorption spectrum is twice the coupling between the diabatic basis states. The bandwidths of the electronic spectra are caused by progressions in totally symmetric modes as well as progressions in the modes along the coupled coordinate. The totally symmetric modes are modeled as displaced harmonic oscillators; the frequencies and displacements are determined from resonance Raman spectra. The absorption, emission, and Raman spectra are fit simultaneously with one parameter set. The coupling in the excited electronic state H(ab)(ex) is 2000 cm(-1). Excited-state mixed valence is expected to be an important contributor to the electronic spectra of many organic and inorganic compounds. The energy separations and relative intensities enable the excited-state properties to be calculated as shown in this paper, and the spectra provide new information for probing and understanding coupling in mixed valence systems.     

Thermal, rheological, and barrier properties of waterborne acrylic nanocomposite coatings based on boehmite or organo-modified montmorillonite

An organo-modified montmorillonite (Cloisite^®30B) or an unmodified boehmite (Disperal^®40) have been added to two acrylic latex dispersions (one of them UV-curable) for obtaining nanocomposite coatings. X-ray diffraction and transmission electron microscopy show a high degree of exfoliation in the nanocoatings based on montmorillonite, together with the deagglomeration of the micrometer-sized boehmite powder and the presence of single boehmite crystallites within the polymer matrix. Such morphologies are found to enhance the thermal and thermo-oxidative stability of the latexes and to significantly decrease their oxygen permeability, as well.