Effect of nitrogen adsorption on the mid-infrared spectrum of water clusters

Experimental Fourier-transform infrared spectra and DFT calculated infrared spectra are compared to investigate the effect of adsorbed nitrogen on the OH-stretch band complex of water clusters. Using a collisional cooling experiment, pure as well as partially and completely N(2)-covered water clusters consisting of 20-200 water molecules have been generated in thermal equilibrium in the aerosol phase within the temperature range of 5-80 K. Computational IR-spectra simulations have been performed for discrete pure and N(2)-covered water clusters including 10, 15, 20, and 30 water molecules. The adsorbed N(2) molecules especially affect the three-coordinated water molecules at the cluster surface which could be observed as a blue shift of the companion O-H band at 2900 cm(-1) and a red shift of the dangling O-H band at 3700 cm(-1) by about 20 cm(-1) in both cases. The most striking effect of the N(2) adsorbate is an intensity increase of the dangling O-H band by a factor of 3-5. Furthermore, the onset temperature of nitrogen adsorption at the water cluster surface was experimentally found to be roughly 30 K for cluster sizes of about 100 water molecules. Experimental and computational results are in good agreement. The presented results are based on and support the work of V. Buch, J. P. Devlin, and co-workers (e.g., J. Phys. Chem. B, 1997; J. Phys. Chem. A, 2003; Int. Rev. Phys. Chem., 2004).     

Several convenient methods for the synthesis of 2-amido substituted furans

Several new methods for the synthesis of differently substituted 2-amidofurans are described. The thermolysis of furan-2-carbonyl azide results in a Curtius rearrangement and the resulting furanyl isocyanate was trapped with various organometallic reagents. A second method consists of a C-N cross-coupling reaction of a bromo-substituted furan with various amides, carbamates, and lactams. The CuI-catalyzed cross-coupling reaction between furanyl bromides and amides furnished 2- and 3-substituted amidofurans in 45-95% yield. The third protocol used involves the reaction of cyclic carbinol amides with triflic anhydride. The reaction proceeds under very mild conditions to provide alpha-(trifluoromethyl)sulfonamido-substituted furans in high yield. The resulting iminium ion derived from the reaction of the hydroxy pyrrolidinone with Tf(2)O undergoes a facile ring opening as a consequence of the adjacent hydroxyl group to produce an imino triflate intermediate. Subsequent cyclization of this highly electrophilic imine with the oxygen atom of the adjacent carbonyl group leads to an imino dihydrofuran that reacts further with another equivalent of Tf(2)O to give the observed product.     

A model to set measurement quality objectives and to establish measurement uncertainty expectations in analytical chemistry laboratories using ASTM proficiency test data

A model is presented that correlates historical proficiency test data as the log of interlaboratory standard deviations versus the log of analyte concentrations, independent of analyte (measurand) or matrix. Analytical chemistry laboratories can use this model to set their internal measurement quality objectives and to apply the uncertainty budget process to assign the maximum allowable variation in each major step in their bias-free measurement systems. Laboratories that are compliant with this model are able to pass future proficiency tests and demonstrate competence to laboratory clients and ISO 17025 accreditation bodies. Electronic supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/ 10.1007/s007690100398-y. Received: 31 March 2001 Accepted: 11 September 2001     

Further studies on the application of vinylogous amides and β-halovinylaldehydes to the regiospecific synthesis of unsymmetrical,polyfunctionalized 2,3,4- and 1,2,3,4- substituted pyrroles

Highly functionalized pyrroles with appropriate regiochemical functionality represent an important class of marine natural products and potential drug candidates. We describe herein a detailed study of the reaction of α-aminoacid esters with vinylogous amides and also β-halovinylaldehydes for the regiospecific synthesis of 2,3,4-trisubstituted and 1,2,3,4-tetrasubstituted pyrroles. Since the vinylogous amides and β-halovinylaldehydes are readily available precursors, rapid access to a wide variety of unsymmetrically substituted pyrroles is accomplished via this methodology.     

Solvent release upon ion association from entropy data

The translational entropy loss on the association of two ions to form an ion pair or 11 complex is overcompensated by a rotational entropy gain, an electrostatic entropy gain, and an entropy gain due to solvent release from translational immobilization. The first three effects can be calculated, leaving the fourth as a difference from the experimental entropy change on association. The ratio of the solvent release entropy gain to the entropy change on melting of the solvent indicates the number of solvent molecules released on the association. A similar value is obtained from data for the volume change on association.Presented as a poster at the 10th International Conference on Non-Aqueous Solvents (ICNAS) at Leuven, Belgium, August 1986, and at the 24th International Congress on Coordination Chemistry (ICCC) at Athens, Greece, August 1986.     

A Surrogate for Debye-Waller Factors from Dynamic Stokes Shifts

We show that the short-time behavior of time-resolved fluorescence Stokes shifts (TRSS) are similar to that of the intermediate scattering function obtained from neutron scattering at q near the peak in the static structure factor for glycerol. This allows us to extract a Debye-Waller (DW) factor analog from TRSS data at times as short as 1 ps in a relatively simple way. Using the time-domain relaxation data obtained by this method we show that DW factors evaluated at times ≥ 40 ps can be directly influenced by α relaxation and thus should be used with caution when evaluating relationships between fast and slow dynamics in glassforming systems.     

Building custom polysaccharides in vitro with an efficient, broad-specificity xyloglucan glycosynthase and a fucosyltransferase

The current drive for applications of biomass-derived compounds, for energy and advanced materials, has led to a resurgence of interest in the manipulation of plant polymers. The xyloglucans, a family of structurally complex plant polysaccharides, have attracted significant interest due to their intrinsic high affinity for cellulose, both in muro and in technical applications. Moreover, current cell wall models are limited by the lack of detailed structure-property relationships of xyloglucans, due to a lack of molecules with well-defined branching patterns. Here, we have developed a new, broad-specificity "xyloglucan glycosynthase", selected from active-site mutants of a bacterial endoxyloglucanase, which catalyzed the synthesis of high molar mass polysaccharides, with complex side-chain structures, from suitable glycosyl fluoride donor substrates. The product range was further extended by combination with an Arabidopsis thaliana α(1→2)-fucosyltransferase to achieve the in vitro synthesis of fucosylated xyloglucans typical of dicot primary cell walls. These enzymes thus comprise a toolkit for the controlled enzymatic synthesis of xyloglucans that are otherwise impossible to obtain from native sources. Moreover, this study demonstrates the validity of a chemo-enzymatic approach to polysaccharide synthesis, in which the simplicity and economy of glycosynthase technology is harnessed together with the exquisite specificity of glycosyltransferases to control molecular complexity.