Prospect for characterizing interacting soft colloidal structures using spin-echo small angle neutron scattering

Spin-echo small angle neutron scattering (SESANS) provides a new experimental tool for structural investigation. Due to the action of spin-echo encoding, SESANS measures a spatial correlation function in real space, as opposed to the structure factor S(Q), I(Q), in momentum (Q) space measured by conventional small angle neutron scattering. To establish the usefulness of SESANS in structural characterization, particularly for interacting colloidal suspensions, we have previously conducted a theoretical study of the SESANS correlation functions for model systems consisting of particles with uniform density profiles [X. Li, C.-Y. Shew, Y. Liu, R. Pynn, E. Liu, K. W. Herwig, G. S. Smith, J. L. Robertson, and W.-R. Chen J. Chem. Phys. 132, 174509 (2010)]. Within the same framework, we explore in the present paper the prospect of using SESANS to investigate the structural characteristics of colloidal systems consisting of particles with nonuniform intraparticle mass distribution. As an example, a Gaussian model of interacting soft colloids is used to investigate the manifestation of structural softness in a SESANS measurement. The exploration shows a characteristically different SESANS correlation function for interacting soft colloids, in comparison to that of a uniform hard sphere system. The difference arises from the Abel transform imbedded in the mathematical formalism bridging the SESANS spectra and the spatial autocorrelation function.     

First principles determination of the bound levels of HeLi-

An analytical potential energy curve is developed from high quality ab initio calculations for the He+Li- interaction. The HeLi- electrostatic complex is found to have an Re of 18.5 bohrs and a De of 0.974 cm(-1). Numerical solution of the rovibrational Schr?dinger equation with this potential indicates two bound levels, (v,J)=(0,0) and (0,1), for all naturally occurring isotopologs (i.e., 4He7Li-, 4He6Li-, 3He7Li-, and 3He6Li-). For the common isotopolog, 4He7Li-, a D0 of 0.207 cm(-1) and an R0 of 26.5 bohrs is determined.     

Multicomponent dynamical nucleation theory and sensitivity analysis

Vapor to liquid multicomponent nucleation is a dynamical process governed by a delicate interplay between condensation and evaporation. Since the population of the vapor phase is dominated by monomers at reasonable supersaturations, the formation of clusters is governed by monomer association and dissociation reactions. Although there is no intrinsic barrier in the interaction potential along the minimum energy path for the association process, the formation of a cluster is impeded by a free energy barrier. Dynamical nucleation theory provides a framework in which equilibrium evaporation rate constants can be calculated and the corresponding condensation rate constants determined from detailed balance. The nucleation rate can then be obtained by solving the kinetic equations. The rate constants governing the multistep kinetics of multicomponent nucleation including sensitivity analysis and the potential influence of contaminants will be presented and discussed.     

"Exact" surface free energies of iron surfaces using a modified embedded atom method potential and lambda integration

Previously a new universal lambda-integration path and associated methodology was developed for the calculation of "exact" surface and interfacial free energies of solids. Such a method is in principle applicable to any intermolecular potential function, including those based on ab initio methods, but in previous work the method was only tested using a relatively simple embedded atom method iron potential. In this present work we apply the new methodology to the more sophisticated and more accurate modified embedded atom method (MEAM) iron potential, where application of other free- energy methods would be extremely difficult due to the complex many-body nature of the potential. We demonstrate that the new technique simplifies the process of obtaining "exact" surface free energies by calculating the complete set of these properties for the low index surface faces of bcc and fcc solid iron structures. By combining these data with further calculations of liquid surface tensions we obtain the first complete set of exact surface free energies for the solid and liquid phases of a realistic MEAM model system. We compare these predictions to various experimental and theoretical results.     

Oxybenziporphyrins, oxypyriporphyrins, benzocarbaporphyrins, and their 23-oxa and 23-thia analogues: synthesis, spectroscopic characterization, metalation, and structural characterization of a palladium(II) organometallic derivative

A series of nine porphyrin analogues have been synthesized using the "3 + 1" variant on the MacDonald condensation. Tripyrrane-type systems with a centrally unsubstituted pyrrole, furan, or thiophene ring were prepared using conventional methods, and these were condensed with indene-1,3-dicarbaldehyde, 5-formylsalicylaldehyde, or 3-hydroxy-2,6-pyridinedicarbaldehyde in the presence of TFA to generate benzocarba-, oxybenzi-, and oxypyriporphyrins, respectively. The furan-containing analogues proved to be highly basic and could only be isolated as the corresponding hydrochloride salts. All nine analogue systems showed porphyrin-like UV-vis spectra with one or two Soret absorptions near 400 nm and a series of weaker bands at longer wavelengths. These systems also showed large diatropic ring currents by proton NMR spectroscopy that were comparable to true porphyrins. In the presence of trace amounts of TFA, benzocarbaporphyrin 12 formed a monocation, and in 50% TFA a C-protonated dication was generated. The 23-oxacarbaporphyrin 14 gave a monocation in chloroform, although the free base was generated in 5% Et(3)N-chloroform. In 50% TFA-CHCl(3), 14 afforded a mixture of mono- and diprotonated species. Thiacarbaporphyrin 15 also formed a monocation in the presence of TFA, but C-protonation was relatively disfavored for this system. Nonetheless, in the presence of TFA-d, 12, 14, and 15 all showed rapid exchange of the internal NH and CH protons. Carbaporphyrin 12 also showed slow exchange at the meso-positions, but this process was not observed for its heteroanalogues 14 and 15. Protonation studies were also conducted for oxybenziporphyrins and oxypyriporphyrins 16-21. Oxacarbaporphyrin 14 was shown to be a superior organometallic ligand and afforded good yields of the related nickel(II) and palladium(II) derivatives under mild conditions. A low yield of the platinum(II) complex could also be isolated. All three complexes retained their aromatic character, although the Pd(II) derivative appeared to possess a slightly larger diatropic ring current. The palladium(II) complex 27 was further characterized by X-ray crystallography. The macrocyclic core was shown to be highly planar where the dihedral angles of the component pyrrole, furan and indene rings relative to the mean [18]annulene plane were all 相似文献   

A multiresidue pesticide monitoring procedure using gas chromatography/mass spectrometry and selected ion monitoring for the determination of pesticides containing nitrogen, sulfur, and/or oxygen in fruits and vegetables

A procedure for the analysis of over 100 pesticides that only contain combinations of carbon, hydrogen, nitrogen, sulfur, and oxygen (i.e., no phosphorous or halogen atoms) has been developed. The procedure employs gas chromatography with a mass selective detector (GC/MSD), electron impact ionization, and selected ion monitoring. This GC/MSD procedure provided lower limits of quantitation and increased confirmational data compared to the traditional element-selective GC procedures that are commonly used for the detection of this "class" of pesticides. These analytical improvements were demonstrated by 26 pesticides that were detected at ng/g levels in a variety of fruit and vegetable matrixes using this procedure; these pesticides were missed by the traditional element-selective GC procedures. Validation of the procedure was performed using acetone extraction with solid-phase extraction cleanup. Twenty representative target pesticides were used to demonstrate repeatability and linearity of the chromatographic response and recovery from fruit and vegetable matrixes.     

Single-shot gradient-assisted photon echo electronic spectroscopy

Two-dimensional electronic spectroscopy (2D ES) maps the electronic structure of complex systems on a femtosecond time scale. While analogous to multidimensional NMR spectroscopy, 2D optical spectroscopy differs significantly in its implementation. Yet, 2D Fourier spectroscopies still require point-by-point sampling of the time delay between two pulses responsible for creating quantum coherence among states. Unlike NMR, achieving the requisite phase stability at optical frequencies between these pulse pairs remains experimentally challenging. Nonetheless, 2D optical spectroscopy has been successfully demonstrated by combining passive and active phase stabilization along with precise control of optical delays and long-term temperature stability, although the widespread adoption of 2D ES has been significantly hampered by these technical challenges. Here, we exploit an analogy to magnetic resonance imaging (MRI) to demonstrate a single-shot method capable of acquiring the entire 2D spectrum in a single laser shot using only conventional optics. Unlike point-by-point sampling protocols typically used to record 2D spectra, this method, which we call GRadient-Assisted Photon Echo (GRAPE) spectroscopy, largely eliminates phase errors while reducing the acquisition time by orders of magnitude. By incorporating a spatiotemporal encoding of the nonlinear polarization along the excitation frequency axis of the 2D spectrum, GRAPE spectroscopy achieves no loss in signal while simultaneously reducing overall noise. Here, we describe the principles of GRAPE spectroscopy and discuss associated experimental considerations.     

Bifunctional polymer brushes for low-bias enrichment of mono- and multi-phosphorylated peptides prior to mass spectrometry analysis

Polymer brushes orthogonally derivatized with oxotitanium and nitrilotriacetate-Fe(III) groups enrich both mono- and multi-phosphorylated peptides for mass spectrometry analysis.     

POTENTIATION OF MEROCYANINE 540-MEDIATED PHOTODYNAMIC THERAPY BY SALICYLATE and RELATED DRUGS

Abstract— Simultaneous exposure to merocyanine 540 (MC540) and light of a suitable wavelength kills leukemia, lymphoma and neuroblastoma cells but is relatively well tolerated by normal pluripotent hematopoietic stem cells. This differential phototoxic effect has been exploited in preclinical models and a phase I clinical trial for the extracorporeal purging of autologous bone marrow grafts. Salicylate is known to potentiate the MC540-mediated photokilling of tumor cells. Assuming that salicylate induces a change in the plasma membrane of tumor cells (but not normal hematopoietic stem cells) that enhances the binding of dye molecules it has been suggested that salicylate may provide a simple and effective means of improving the therapeutic index of MC540-mediated photodynamic therapy. We report here on a direct test of this hypothesis in a murine model of bone marrow transplantation as well as in clonal cultures of normal murine hematopoietic progenitor cells. In both systems, salicylate enhanced the MC540-sensitized photoinactivation of leukemia cells and normal bone marrow cells to a similar extent and thus failed to improve the therapeutic index of MC540 significantly. On the basis of a series of dye-binding studies, we offer an alternative explanation for the potentiating effect of salicylate. Rather than invoking a salicylate-induced change in the plasma membrane of tumor cells, we propose that salicylate displaces dye molecules from serum albumin, thereby enhancing the concentration of free (active) dye available for binding to tumor as well as normal hematopoietic stem cells.     

Enantiomerically pure phosphaalkene-oxazolines (PhAk-Ox): synthesis, scope and copolymerization with styrene

The design of a synthetic route to a class of enantiomerically pure phosphaalkene-oxazolines (PhAk-Ox) is presented. The condensation of a lithium silylphosphide and a ketone (the phospha-Peterson reaction) was used as the P=C bond-forming step. Attempted condensation of PhC(=O)Ox (Ox = CNOCH(iPr)CH(2)) and MesP(SiMe(3))Li gave the unusual heterocycle (MesP)(2)C(Ph)=CN-(S)-CH(iPr)CH(2)O (3). However, PhAk-Ox (S,E)-MesP=C(Ph)CMe(2)Ox (1?a) was successfully prepared by treating MesP(SiMe(3))Li with PhC(=O)CMe(2)Ox (52?%). To demonstrate the modularity and tunability of the phospha-Peterson synthesis several other phosphaalkene-oxazolines were prepared in an analogous manner to 1?a: TripP=C(Ph)CMe(2)Ox (1?b; Trip = 2,4,6-triisopropylphenyl), 2-iPrC(6)H(4)P=C(Ph)CMe(2)Ox (1?c), 2-tBuC(6)H(4)P=C(Ph)CMe(2)Ox (1?d), MesP=C(4-MeOC(6)H(4))CMe(2)Ox (1?e), MesP=C(Ph)C(CH(2))(4)Ox (1?f), and MesP=C(3,5-(CF(3))(2)C(6)H(3))C(CH(2))(4)Ox (1?g). To evaluate the PhAk-Ox compounds as prospective precursors to chiral phosphine polymers, monomer 1?a and styrene were subjected to radical-initiated copolymerization conditions to afford [{MesPC(Ph)(CMe(2)Ox)}(x){CH(2)CHPh}(y)](n) (9?a: x = 0.13n, y = 0.87n; GPC: M(w) = 7400?g mol(-1) , PDI = 1.15).