Palladium-catalyzed Suzuki cross-coupling of aryl halides with aryl boronic acids in the presence of glucosamine-based phosphines

Carbohydrate-substituted phosphines are easily obtained in quite good yields by coupling of protected or non-protected d-glucosamine with the corresponding diphenylphosphino acid. These neutral ligands, in association with palladium acetate, are very active catalysts in the Suzuki cross-coupling reaction. The polyhydroxy phosphines are more active than the peracetylated phosphines. The process tolerates electron-rich as well as electron-poor substituents. Excellent turnovers, up to 97?000 are observed.     

Diffusion coefficient measurement in a microfluidic analyzer using dual-beam microscale-refractive index gradient detection. Application to on-chip molecular size determination

We report a microchip-based detection scheme to determine the diffusion coefficient and molecular mass (to the extent correlated to molecular size) of analytes of interest. The device works by simultaneously measuring the refractive index gradient (RIG) between adjacent laminar flows at two different positions along a microchannel. The device, referred to as a microscale molecular mass sensor (micro-MMS), takes advantage of laminar flow conditions where the mixing of two streams occurs essentially by diffusion across the boundary between the two streams. Two flows merge on the microchip, one containing solvent only, referred to as the mobile phase stream and one which contains the analyte(s) of interest in the solvent, i.e. the sample stream. As these two streams merge and flow parallel to each other down the microchannel a RIG is created by the concentration gradient. The RIG is further influenced by analyte diffusion from the sample stream into the mobile phase stream. Measuring the RIG at a position close to the merging point (upstream signal) and simultaneously a selected distance further down the microchannel (downstream signal) provides real-time data related to the extent a given analyte has diffused, which can be readily correlated to analyte molecular mass by taking the ratio of the downstream-to-upstream signals. For the dual-beam RIG measurements, a diode laser output is coupled to a single mode fiber optic splitter with two output fibers. Light from each fiber passes through a graded refractive index (GRIN) lens forming a collimated beam that then passes through the microchannel and then on to a position sensitive detector (PSD). The RIG at both detection positions deflects the two collimated probe beams. The deflection angle of each beam is then measured on two separate PSDs. The micro-MMS was evaluated using polyethylene glycols (PEGs), sugars, and as a detector for size-exclusion chromatography (SEC). Peak purity can be readily identified using the micro-MMS with SEC. The limit of detection was 0.9 ppm (PEG at 11 840 g/mol) at the upstream detection position corresponding to a RI limit of detection (LOD) (3sigma) of 7-10(-8) RI. The pathlength for the RIG measurement was 200 microm and the angular LOD was 0.23 micro(rad) with a detection volume of 8 nl at both positions. The average molecular mass resolution was 9% (relative standard deviation) for a series of PEGs ranging in molecular mass from 106 to 22 800 g/mol. With this excellent mass resolution, small molecules such as monosaccharides, disaccharides, and so on, are readily distinguished. The sensor is demonstrated to readily determine unknown diffusion coefficients.     

The dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase from Haemophilus influenzae is a dinuclear metallohydrolase

The Zn K-edge extended X-ray absorption fine structure (EXAFS) spectra, of the dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase (DapE) from Haemophilus influenzae have been recorded in the presence of one or two equivalents of Zn(II) (i.e. [Zn_(DapE)] and [ZnZn(DapE)]). The Fourier transforms of the Zn EXAFS are dominated by a peak at ca. 2.0 A, which can be fit for both [Zn_(DapE)] and [ZnZn(DapE)], assuming ca. 5 (N,O) scatterers at 1.96 and 1.98 A, respectively. A second-shell feature at ca. 3.34 A appears in the [ZnZn(DapE)] EXAFS spectrum but is significantly diminished in [Zn_(DapE)]. These data show that DapE contains a dinuclear Zn(II) active site. Since no X-ray crystallographic data are available for any DapE enzyme, these data provide the first glimpse at the active site of DapE enzymes. In addition, the EXAFS data for DapE incubated with two competitive inhibitors, 2-carboxyethylphosphonic acid and 5-mercaptopentanoic acid, are also presented.     

Ambident reactivity of the thiocyanate anion revisited: can the product ratio be explained by the hard soft acid base principle?

Laser flash photolysis and stopped-flow methods have been employed to determine the kinetics of the reactions of benzhydrylium ions with both termini of the thiocyanate ion. In contrast to previous investigations which reported sulfur/nitrogen ratios of k(S)/k(N) = 2-10 for the reactions of carbocations with SCN(-), values of k(S)/k(N) = 10(3)-10(4) are now derived from absolute rate constants. This discrepancy is explained by the fact that the data determined in this investigation are the first which refer to activation-controlled attack of carbocations at both termini of the thiocyanate ion, while previous reactivity ratios included diffusion-controlled reactions. It is concluded that the selectivities of the reactions of carbocations with the thiocyanate ion cannot be explained by the hard soft acid base principle.     

Sidewall functionalization of single-walled carbon nanotubes by addition of dichlorocarbene

We report the sidewall functionalization of soluble HiPco single-walled carbon nanotubes (SWNTs) by addition of dichlorocarbene. The dichlorocarbene-functionalized SWNTs [(s-SWNT)CCl(2)] retain their solubility in organic solvents such as tetrahydrofuran and dichlorobenzene. The degree of dichlorocarbene functionalization was varied between 12% and 23% by using different amounts of the dichlorocarbene precursor. Because the addition of dichlorocarbene saturates the carbon atoms on the sidewall of the SWNTs and effectively replaces the delocalized partial double bonds with a cyclopropane functionality, the optical spectra of the SWNTs change dramatically. We estimate that the saturation of 25% of the pi-network electronic structure of the SWNTs is sufficient to remove all vestiges of the interband transitions in the infrared spectrum. The transitions at the Fermi level in the metallic SWNTs that appear in the far-infrared (FIR) region of the spectrum show a dramatic decrease of intensity on dichlorocarbene functionalization. The FIR region of the spectrum allows a clear differentiation between the covalent and the ionic chemistry of SWNTs. In contrast with covalent functionalization, we show that reaction of the SWNTs with bromine vapor leads to a strong increase in absorptions at the Fermi level that is observable in the FIR due to hole doping of the semiconducting SWNTs. Thermal treatment of the (s-SWNT)CCl(2) above 300 degrees C resulted in the breakage of C-Cl bonds, but did not restore the original electronic structure of the SWNTs.     

Enantiospecific total synthesis of (-)-polyoxamic acid using 2,3-aziridino-gamma-lactone methodology

The non-natural enantiomer of polyoxamic acid was synthesized in six steps from 2,3-aziridino-gamma-lactone 7 with an overall yield of 10%. The key step of the strategy is a deprotection-protection sequence on the nitrogen atom of the aziridine ring required for aziridine activation toward nucleophilic ring opening.     

Compositional and 2H NMR studies of bis(benzene)chromium composites of mesoporous vanadium-niobium mixed oxides

New mesoporous niobium oxides with 5, 10, and 15 mol% vanadium(V) doped into the walls of the structure were synthesized by the ligand-assisted templating method with an octadecylamine template. These materials were characterized by XRD, XPS, EPR, elemental analysis, and nitrogen adsorption before being treated with excess bis(benzene)chromium to give new composites with an organometallic phase in the walls. All materials were also characterized by EPR, XRD, nitrogen adsorption, XPS, SQUID magnetometry, and elemental analysis. The materials with higher percentages of vanadium absorbed more bis(benzene)chromium, because this process depends largely on the electron transfer between the organometallic and the walls of the mesostructure and vanadium(V) is a stronger oxidant than niobium(V). Conductivity studies on these materials revealed that the ratio of Cr(0) to Cr(l) in the pores was more important than the absolute Cr loading level in governing electron transport properties but that increasing the V content led to more insulating behavior regardless of the Cr concentration. Solid-state 2H NMR studies on perdeuteriobenzene analogues of these composites showed the presence of the neutral and cationic Cr species in different ratios depending on the loading. Tumbling of these species was also slow on the NMR time scale, indicating that the charge-carrying Cr species are not rapidly moving through the pore channels of the mesostructure. This suggests that the walls of the structure may play a key role in charge transfer in these composites, contrary to what was previously believed.     

The effect of ion energy upon plasma polymerization deposition rate for acrylic acid

A novel technique, which allows the importance of ion energy in plasma polymer film growth to be investigated, without perturbation of any other plasma parameter (particle densities or temperatures) or, in principle, perturbation of particle (neutral or ion) fluxes is applied in the plasma polymerisation of acrylic acid and new insight into polymer formation is gleaned.     

Anchor chain length alters the apparent mechanism of chloride channel function in SCMTR derivatives

Two membrane-anchored heptapeptides have been prepared and their pore-formation behavior in phospholipid bilayer membranes has been found to differ profoundly as a result only of alkyl chain length.     

Synthesis and structure of [(Sn(mu-PCy))3(Na x PMDETA)2], containing an electron-deficient [(Sn(mu-PCy))3]2- dianion

The reaction of CyPHNa with Sn(NMe2)2 in the presence of PMDETA (= (Me2NCH2CH2)2NMe) gives the title compound [(Sn(mu-PCy))3(Na x PMDETA)2] (1), containing an electron-deficient [(Sn(mu-PCy))]3(2-) dianion with a novel two-electron, three centre (2e-3c) bonding arrangement.