Dehydrochlorination of monodisperse poly(vinylidene chloride) latex

The objective of the work described in this paper was to produce dispersions of small spherical carbon particles, having particle diameters in the region of 0.1 μm. To this end, the dehydrochlorination of poly(vinylidene chloride) (PVDC) latex particles was attempted. The PVDC latex was prepared by a dispersion polymerization route. Both chemical and thermal dehydrochlorination routes were attempted. Chemical dehydrochlorination, using a variety of base/solvent systems, led to nonporous, spherical black particles of the required size, but which contained only 60% carbon; most of the remainder was oxygen, introduced by nucleophilic substitution reactions. Thermal dehydrochlorination, at 700°C under a nitrogen atmosphere, using a fluidized bed arrangement, on the other hand, led to black particles, having 90% carbon and which retained their sphericity, but which were highly porous. Initial chemical dehydrochlorination, prior to thermal treatment, did not seem to reduce the porosity of the final carbons. Dispersions of the carbon particles in a variety of solvents were readily achieved.     

Dispersion effects of laminar flow and spray chamber volume in capillary electrophoresis-inductively coupled plasma-mass spectrometry: a numerical and experimental approach

Band broadening related to laminar flow and spray chamber dead volume is a potential problem in flow injection (FI)-inductively coupled plasma-mass spectrometry (ICP-MS). We studied these two dispersion effects with a sheath flow capillary electrophoresis (CE)-ICP-MS interface. A numerical model was used to simulate advection diffusion processes in the CE-capillary and dispersion in the spray chamber. Experimental results of FI with this CE-ICP-MS interface agree well with numerical modeling results. Dispersion due to laminar flow depends strongly on capillary diameter and analyte diffusion coefficient and to a lesser extent on laminar velocity and capillary length and typically amounts to one order of magnitude peak width increase. Three spray chambers of 5, 20 and 150 ml dead volume showed an increase in band broadening and peak tailing with increasing dead volume. The use of standard Scott-type spray chambers (>90 ml volume) increases peak widths by 5-10 s regardless of injection time. The use of a low dead volume spray chamber is recommended for experiments where resolution is critical. The modeling approach can be extended to the coupling of other flow injection techniques, like micro-LC and nano-LC with ICP-MS.     

Synthetic erythropoietic proteins: tuning biological performance by site-specific polymer attachment

Chemical synthesis in combination with precision polymer modification allows the systematic exploration of the effect of protein properties, such as charge and hydrodynamic radius, on potency using defined, homogeneous conjugates. A series of polymer-modified synthetic erythropoiesis proteins were constructed that had a polypeptide chain similar to the amino acid sequence of human erythropoietin but differed significantly in the number and type of attached polymers. The analogs differed in charge from +5 to -26 at neutral pH and varied in molecular weight from 30 to 54 kDa. All were active in an in vitro cell proliferation assay. However, in vivo potency was found to be strongly dependent on overall charge and size. The trends observed in this study may serve as starting points for the construction of more potent synthetic EPO analogs in the future.     

Synthesis and anion binding properties of 2,5-diamidothiophene polypyrrole Schiff base macrocycles

[reaction: see text] Two easy-to-synthesize polypyrrolic 2,5-diamidothiophene Schiff base macrocycles are reported, along with their anion binding properties as determined via UV-vis spectroscopic titrations carried out in dichloroethane. There is a striking difference between the interactions with anions of the two macrocycles, a finding ascribed to differences in their rigidity. For example, the more flexible dipyrromethane-derived macrocycle displays a 1.2:1 hydrogen sulfate versus nitrate selectivity, while its more rigid bipyrrole-derived congener shows a 7.4:1 selectivity in favor to hydrogen sulfate.     

‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp³-hybridized nanothreads from sp²-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.      

Bidentate ligands formed by self-assembly

A novel supramolecular strategy to prepare bidentate ligands via the assembly of functionalised monomeric ligands on a dimeric zinc(II) porphyrin template is presented; the assembled bidentate ligands show chelating behaviour and their rhodium complexes display enhanced selectivity in the hydroformylation compared to the non-template analogue.     

Oxidation of organic sulfides by vanadium haloperoxidase model complexes

In addition to halide oxidation, the vanadium haloperoxidases are capable of oxidizing sulfides to sulfoxides. Four vanadium complexes with tripodal amine ligands, K[VO(O(2))(heida)] (1), VO(2)(bpg) (2), K[VO(2)(ada)] (3), and K(2)[VO(O(2))(nta)] (4), previously shown to perform bromide oxidation (Colpas, G. J.; Hamstra, B. J.; Kampf, J. W.; Pecoraro, V. L. J. Am. Chem. Soc. 1996, 118, 3469-3477), have now been shown to oxidize aryl alkyl sulfides to the corresponding sulfoxides. The oxidation was observed by the disappearance of thioanisole's ultraviolet absorption at 290 nm, by the change in the aromatic region of the (1)H NMR spectrum of the sulfides, and by changes in the complexes' (51)V NMR spectra. The amount of methyl phenyl sulfide oxidized in 3 h was 1000 equiv (per metal complex). The oxidation product is almost exclusively sulfoxide, with very little sulfone (less than 3% over a 3 h experiment) formed. This is consistent with an electrophilic oxidation mechanism, as had been proposed for oxidation of bromide by 1-4. The rate was found to be first order in substrate concentration, similar to the rate law observed for bromide oxidation. Unlike the bromide oxidation, the equivalent of acid required for peroxovanadium complex activation is not consumed. The complexes 1-4 are not reactive with styrene or cyclooctene. The relevance of these reactions to the mechanism of the vanadium haloperoxidases and, more generally, peroxovanadium oxygenation of sulfides will be discussed.     

Integrated microfabricated systems including a purification module and an on-chip nano electrospray ionization interface for biological analysis

We report here on an integrated microfabricated device dedicated to the preparation of biological samples prior to their on-line analysis by electrospray ionization-mass spectrometry (ESI-MS). This microfluidic device is fabricated using the negative photoresist SU-8 by microtechnology techniques. The device includes a chromatographic module plus an ESI interface for MS. The chromatographic module is dedicated to sample purification and is based on a polymer monolithic phase which includes hydrophobic moieties. The ESI interface is integrated onto the chip and is based on a capillary slot. We present here the integration of these different modules onto a single system that is fabricated via a SU-8-based microtechnology route. We present also their testing for the purification of peptide samples. This started with a partial integration step with the combination of at least two of the modules (microsystem + monolith; microsystem + nib) and their test before the fabrication and testing of fully integrated microsystems.     

Local and global chirality at surfaces: succinic acid versus tartaric acid on Cu110

A detailed comparison of tartaric acid (HOOC-CHOH-CHOH-COOH) and succinic acid (HOOC-CH(2)-CH(2)-COOH) molecules on a Cu(110) surface is presented with a view to elucidate how the two-dimensional chirality exhibited by such robust, chemisorbed systems is affected when both OH groups of the former molecule are replaced with H groups, a stereochemical change that leaves the metal-bonding functionalities of the molecule untouched but destroys both chiral centers. It is found that this change does not significantly affect the thermodynamically preferred chemical forms that are adopted, namely the doubly deprotonated bicarboxylate at low coverages (theta 相似文献   

A stereoelectronic effect on turn formation due to proline substitution in elastin-mimetic polypeptides

Stereoelectronic effects have been identified as contributing factors to the conformational stability of collagen-mimetic peptide sequences. To assess the relevance of these factors within other protein structural contexts, three polypeptide sequences were prepared in which the sequences were derived from the canonical repeat unit (Val-Pro-Gly-Val-Gly) of the protein material elastin. These elastin-mimetic polypeptides, elastin-1, elastin-2, and elastin-3, incorporate (2S)-proline, (2S,4S)-4-fluoroproline, and (2S,4R)-4-fluoroproline, respectively, at the second position of the elastin repeat. Calorimetric and spectroscopic investigations of these three polypeptides indicate that the incorporation of the substituted proline residues had a dramatic effect upon the self-assembly of the corresponding elastin peptide. The presence of (2S,4R)-4-fluoroproline in elastin-3 lowered the temperature of the phase transition and increased the type II beta-turn population with respect to the parent polypeptide, while the presence of (2S,4S)-4-fluoroproline in elastin-2 had the opposite effect. These results suggest that stereoelectronic effects could either enhance or hinder the self-assembly of elastin-mimetic polypeptides, depending on the influence of the proline analogue on the energetics of the beta-turn conformation that develops within the pentapeptide structural repeats above the phase transition. Density functional theory (DFT) was employed to model three possible turn types (betaI-, betaII-, and inverse gamma-turns) derived from model peptide segments (MeCO-Xaa-Gly-NHMe) (Xaa = Pro, 4S-F-Pro, or 4R-F-Pro) corresponding to the turn-forming residues of the elastin repeat unit (Val-Pro-Gly-Val-Gly). The results of the these calculations suggested a similar outcome to the experimental data for the elastin-mimetic polypeptides, in that type II beta-turn structures were stabilized for peptide segments containing (2S,4R)-fluoroproline and destabilized for segments containing (2S,4S)-fluoroproline relative to the canonical proline residue.