Polymer-supported salen complexes for heterogeneous asymmetric synthesis: Stability and selectivity

This paper details the enantioselective performance of styrene/divinylbenzene-supported Mn- and Cr-based salen complexes for the epoxidation of olefins and the ring-opening of epoxides to azido-silyl ethers. The Mn catalyst produced the epoxides of 1,2-dihydronaphthalene, styrene, and cis-β-methylstyrene with enantiomeric excesses (ee's) of 46, 9, and 79%, respectively. For the Cr catalyst, the enantioselective ring-opening of epoxyhexane, propylene oxide, and cyclohexene oxide with trimethylsilyl azide proceeded with ee's of 34, 36, and 6%, respectively. Upon recycle of these heterogeneous catalysts, a degradation process was noted for the Mn-catalyst under the conditions for epoxidation that resulted in oxidation and decomposition of the ligand. This process also affects the homogeneous catalyst, thereby limiting the recyclability of both the homogeneous Mn catalyst and its heterogenized version for this reaction. The Cr-catalyzed reaction to ring-open epoxides employs milder conditions and allowed reuse of the heterogeneous catalyst without loss of activity or enantioselectivity through three runs with epoxyhexane. During reaction, the leaching of Cr from the heterogeneous catalyst is less than 0.1%, suggesting possible reuse of the catalyst over hundreds of cycles before reloading the polymer-supported salen ligand with metal would be necessary. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3888–3898, 1999     

Structure of polymer-stabilized magnetic fluids: small-angle neutron scattering and mean-field lattice modeling

Small-angle neutron scattering and mean-field lattice modeling were used to characterize a class of water-based magnetic fluids tailored specifically to extract soluble organic compounds from water. The fluids consist of a suspension of approximately 7 nm magnetite (Fe3O4) nanoparticles coated with a bifunctional polymer layer comprised of an outer hydrophilic poly(ethylene oxide) (PEO) region for colloidal stability and an inner hydrophobic poly(propylene oxide) (PPO) region for solubilization of organic compounds. The inner region of the polymer shell is increasingly depleted of water as the fraction of PPO side chains increases. The incorporation of PPO side chains also leads to a small increase in interparticle attraction. The lattice model predicted a shell structure similar to that of a PEO-PPO-PEO triblock copolymer (Pluronic) micelle, with equivalent levels of hydration but with more PEO present in the PPO-rich regions, as the side chains grafted to the surface are less able to segregate than when in free micellar systems.     

Odd-even variations in the wettability of n-alkanethiolate monolayers on gold by water and hexadecane: a molecular dynamics simulation study

Molecular dynamics (MD) simulations were performed to investigate odd-even chain length dependencies in the wetting properties of self-assembled monolayers (SAMs) of n-alkanethiols [CH3(CH2)n-1SH] on gold by water and hexadecane. Experimentally, the contact angle of hexadecane on the SAMs depends on whether n is odd or even, while contact angles for water show no odd-even dependence. Our MD simulations of this system included a microscopic droplet of either 256 water molecules or 60 hexadecane molecules localized on an n-alkanethiolate SAM on gold with either an even or odd chain length. Contact angles calculated for these nanoscopic droplets were consistent with experimentally observed macroscopic trends in wettability, namely, that hexadecane is sensitive to structural differences between odd- and even-chained SAMs while water is not. Structural properties for the SAMs (including features such as chain tilt, chain twist, and terminal methyl group tilt) were calculated during the MD simulations and used to generate IR spectra of these films that compared favorably with experimental spectra. MD simulations of SAMs in contact with slabs of water and hexadecane revealed that the effects of these solvents on the structure of the SAM was restricted to the chain terminus and had no effect on the inner structure of the SAM. The density profiles for water and hexadecane on the SAMs were different in that water displayed a significant depletion in its density at the liquid/SAM interface from its bulk value, while no such depletion occurred for hexadecane. This difference in contact may explain the lack of an odd-even variation in the wetting characteristics of water on these surfaces, because the water molecules are positioned further away from the surface and, therefore, are not sensitive to the structural differences in the average orientations for the terminal methyl groups in odd- and even-chained SAMs. In contrast, the differences in the wetting properties of hexadecane on the odd- and even-chained SAMs may reflect the closer proximity of these molecules to the SAM surface and a resulting greater sensitivity to the differences in the terminal methyl group orientations in the SAMs. SAM-solvent interaction energies were calculated during the MD simulations, yielding interaction energies that differed on the even- and odd-chained surfaces by approximately 10% for hexadecane and negligibly for water, in accord with estimates using experimental wetting results.     

Rigid, superparamagnetic chains of permanently linked beads coated with magnetic nanoparticles. Synthesis and rotational dynamics under applied magnetic fields

An inexpensive and versatile approach is reported for the synthesis of monodisperse magnetoresponsive rods of desired diameter, length, and magnetic susceptibility based on the confined alignment of magnetic beads in microchannels of selected channel height, followed by localized hydrolysis of sol-gel precursors within polyelectrolyte shells adsorbed on the beads. The layer-by-layer technique was used to coat the polystyrene beads with polyelectrolytes of alternating charge and with charged magnetic nanoparticles, and the polystyrene cores could be removed either by solvent dissolution or by calcination to form hollow-shelled chains. The reorientation dynamics of single and clustered chains following the application of an external magnetic field was evaluated theoretically, with favorable comparisons with the experimental data.     

A very thin coating for capillary zone electrophoresis of proteins based on a tri(ethylene glycol)-terminated alkyltrichlorosilane

We describe the use of a tri(ethylene glycol)-terminated alkyltrichlorosilane to create a very thin, protein-resistant "self-assembled monolayer" coating on the inner surface of a fused-silica capillary. The same compound has been demonstrated previously on flat silica substrates to resist adsorption of many proteins. As a covalently bound capillary coating, it displays good resistance to the adsorption of cationic proteins, providing clean separations of a mixture of lysozyme, cytochrome c, ribonuclease A, and myoglobin for more than 200 consecutive runs. Electroosmotic flow (EOF) was measured as a function of pH; the coated capillary retains significant cathodal EOF, with roughly 50% of the EOF of an uncoated capillary at neutral pH, making this coating promising for applications requiring some EOF. The EOF was reasonably stable, with a 2.9% relative standard deviation during a 24 h period consisting of 72 consecutive separations of cationic proteins. Efficiencies for cationic protein separations were moderate, in the range of 190,000-290,000 theoretical plates per meter. The coating procedure was simple, requiring only a standard cleaning procedure followed by a rinse with the silane reagent at room temperature. No buffer additives are required to maintain the stability of the coating, making it flexible for a range of applications, potentially including capillary electrophoresis-mass spectrometry (CE-MS).     

Electrochemical Sensing of Thiocyanate Using Gold Electrodes Modified with an Underpotentially Deposited Silver Monolayer

Gold electrodes modified by underpotential deposition to expose a layer of silver atoms on their surfaces were used to measure thiocyanate concentrations in aqueous solutions. When exposed to thiocyanate, the ion adsorbs onto the modified electrode and causes changes in the electrochemical properties of the silver adlayer. Coulometric measurement of the fraction of the silver adlayer that remains in its original state provides a means for determining thiocyanate concentrations. The adsorption of thiocyanate onto the electrode follows a first‐order process with a rate constant of ca. 440 L/mol s that defines its concentration/time response.     

Structural effects on the barrier properties of self-assembled monolayers formed from long-chain omega-alkoxy-n-alkanethiols on copper

The adsorption of long-chain omega-alkoxy-n-alkanethiols [CH(3)(CH(2))(p-1)O(CH(2))(m)SH; m = 11, 19, 22; p = 18, 22] onto copper produces self-assembled monolayers (SAMs) that can provide protection against corrosion of the underlying metal substrate. The resulting films are 40-60 A in thickness and are isostructural with SAMs formed on copper from unsubstituted n-alkanethiols. As evidenced by electrochemical impedance spectroscopy (EIS), the barrier properties of these ether-containing SAMs depend on the chain length of the adsorbate and the position of the ethereal unit along the hydrocarbon chain. For SAMs where the ether substitution is farther from the copper surface, the initial coating resistances are similar to those projected for unsubstituted n-alkanethiolate SAMs of similar thickness. For SAMs where the ether substitution is nearer to the copper surface (m = 11), the resistances are significantly less than those for unsubstituted n-alkanethiolate SAMs of similar thickness, reflecting the effect of the molecular structure on the barrier properties of the film. Upon exposure to 1 atm of O(2) at 100% RH, the SAMs become less densely packed as observed by infrared (IR) spectroscopy, and their barrier properties deteriorate as observed by EIS. The rate that the SAMs lose their barrier properties upon exposure to oxidizing conditions is correlated to the strength of intermolecular interactions within the bulk state of the adsorbate.     

Trypsin and MALDI matrix pre‐coated targets simplify sample preparation for mapping proteomic distributions within biological tissues by imaging mass spectrometry

Prefabricated surfaces containing α‐cyano‐4‐hydroxycinnamic acid and trypsin have been developed to facilitate enzymatic digestion of endogenous tissue proteins prior to matrix‐assisted laser desorption/ionization (MALDI) imaging mass spectrometry (IMS). Tissue sections are placed onto slides that were previously coated with α‐cyano‐4‐hydroxycinnamic acid and trypsin. After incubation to promote enzymatic digestion, the tissue is analyzed by MALDI IMS to determine the spatial distribution of the tryptic fragments. The peptides detected in the MALDI IMS dataset were identified by Liquid chromatography‐tandem mass spectrometry/mass spectrometry. Protein identification was further confirmed by correlating the localization of unique tryptic fragments originating from common parent proteins. Using this procedure, proteins with molecular weights as large as 300 kDa were identified and their distributions were imaged in sections of rat brain. In particular, large proteins such as myristoylated alanine‐rich C‐kinase substrate (29.8 kDa) and spectrin alpha chain, non‐erythrocytic 1 (284 kDa) were detected that are not observed without trypsin. The pre‐coated targets simplify workflow and increase sample throughput by decreasing the sample preparation time. Further, the approach allows imaging at higher spatial resolution compared with robotic spotters that apply one drop at a time. Copyright © 2016 John Wiley & Sons, Ltd.