A method for creating a non-equilibrium NT(P1-P2) ensemble in molecular dynamics simulation

A method is proposed for creating a non-equilibrium ensemble with a constant number of molecules, constant temperature and constant pressures with different target values in two reservoirs [referred to as NT(P(1)-P(2)) ensemble] that are connected by a finite length nanopore. This method includes two steps. The first step places a partition between the two reservoirs and then creates a static pressure field and a proper system volume by using two self-adjusting plates on which two external forces/pressures with different target values are exerted. The second step removes the partition and the two self-adjusting plates and the pressure difference between the two reservoirs is maintained by a "pump" designed to simultaneously create a periodic boundary condition between the two reservoirs and supply the necessary force (work) to a subset of molecules for a steady state flow. To examine this method, several cases using liquid argon with a truncated and shift Lennard-Jones potential under different target pressures and pump sizes were studied. Results show that the method proposed in this paper works well. In addition, the method proposed in this paper was compared with the other external force field methods. The results show that as long as the external force is applied to a restricted set of molecules away from the channel a constant pressure difference between two reservoirs is maintained. The advantage of the algorithm proposed here also sets the absolute pressures with different target levels in two reservoirs instead of it being arbitrary. Studies show that the fluid flow rate or permeability through a nanopore depends not only on the pressure difference between two reservoirs, but also on the absolute pressures in two reservoirs.     

The effects of dissolved halide anions on hydrogen bonding in liquid water

It is widely believed that the addition of salts to water engenders structural changes in the hydrogen-bond network well beyond the adjacent shell of solvating molecules. Classification of many ions as "structure makers" and "structure breakers" has been based in part on corresponding changes in the vibrational spectra (Raman and IR). Here we show that changes in O-H vibrational spectra induced by the alkali halides in liquid water result instead from the actions of ions' electric fields on adjacent water molecules. Computer simulations that accurately reproduce our experimental measurements suggest that the statistics of hydrogen-bond strengths are only weakly modified beyond this first solvation shell.     

Cooperativity of Catechols and Amines in High‐Performance Dry/Wet Adhesives

The outstanding adhesive performance of mussel byssal threads has inspired materials scientists over the past few decades. Exploiting the amino‐catechol synergy, polymeric pressure‐sensitive adhesives (PSAs) have now been synthesized by copolymerizing traditional PSA monomers, butyl acrylate and acrylic acid, with mussel‐inspired lysine‐ and aromatic‐rich monomers. The consequences of decoupling amino and catechol moieties from each other were compared (that is, incorporated as separate monomers) against a monomer architecture in which the catechol and amine were coupled together in a fixed orientation in the monomer side chain. Adhesion assays were used to probe performance at the molecular, microscopic, and macroscopic levels by a combination of AFM‐assisted force spectroscopy, peel and static shear adhesion. Coupling of catechols and amines in the same monomer side chain produced optimal cooperative effects in improving the macroscopic adhesion performance.     

Insertion/isomerization polymerization of 1,5-hexadiene: synthesis of functional propylene copolymers and block copolymers

Polymerization of 1,5-hexadiene with a bis(phenoxyimine) titanium catalyst system is reported. The microstructure of the polymer contains the expected methylene-1,3-cyclopentane units as well as the unexpected 3-vinyl tetramethylene units. A mechanism for formation of this polymer is proposed. This unusual reaction is also employed in the synthesis of vinyl-functional polypropylene copolymers and block copolymers with low polydispersity indices.     

Catalysts for the living insertion polymerization of alkenes: access to new polyolefin architectures using Ziegler-Natta chemistry

Coordination-insertion polymerization systems have long been superior to their anionic, cationic, and radical polymerization counterparts with regard to stereochemical control. However, until five years ago, these metal-based insertion methods were inferior to ionic and radical mechanisms in the category of living polymerization, which is simply a polymerization that occurs with rapid initiation and negligible chain termination or transfer. In the last half decade, the living insertion polymerization of unactivated olefins has emerged as a powerful tool for the synthesis of new polymer architectures. Materials available today by this route range from simple homopolymers such as linear and branched polyethylene, to atactic or tactic poly(alpha-olefins), to end-functionalized polymers and block copolymers. This review article summarizes recent developments in this rapidly growing research area at the interface of synthetic and mechanistic organometallic chemistry, polymer chemistry, and materials science. While special emphasis is placed on polymer properties and novel polymeric architectures, most of which were inaccessible just a decade ago, important achievements with respect to ligand and catalyst design are also highlighted.     

Structures and cytotoxicities of fascaplysin and related alkaloids from two marine phyla—Fascaplysinopsis sponges and Didemnum tunicates

The structural variations and bioactivity properties of the alkaloids in the fascaplysin (1) and the reticulatine (3) families were examined. Four organisms were analyzed consisting of two collections of the sponge Fascaplysinopsis reticulata and two collections of the tunicate Didemnum sp. Reported are the isolation of three new compounds: 3-bromofascaplysin (2), 14-bromoreticulatine (4), and 14-bromoreticulatate (6) along with reticulatate (5) previously known as a semi-synthetic product of 1. Compounds 1 and 5 showed selectivity in a cell based cytotoxicity assay.     

Embedded passivated-electrode insulator-based dielectrophoresis (EπDEP)

Here, we introduce a new technique called embedded passivated-electrode insulator-based dielectrophoresis (EπDEP) for preconcentration, separation, or enrichment of bioparticles, including living cells. This new method combines traditional electrode-based DEP and insulator-based DEP with the objective of enhancing the electric field strength and capture efficiency within the microfluidic channel while alleviating direct contact between the electrode and the fluid. The EπDEP chip contains embedded electrodes within the microfluidic channel covered by a thin passivation layer of only 4 μm. The channel was designed with two nonaligned vertical columns of insulated microposts (200 μm diameter, 50 μm spacing) located between the electrodes (600 μm wide, 600 μm horizontal spacing) to generate nonuniform electric field lines to concentrate cells while maintaining steady flow in the channel. The performance of the chip was demonstrated using Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacterial pathogens in aqueous media. Trapping efficiencies of 100 % were obtained for both pathogens at an applied AC voltage of 50 V peak-to-peak and flow rates as high as 10 μl/min.     

Complexation of the triply-bonded dirhenium(II) complex Re(2)Cl(4)(mu-dppm)(2) (dppm = Ph(2)PCH(2)PPh(2)) by up to three acetylene molecules

The triply bonded dirhenium(II) synthons Re(2)X(4)(mu-dppm)(2) (X = Cl, Br; dppm = Ph(2)PCH(2)PPh(2)) react with acetylene at room temperature in CH(2)Cl(2) and acetone to afford the bis(acetylene) complexes Re(2)X(4)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(eta(2)-HCCH) (X = Cl (3), Br(4)). Compound 3 has been derivatized by reaction with RNC ligands in the presence of TlPF(6) to give unsymmetrical complexes of the type [Re(2)Cl(3)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(eta(2)-HCCH)(CNR)]PF(6) (R = Xyl (5), Mes (6), t-Bu (7)), in which the RCN ligand has displaced the chloride ligand cis to the eta(2)-HCCH ligand. The reaction of 3 with an additional 1 equiv of acetylene in the presence of TlPF(6) gives the symmetrical all-cis isomer of [Re(2)Cl(3)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(eta(2)-HCCH)(2)]PF(6) (8). The two terminal eta(2)-HCCH ligands in 8 are very labile and can be displaced by CO and XylNC to give the complexes [Re(2)Cl(3)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(L)(2)]Y (L = CO when Y = PF(6) (9); L = CO when Y = (PF(6))(0.5)/(H(2)PO(4))(0.5) (10); L = XylNC when Y = PF(6) (11)). These substitution reactions proceed with retention of the all-cis stereochemistry. Single-crystal X-ray structure determinations have been carried out on complexes 3, 5, 8, 10, and 11. In no instance have we found that the acetylene ligands undergo reductive coupling reactions.