Inhibition of cell adhesion to fibronectin by oligopeptide-substituted polynorbornenes.

Polynorbornenes substituted with two different peptide sequences from the RGD-containing integrin cell-binding domain of fibronectin are potent inhibitors of human foreskin fibroblast cell adhesion to fibronectin-coated surfaces. Ring-opening metathesis polymerization (ROMP) using Ru==CHPh(Cl)(2)(PCy(3))(DHIMes) (1) as an initiator produced polymers substituted with GRGDS and PHSRN peptide sequences. The inhibitory activity was quantified for these polymers and compared to the free peptides and GRGES-containing controls. A homopolymer substituted with GRGDS peptides was significantly more active than the free GRGDS peptide (IC(50) of 0.18 +/- 0.03 and 1.33 +/- 0.20 mM respectively), and the copolymer containing both GRGDS and PHSRN is the most potent inhibitor (IC(50) of 0.04 +/- 0.01 mM). These results demonstrate that significant enhancements of observed biological activity can be obtained from polymeric materials containing more than one type of multivalent ligand and that ROMP is a useful method to synthesize such well-defined copolymers.     

Permeation and sorption in polynorbornenes with organosilicon substituents

Gas sorption properties, permeability coefficients, and diffusion coefficients of a series of norbornene polymers are presented. Introduction of the Si(CH₃)₃ group into the polynorbornene (PNB) backbone chain results in significant increases in glass transition temperature, permeability, and diffusion coefficient for a number of gases (H₂, O₂, N₂, CO₂, CH₄, C₂H₆). The transport properties and sorption isotherms for poly(5-trimethylsilyl norbornene) (PTMSNB) are very similar to those for poly(vinyltrimethyl silane) (PVTMS), which contains the same side-chain group but differs from PTMSNB by the structure of its main chain. For another silicon-containing polymer poly[5-(1,1,3,3-tetramethyl-1,3-disilabutyl) norbornene] (PDSNB) having a bulkier side-chain group, the glass-transition temperature is decreased in comparison with that of PNB, presumably owing to self-plasticization. Both silicon-containing norbornene polymers (PTMSNB and PDSNB) have permeability coefficients for “rapid” gases like H₂ or CO₂ of about 10² Barrer. The high values of the Langmuir sorption capacity C′_H for PTMSNB and PVTMS, as well as the high diffusivity and mobility of spin probes in these polymers, were attributed to a large free volume related to the bulky Si(CH₃)₃ groups attached directly to the main chain. © 1993 John Wiley & Sons, Inc.     

On the rigidity of polynorbornenes with dipolar pendant groups

A range of polynorbornenes (PNBs) with fused dipolar pendant groups at C-5,6 positions was synthesized by ring-opening metathesis polymerization catalyzed by a ruthenium carbene complex (Grubbs I). Photophysical studies, EFISH measurements, and atomic force microscopy images have been used to investigate the structures and morphology of these polymers. These results suggest that the polymers may adopt rigid rod-like structures. The presence of the double bonds in PNBs appeared to be indispensable for the rigidity of the polymers. Interaction between unsaturated pendant groups may result in coherent alignment leading to a rod-like structure.     

Gas-transport properties of epoxidated metathesis polynorbornenes

The effect of postpolymerization epoxidation of metathesis polynorbornenes on their gas-transport behavior is studied. For two polymers, unsubstituted polynorbornene and poly(trimethylsilylnorbornene), postpolymerization modification via double bonds is implemented by epoxidation under the action of m-chloroperbenzoic acid to high conversions (95–100%). For initial polymers and their epoxidation products, the permeability and diffusion coefficients are measured and the solubility coefficients are estimated. It is shown that, for both initial polymers, functionalization leads to a marked reduction in permeability (by a factor of 2–10) and diffusion coefficients (by a factor of 3–10); simultaneously, the separation factors increase by a factor of 2–6. Although for all gases the solubility coefficients decrease as a result of epoxidation, the coefficients of CO₂ solubility in both epoxidated polymers increase. This effect may be explained by specific interactions of a СО₂ molecule possessing the quadrupole moment with С–О–С bonds appearing in a polymer.     

Organoiron polynorbornenes with pendent arylazo and hetarylazo dye moieties

Organoiron polynorbornene containing arylazo or hetarylazo dye chromophores has been prepared via ring opening metathesis polymerization using Grubbs' catalyst. The obtained polymers were isolated as brightly colored materials and displayed good solubility in polar organic solvents. The colors of these polymers were affected by the nature of the incorporated azo chromophores. Thermogravimetric analysis of these materials showed that the cleavage of the cyclopentadienyliron (CpFe⁺) moieties was between 225 and 231 °C, while the degradation of the polymer backbones occurred between 400 and 450 °C. UV-vis studies in DMF showed that the organoiron polymers containing arylazo dyes exhibit wavelength maxima around 425 nm. However, the replacement of these arylazo moieties with hetarylazo dyes displayed substantial bathochromic shifts in the λ_max values (≈ 511 nm).     

Telechelic polynorbornenes with hydrogen bonding moieties by direct end capping of living chains

We present two novel symmetric olefins bearing hydrogen bonding moieties for the direct capping of living ring opening metathesis polymerization‐chains using Grubbs catalyst 1st‐ and 3rd‐generation. The symmetric olefins are generated via homo metathesis of the corresponding α‐olefins under aid of microwave irradiation and are used to prepare polynorbornene‐chains (M_n = 4,000–10,000 g/mol, M_w/M_n = 1.1–1.4) bearing barbiturate and thymine‐moieties. A qualitative and quantitative analysis of the generated polymers is done via MALDI‐TOF MS proving the introduction of hydrogen‐bonding moieties into the polymer chain and revealing the strong dependence of the desorption on the chemical structure of the different polymer species and high efficiencies for the end group introduction (90–99%). The efficiency of this process depends strongly on the reaction time and the equivalents of terminating agent with respect to the living end. The best results for the end group introduction are achieved by reacting the living chains with an excess of the terminating agent (5–20 equiv) for 100 h. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and luminescent properties of functionalized polynorbornenes with boron-containing fragments in side chains

Russian Chemical Bulletin - New norbornene monomer, viz., 5-[(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl]-8-[(dimesitylboryl)oxy]quinoline (1), was synthesized. The copolymers based on monomer 1...     

Two pseudopolymorphs of LiCl trimers with semicubane structures

The title compounds, trichlorido(μ₃‐triethylphosphine oxide‐κ³O:O:O)tris(μ₂‐triethylphosphine oxide‐κ²O:O)trilithium(I) toluene solvate, [Li₃Cl₃(C₆H₁₅OP)₄]·C₇H₈, (I), and trichlorido(μ₃‐triethylphosphine oxide‐κ³O:O:O)tris(μ₂‐triethylphosphine oxide‐κ²O:O)trilithium(I), [Li₃Cl₃(C₆H₁₅OP)₄], (II), adopt separated semicubane structures in the solid state which are the first such structures to be reported for LiCl solvates. One triethylphosphine oxide ligand bonds via its O atom to the three Li atoms in a μ₃ manner, while the other three triethylphosphine oxide ligands bridge three Li atoms in μ₂ manners. The Cl atoms are in terminal instead of bridging positions, which is rather unusual for lithium chloride solvates.     

Increased dwell time and occurrence of dsDNA translocation events through solid state nanopores by LiCl concentration gradients

Solid‐state nanopore based biosensors are cost effective, high‐throughput engines for single molecule detection of biomolecules with the added benefit of size modification. Progress in the translation of the science into a viable diagnostic tool is impeded by inadequate sensitivity of data acquisition systems in detection of fast DNA translocations through the pore. To combat this, slowing the transport of DNA through the nanopore by use of various media or by altering experimental parameters is common. Applying a concentration gradient of KCl in the experimental ionic solution has been shown to effectively prolong dwell times as well as increase the capture rate of DNA by the nanopore. Our previous work has corroborated the ability of LiCl ionic solution to slow down the transport of dsDNA through the nanopore by up to 10‐fold through cation‐DNA interactions. However, this drastically reduced the event occurrence frequency, thus hindering the efficacy of this system as a reliable biosensor downstream. Here, we present the use of a concentration gradient of lithium chloride ionic solution to increase the event frequency of single molecule dsDNA translocation through a solid state nanopore. By using 0.5 M/3 M LiCl on the cis/trans chambers respectively, average dwell times experienced up to a 3‐fold increase when compared to experiments run in symmetric 1 M LiCl. Additionally, experiments using the 0.5 M/3 M displayed a greater than 10‐fold increase in event frequency, confirming the capture propensity of the asymmetric conditions.     

Effects of polymer chain length and stiffness on phase separation dynamics of semidilute polymer solution

Three-dimensional dissipative particle dynamics (DPD) simulations were performed to investigate the phase separation dynamics of semidilute polymer solutions with different polymer chain length and stiffness. For the polymer solution composed of shorter and more flexible chains, a crossover of the domain growth exponent from 1/3 to 2/3 was observed during the course of phase separation, indicating that the growth mechanism altered from diffusion to interfacial-tension driven flow. When the chain flexibility was kept the same but the chain was lengthened to allow for the chain entanglement to occur, the growth exponent changed to 1/4 in the diffusion-dominating coarsening regime while the growth exponent remained 2/3 in the flow-dominating regime. When the chain length was kept short but the stiffness was increased, the growth exponent became 1/6 in the diffusion-dominating regime and little effect was observed in the flow-dominating coarsening regime. The slow down of the phase separation dynamics in the diffusion-dominating coarsening could be explained by that the polymer chains could only perform wormlike movement when chain entanglements occurred or when the chain motion was limited by chain stiffness during phase separation. Moreover, when both the effects of chain length and stiffness were enhanced, polymer networks composed of longer and stiffer chains appeared and imposed an energy barrier for phase separation to occur. As a result, the polymer solution with stiffer and longer chains required a larger quench depth to initiate the phase separation and caused the delay in crossover of the coarsening mechanism from diffusion to flow.     

Functionalized polynorbornenes with organosilicon groups in the side chains. Synthesis and photophysical properties

Using the method of metathesis polymerization carbon-chain homopolymers containing triрhenylsilyl, tritolylsilyl and trithienylsilyl groups in the side chains, as well as their copolymers with additional carbazole-containing units have been synthesized. Photophysical properties of the obtained compounds were investigated. All polymer products show an intense photoluminescence in the blue region of the spectrum. The largest quantum yield (61.4%) was shown by the copolymer with triphenylsilyl and carbazole side groups.     

Gas transport properties of a series of high Tg polynorbornenes with aliphatic pendant groups

A study of gas transport properties of novel polynorbornenes with increasing length of an aliphatic pendant group R (CH₃ , CH₃(CH₂)₃ , CH₃(CH₂)₅ , CH₃(CH₂)₉ ) has been performed. These polymers were synthesized using novel organometallic complex catalysts via an addition polymerization route. This reaction route maintained the bridged norbornene ring structure in the final polymer backbone. Gas permeability and glass transition temperature were found to be higher than those for polynorbornenes prepared by ring-opening metathesis and reported in the literature. It was shown that for noncondensable gases such as H₂ and He the selectivity over N₂ decreased when the length of the pendant group increased, but remained relatively stable for the more condensable gases (O₂ and CO₂). The permeability coefficient is correlated well to the inverse of the fractional free volume of the polymers. The more condensable gases showed a deviation from this correlation for the longest pendant group, probably due to an increase of the solubility effect. This polymer series demonstrated a simultaneous increase in permeability and selectivity, uncommon for polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 797–803, 1998     

Simulations of gas transport in membranes based on polynorbornenes functionalized with substituted imide side groups

This paper studies the diffusive and sorption steps of several gases across membranes cast from poly(N-phenyl-exo,endo-norbornene-5,6-dicarboximide) chloroform solutions. Chains packing effects on gas transport was investigated by conducting a parallel study on the permeation characteristics of membranes cast from hydrogenated poly(N-phenyl-exo,endo-norbornene-5,6-dicarboximide) chloroform solutions. The permeability coefficients of several gases in the two membranes were measured finding that hydrogenation of the norbornene moieties decreases gas permeability. The transition states approach was used to determine the trajectories of the gases in the two types of membranes from which the diffusion coefficients were obtained. Monte Carlo techniques based on the Widom method were used to simulate gas sorption process as a function of pressure. The values of the solubility coefficients thus obtained undergo a relatively sharp drop at low pressures approaching to a constant value as pressure increases. With the exception of carbon dioxide, pretty good agreement between the experimental and simulated values of the permeability coefficient is found for the gases studied.     

Evidence of deeply supercooled liquid water in interaction with LiCl

The properties of water above the glass transition temperature are highly controversial. By using time-of-flight secondary ion mass spectrometry (TOF-SIMS), the presence of deeply supercooled water is manifested by dissolution of LiCl in the pure amorphous water films heated at 140-155 K and the formation of aqueous LiCl solutions. Two phases of deeply supercooled water, that lead to the dilute and concentrated LiCl solutions, are clearly identified. The former is short-lived and merges into the latter, whereas the latter is basically identical to normal liquid water as far as the solubility of LiCl is concerned.     

Synthesis of substituted norbornenes and their polymerization to polynorbornenes with flexible aliphatic side‐chains

Synthesis and characterization of new thermally stable polynorbornenes functionalized with pendent flexible side‐chains are reported. The flexible side‐chains with terminal hydroxy groups were synthesized via S_NAr reactions of cyclopentadienyliron‐complexed chlorobenzenes with aliphatic diols. Condensation of these side‐chains with exo,endo‐5‐norbornene‐2‐carboxylic acid led to the formation of substituted monomers which were characterized using one‐ and two‐dimensional NMR techniques. Ring‐opening metathesis polymerization of these monomers yielded polynorbornenes with pendent side‐chains.