Molecular recognition of DNA by rigid [n]-polynorbornane-derived bifunctional intercalators: synthesis and evaluation of their binding properties

We have exploited the concept of multivalency in the context of DNA recognition, using novel chemistry to synthesize a new type of bis-intercalator with unusual sequence-selectivity. Bis-intercalation has been observed previously, but design principles for de novo construction of such molecules are not known. Our compounds feature two aromatic moieties projecting from a rigid, polynorbornane-based scaffold. The length and character of the backbone as well as the identity of the intercalators were varied, resulting in mono- or divalent recognition of the double helix with varying affinity. Our lead compound proved to be a moderately sequence-selective bis-intercalator with an unwinding angle of 27 and a binding constant of about 8 M. 9-Aminoacridine rings were preferred over acridine carboxamides or naphthalimides, and a rigid [3]-polynorbornane scaffold was superior to a [5]-polynorbornane. The flexibility of the linker connecting the rings to the scaffold, although less influential, could affect the strength and character of the DNA binding.

CoP2 nanoparticles on reduced graphene oxide sheets as a super-efficient bifunctional electrocatalyst for full water splitting

In this communication, we report an electrocatalyst for full water splitting based on CoP2 nanoparticles grown on reduced graphene oxide sheets (CoP2/RGO). As a novel non-noble-metal electrocatalyst, CoP2/RGO shows an ultra-high catalytic activity in alkaline electrolyte which only requires a cell voltage of 1.56 V to attain a current density of 10 mA cm-2 for full water splitting.

Characterization of conductive polyprrole coated wool yarns

Wool yarns were coated with conducting polypyrrole by chemical synthesis methods. Polymerization of pyrrole was carried out in the presence of wool yarn at various concentrations of the monomer and dopant anion. The changes in tensile, moisture absorption, and electrical properties of the yarn upon coating with conductive polypyrrole are presented. Coating the wool yarns with conductive polypyrrole resulted in higher tenacity, higher breaking strain, and lower initial modulus. The changes in tensile properties are attributed to the changes in surface morphology due to the coating and reinforcing effect of conductive polypyrrole. The thickness of the coating increased with the concentration of p-toluene sulfonic acid, which in turn caused a reduction in the moisture regain of the wool yarn. Reducing the synthesis temperature and replacing p-toluenesulfonic acid by anthraquinone sulfonic acid resulted in a large reduction in the resistance of the yarn.

Expression, localisation and hormone regulation of the human copper transporter hCTR1 in placenta and choriocarcinoma Jeg-3 cells

Copper is an essential trace element necessary for normal growth and development. During pregnancy, copper is transported from the maternal circulation to the fetus by mechanisms which have not been clearly elucidated. The copper uptake protein, hCTR1 is predicted to play a role in copper transport in human placental cells. This study has examined the expression and localisation of hCTR1 in human placental tissue and Jeg-3 cells. In term placental tissue the hCTR1 protein was detected as a 105 kDa protein, consistent with the size of a trimer which may represent the functional protein. A 95 kDa band, possibly representing the glycosylated protein, was also detected. hCTR1 was localised within the syncytiotrophoblast layer and the fetal vascular endothelial cells in the placental villi and interestingly was found to be localised toward the basal plasma membrane. It did not co-localise with either the Menkes or the Wilson copper transporting ATPases. Using the placental cell line Jeg-3, it was shown that the 35 kDa monomer was absent in the extracts of cells exposed to insulin, estrogen or progesterone and in cells treated with estrogen an additional 65 kDa band was detected which may correspond to a dimeric form of the protein. The 95 kDa band was not detected in the cultured cells. These results provide novel insights indicating that hormones have a role in the formation of the active hCTR1 protein. Furthermore, insulin altered the intracellular localisation of hCTR1, suggesting a previously undescribed role of this hormone in regulating copper uptake through the endocytic pathway.

Synthesis, polymerization and wool coating studies of 3-iso-butylpyrrole and 3-iso-pentylpyrrole

In a four-step method starting from pyrrole, the synthesis of 3-iso-butylpyrrole and 3-iso-pentylpyrrole, was achieved in 45 and 44% yields, respectively. Polymerization studies of these branched alkyl pyrroles are described and the results compared with those obtained for the unbranched structural isomers n-butyl and n-pentylpyrrole. A series of conductive textiles were produced by the chemical polymerization of the iso-alkylpyrroles using both solution and vapour polymerization techniques. Fabrics coated with poly-iso-alkylpyrrole formed using the solution polymerization method had a lower surface resistance than those formed using the vapour polymerization method. These conductivity results were in direct contrast to those previously obtained for 3-n-alkylpyrroles on fabrics. A remarkable crystal-like growth on the surface of the textile fabric was observed when solution polymerization of 3-iso-pentylpyrrole was employed—reinforcing the notion that subtle changes in monomer structure can drastically affect bulk polymer properties.

Polymerising pyrrole on polyester textiles and controlling the conductivity through coating thickness

The surface resistance of polypyrrole (PPy)-coated polyester fabrics was investigated and related to coating thickness, which was controlled by adjusting the reactant concentrations. The thickness of the coating initially increased rapidly followed by a steady increase when the concentration of pyrrole (Py) was larger than a concentration of approximately 0.4 mg/ml. The surface resistance decreased from 10⁶ to 10³ Ω with increase in pyrrole concentration within 0.2 mg/ml until the concentration reached a value of about 0.4 mg/ml, above which the rate of decrease diminished. The effect of initial treatment with monomer or oxidant prior to polymerisation reaction with regards to thickness and surface resistance was minimal. The immersion time of the textile into the monomer solution prior to polymerisation reaction did not have a significant effect on the abrasion resistance.

Conductive fabrics for heating applications

By coating textiles with electrically conductive organic polymers, we are able to produce functional, intelligent fabrics. These fabrics can be utilised in applications such as gas sensors, actuators, electromagnetic shielding, radar absorption, selected frequency filtering in indoor wireless applications, and heating applications where vital parts of the body can be heated without embedding any wiring through the fabric.

Heat generation in fabrics coated with the conductive polymer polypyrrole was investigated. The fabrics were coated by chemical synthesis methods by oxidizing the pyrrole monomer in the presence of the fabric substrate. Ferric chloride was selected as the oxidizing agent and anthraquinone-2-sulfonic acid (AQSA) sodium salt monohydrate as the dopant.

Conductive fabrics were characterized by resistivity measurements, scanning electron microscopy, thermal imaging, current transmission over a period of time and calculations of power density per unit area. Effects of reaction conditions on the electrical properties and heat generated are presented. Polypyrrole coated fabrics were stable and possessed high electrical conductivity. Resistivity values ranged from 100-500 ohms/square depending on the reaction parameters. When subjected to a constant voltage of 24V, the polypyrrole coated polyester-Lycra® fabric doped with AQSA reached a maximum temperature of 42°C and a power density per unit area of 430 W/m² was achieved.

Complexes of the tripodal nitrilotrimethylenetrisphosphonic (H6L) and P,P',P''-triphenylnitrilotrimethylenetrisphosphinic (H3L) acids with the copper(II) ion. Synthesis and charaterization of [Hpy][Cu(H3L)(H2O)] and [Cu(HL)(py)]2.2Me2CO

The complexes [Hpy][Cu(H₃L)(H2O)] 1 (L⁶ = nitrilotrimethylenetrisphosphonate) and [Cu(HL°)(py)]₂·2Me₂CO 2 [(L°)³ = P,P,P" -triphenylnitrilotrismethylenetrisphosphinate)] have been isolated and characterized by X-ray crystallography, near IR-visible spectroscopy and magnetic measurements. The structure determination has shown the complexes to be constituted by monomeric and dimeric units respectively. In the monomer the metal atom is surrounded by the phosphonate ligand and a water molecule, with a geometry between a trigonal bipyramid and a square pyramid. The two copper atoms in the dimer are held together by an arm of the tripod ligand, with a pyridine molecule as additional ligand, and display octahedral geometry. The presence of monomeric and dimeric species in aqueous solutions of 1 and 2 has been shown by ESMS studies. The formation in water solution of the dimer [{Cu(H₃L)}₂]^2-, as a minor species, has been supported by potentiometric measurements, whereas only the monomeric anion [CuL°] has been ascertained to be present. In general the ligand H₃L° forms less stable copper(II) complexes than H₆L.

Inorganic-organic hybrids of the p,p'-diphenylmethylenediphosphinate, pcp2-. synthesis, characterization and XRPD structures of [Sn(pcp)] and [Cu(pcp)]

Two new inorganic-organic polymeric hybrids [Sn(pcp)] and [Cu(pcp)], pcp = CH₂(PhPO₂)₂^2-, have been synthesized and structurally chracterized. The tin derivative has been obtained by reaction of the p,p'-diphenylmethylenediphosphinic acid (H₂pcp) in water with SnCl₂·2H₂O, while the copper derivative has been synthesized through a hydrothermal reaction from the same H₂pcp acid and Cu(O₂CMe)₂·H₂O. The structures of these compounds have been solved "ab initio" by X-ray powder diffraction (XRPD) data. [Sn(pcp)] has a ladder-like polymeric structure, with tin(II) centers bridged by diphenylmethylenediphosphinate ligands, and alternating six- and eight-membered rings. The hemilectic coordination around the metal shows the tin(II) lone pair to be operative, resulting in significant interaction mainly with a C-C bond of one phenyl ring. The [Cu(pcp)] complex displays a polymeric columnar structure formed by two intersecting sinusoidal ribbons of copper(II) ions bridged by the bifunctional phosphinate ligands. The intersections of the ribbons are made of dimeric units of pentacoordinated copper ions. Crystal data for [Sn(pcp)]: monoclinic, space group P2₁Ic, a = 11.2851(1), b = 15.4495(6), c = 8.6830(1) Å, ^β= 107.546(1)°, V = 1443.44(9) Å, Z = 4. Crystal data for [Cu(pcp)]: triclinic, space group P, a = 10.7126(4), b = 13.0719(4), c = 4.9272(3) Å, α= 92.067(5), β= 95.902(7), γ= 87.847(4)°, V = 685.47(7), Z = 2. The tin compound has been characterized by ¹¹⁹Sn MAS NMR (magic-angle spinning NMR), revealing asymmetry in the valence electron cloud about tin. Low-temperature magnetic measurements of the copper compound have indicated the presence of weak antiferromagnetic interactions below 50 K.

The first dimeric trioganotin fluoride : stabilization by unsymmetrically oriented menthyl substituents

In the solid state, (-)-tris([1R,2S,5R]-menthyl)tin fluoride, Men₃SnF (6), exhibits a dimeric structure in which one tin atom is four-coordinate and the other five-coordinate. This novel dimeric association mode is attributed to the orientation of the unsymmetrical menthyl groups, which are arranged to allow a minimum Sn···Sn separation of 4.84 Å within the dimer. The exocyclic isopropyl groups of the menthyl groups point in opposite directions on each tin atom of the dimer, thus preventing further association (Sn···Sn separation outside the dimer 10.49 Å). ¹¹⁹Sn and ¹⁹F MAS NMR spectroscopy were utilized to probe the diverse coordination numbers found by X-ray crystallography for the geometries of the two tin and fluorine sites. In solution, 6 is a monomer at both room temperature and -100 °C. However, upon addition of Bu₄NF, 6 is in equilibrium with [(Men₃SnF)₂F]- (6a), [Men₃SnF₂]^- (6b), and noncoordinating fluoride anions.

Nanostructures and nanoporosity in thermoset epoxy blends with an amphiphilic polyisoprene-block-poly(4-vinyl pyridine) reactive diblock copolymer

Nanostructured thermoset blends were prepared based on a bisphenol A-type epoxy resin and an amphiphilic reactive diblock copolymer, namely polyisoprene-block-poly(4-vinyl pyridine) (PI-P4VP). Infrared spectra revealed that the P4VP block of the diblock copolymer reacted with the epoxy monomer. However, the non-reactive hydrophobic PI block of the diblock copolymer formed a separate microphase on the nanoscale. Ozone treatment was used to create nanoporosity in nanostructured epoxy/PI-P4VP blends via selective removal of the PI microphase and lead to nanoporous epoxy thermosets; disordered nanopores with the average diameter of about 60 nm were uniformly distributed in the blend with 50 wt% PI-P4VP. Multi-scale phase separation with a distinctly different morphology was observed at the air/sample interface due to the interfacial effects, whereas only uniform microphase separated morphology at the nanoscale was found in the bulk of the blend.

Fibre coating composition

An abrasion-resistant, electrically conductive material comprising a natural fibre-containing substrate and an electrically conductive conjugated polymer coating thereon is disclosed. A process for preparing an abrasion-resistant, electrically conductive material is also disclosed. The process comprises providing at least one monomer capable of forming an electrically conductive conjugated polymer, and a suitable substrate having a substrate surface, subjecting the substrate surface to a surface treatment step to improve abrasion resistance, and exposing the substrate surface to a vapour of the monomer to form an electrically conductive conjugated polymer coating thereon.

Studies on the behaviour of polystyrene in reversed phase chromatography

Polystyrene behaviour in reversed phase high performance liquid chromatography was influenced mainly by the solvent system, but secondary affects were observed depending on the stationary phase. A variety of reversed phase columns were investigated using mobile phase combinations of dichlorom ethane-methanol, dichloromethane-acetonitrile, ethyl acetate-methanol and ethyl acetate-acetonitrile. Several different modes of behaviour were observed depending on the polymer solubility in the solvent system. In the dichloromethane-methanol solvent system, polymer-stationary phase interactions only occurred when the molecules had pore access. Retention of excluded polystyrene depended on the kinetics of precipitation and redissolution of the polymer. Peak splitting and band broadening occurred when the kinetics were slow and molecular weight separations were limited !o oligomers and polystyrenes lower than 5-10(4) dalton. Excellent molecular weight separations of polystyrenes were obtained using gradient elution reversed phase chromatography with a dichloromethane-acetonitrile mobile phase on C18 columns. The retention was based on polymer-stationary phase interactions regardless of the column pore size. Separations were obtained on large diameter pellicular adsorbents that were almost as good as those obtained on porous adsorbents, showing that pore access was not essential for the retention of high molecular weight polystyrenes. In the best example, the separation ranged from the monomer to 10(6) dalton in a single analysis. Very little adsorption of excluded polymers was observed on C8 or phenyl columns. Polystyrene molecular weight separations to 7-10(5) dalton were obtained in an ethyl acetate-acetonitrile solvent system on C18 columns. Adsorption was responsible for retention. When an ethyl acetate-methanol solvent system was used, no molecular weight separations were obtained because of complex peak splitting. Reversed phase chromatography was compared to size exclusion chromatography for the analysis of polydisperse polystyrenes. Similar results were obtained using both methods. However, the reversed phase method was less sensitive to concentration effects and gave better resolution.

Pulsed plasma polymerization of hexamethyldisiloxane onto wool : control of moisture vapor transmission rate and surface adhesion

A new fabric with potential in medical textiles has been developed by application of a surface coating on wool using pulsed plasma polymerization of HMDSO. This coating enabled a controllable MVTR and surface adhesion. MVTR in the range recommended for optimum wound healing was obtained by varying frequency, monomer pressure and deposition time. Lower surface adhesion was achieved. Peeling tests, contact angle measurements, SPM force curves and ATR FT-IR were used to characterize the surfaces for both wool and a PE model substrate. All these results were consistent with a decrease in surface energy after PP-HMDSO treatment. ATR FT-IR results showed a siloxane film with less organic Si(CH₃)_n groups and more SiOSi cross-links.