Interfacial supramolecular self-assembled monolayers of C-60 by thiolated beta-cyclodextrin on gold surfaces via monoanionic C-60

The supramolecular self-assembled monolayers (SAMs) of C-60 by thiolated beta-cyclodextrin (CD) on gold surfaces were constructed for the first time using C-60 monoanion. The results indicate that monoanionic C-60 plays a crucial role in the formation of the C-60-containing self-assembled monolayers. The generation of C-60 monoanion and the formation process of C-60 SAMs were monitored in-situ by UV-visible and near-IR spectroscopy. The resulting C-60 SAMs were fully characterized by spectroscopic ellipsometry (SE), cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and water contact angle measurements. After the immobilization of C-60 by the SAMs of thiolated beta-CD, the film thickness increased by approximately 1 nm from 0.8 to 1.8 nm as determined by SE, demonstrating the formation of the supramolecular self-assembled monolayers of thiolated beta-CD/C-60. The new C-60 SAMs exhibited one quasi-reversible redox couple at half wave potential of -0.57 V vs SCE in aqueous solution containing 0.1 M KCl. The surface coverage of C-60 on the gold surfaces was estimated to be 1.1 x 10(-10) mol cm(-2). The XPS showed the assembly of C-60 over the thiolated beta-CD SAMs.

Superhydrophobic PTFE surfaces by extension

A rather simple but yet effective way to achieve a superhydrophobic film by extending a Teflon film is proposed. The water contact angle can be increased from 118 to 165degrees by extending to ca. 190%. The fibrous crystals and the increasing distance between the fibrous crystals are believed responsible for the high water-contact angle. It indicates that the density of the aligned microstructures is very important for the superhydrophobicity.

Low-density polyethylene superhydrophobic surface by control of its crystallization behavior

A simple and inexpensive method for forming a low-density polyethylene (LDPE) superhydrophobic surface by controlling the crystallization behavior of LDPE by adjusting the crystallization time and nucleation rate has been proposed. The resulting porous surface, with hierarchical micro- and nanostructures on the beautiful floral designs, has a water contact angle of 173.0degrees +/- 2.5degrees.

Preparation and properties of microporous membrane from poly(vinylidene fluoride-co-tetrafluoroethylene) (F2.4) for membrane distillation

Flat-sheet microporous membranes from F2.4 for membrane distillation (MD) were prepared by phase inversion process. Dimethylacetamide (DMAC) and LiClO(4)(.)3H(2)O/trimethyl phosphate (TMP) were, respectively, used as solvent and pore-forming additives. The effects of casting solution composition, exposure time prior to coagulation and temperature of precipitation bath on F2.4 membrane structure were investigated. The morphology of resultant porous membrane was observed by scanning electron microcopy. Some natures of F2.4 porous membrane after drying in air, such as mechanical properties and hydrophobicity, were exhibited and compared with poly(vinylidene fluoride) (PVDF) membrane prepared by the same ways. Stress-at-break and strength stress of F2.4 microporous membrane are higher than that of PVDF membrane, and elongation percentage of F2.4 membrane at break is about eight-fold as great as that of PVDF membrane. Contact angle of F2.4 microporous membrane to water (86.6 +/- 0.51degrees) was also larger than that of PVDF mernbrane (80.0 +/- 0.78degrees). MD experiment was carried out using a direct contact membrane distillation (DCMD) configuration as final test to permeate performance of resultant microporous membrane.

Preliminary research on microporous membrane from F2.4 for membrane distillation

An asymmetric hydrophobic microporous membrane from the copolymer of tetrafluoroethylene and vinyliden fluoride (F2.4) has been fabricated by phase inversion process. Some characteristics, such as mechanical properties and hydrophobicity, have been examined and compared with polyvinylidenefluoride (PVDF) membrane. Experimental data exhibit F2.4 membrane excellent mechanical properties and hydrophobicity. F2.4 microporous membrane was approximately 6-8 times as high as PVDF membrane in stretching strain and extension ratio at break, and contact angle to distilled water of the fore (88.5degrees) was larger than the latter (80.0degrees), too. The results from membrane distillation (MD) process were well agreed with the fundamental laws of membrane distillation.

Polyhedral oligomeric silsesquioxane nanocomposite thin films via layer-by-layer electrostatic self-assembly

Fabrication of ultrathin polymer composite films with low dielectric constants has been demonstrated. Octa( aminophenyl) silsesquioxane (OAPS) was synthesized and assembled with poly( acrylic acid) (PAA) and poly( styrene sulfonate) (PSS) via a layer-by-layer electrostatic self-assembly technique to yield nanoporous ultrathin films. The OAPS was soluble in water at pH 3 or lower, and suitable pH conditions for the OAPS/PAA and OAPS/PSS assemblies were determined. The multilayer formation process was studied by contact angle analysis, X-ray photoelectron spectroscopy, atomic force microscopy, quartz crystal microgravimetry, UV-vis spectroscopy, and ellipsometry. The multilayer growth was found to be steady and uniform, and the analysis of the film surface revealed a rough topography due to OAPS aggregates. The incorporation of porous OAPS molecules into the thin films significantly lowered their dielectric constants. The OAPS/PAA multilayer thin film thus prepared exhibited a dielectric constant of 2.06 compared to 2.58 for pure PAA film. The OAPS/PAA multilayer film was heated to effect cross-linking between the OAPS and the PAA layers, and the transformation was verified by reflection-absorption Fourier transform infrared spectroscopy.

Wettability of zinc oxide surfaces with controllable structures

Zinc oxide (ZnO) surfaces with controllable structures (i.e, microstructure, nanostructure, and micronanobinary structure) have been created by controlling pH at < 4 or > 10.5 in the Zn(gray) + H2O2 reaction. The resulting surface shows superhydrophobicity. It is found that the water contact angle (CA) of the surface with micronanobinary structure is greater than that of nanostructure and that of nanostructure is greater than that of the microstructure. Theoretical analysis is completely in agreement with the experimental results.

A polymer composite film with reversible responsive behaviors

A responsive polymer composite film was generated by the use of reversibly switchable Surface morphology of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films in response to different block selective solvents on the rough isotactic poly(propylene) (i-PP) substrate. The Maximum difference of the water contact angle of the composite films increased from 22.6 degrees of PS-b-PMMA films on the smooth substrate to 42.6 degrees when they were treated by PS and PMMA selective solvents, respectively. The mechanisms of the responsive extent enhanced and the superhydrophobicity of the composite films were discussed in detail.

Factors affecting pore structure and performance of poly(vinylidene fluoride-co-hexafluoro propylene) asymmetric porous membrane

Preparation of poly(vinylidene fluoride-co-hexafluoro propylene) (F2.6) flat-sheet asymmetric porous membrane has been studied for the first time. Factors affecting F2.6 membrane pore structure and permeate performance, such as macromolecule pore formers (polyethylene glycol-400, 1000, 1540, 2000 and 6000), the small molecule former (glycerol), swelling agent (trimethyl phosphate) in casting solution, precipitating bath component and temperature, exposure time and ambient humidity, were investigated in detail. Average pore radius and porosity were used to characterize F2.6 membrane structure, and respectively, determined by ultrafiltration and gravimetric method for the wet membrane. Morphology of the resultant membranes was observed by scanning electronic microscopy (SEM). Final test on permeate performance of F2.6 porous membrane was carried out by a direct contact membrane distillation (DCMD) setup. The experimental F2.6 membrane exhibits a higher distilled flux than PVDF membrane under the same operational situations. The determination of contact angle to distilled water also reveals higher hydrophobic nature than that of PVDF membrane.

Poly(L-lactide)/starch blends compatibilized with poly(L-lactide)-g-starch copolymer

The poly(L-lactide) (PLLA)/starch blends were prepared by the PLLA grafting starch (PLLA-g-St) copolymers as a compatibilizer, and their thermal, mechanical and morphological characterizations were performed to show the better performance of these blends compared to the virgin PLLA/starch blend without the compatibilizer, including PLLA crystallinity, interfacial adhesion between the PLLA matrix and starch dispersive phases, mechanical test, medium resistance, and contact angle. The 50/50 composite of PLLA/starch compatibilized by 10% PLLA-g-St gave a tensile strength of 24.7 MPa and an elongation at break of 8.7%, respectively, vs. 11.3 MPa and 1.5%, respectively, for the simple 50/50 blend of PLLA/starch.

Macroporous fluoropolymeric films templated by silica colloidal assembly: A possible route to super-hydrophobic surfaces

A super-hydrophobic surface was obtained on a three-dimensional (313) polyvinylidene fluoride (PVDF) macroporous film. The porous films were fabricated through self-assembled silica colloidal templates. The apparent water contact angle of the surface can be tuned from 106 degrees to 153 degrees through altering the sintering temperature and the diameter of the colloidal templates. A composite structure of micro-cavities and nanoholes on the PVDF surface was responsible for the super-hydrophobicity. The wettability of the porous surfaces was described by the use of the Cassie-Baxter model and Wenzel's equation.

Direct oxidation of benzene to phenol on manganese pyrophosphate with hydrogen peroxide

A solid catalyst manganese pyrophosphate based on non-sieves to oxidize benzene to phenol with oxidant hydrogen peroxide has shown good conversion with good selectivity in CH3CN at 65 degrees C investigating water contact angle data of three manganese salts, it is found manganese pyrophosphate has certain repulsive water character. It is further to be confirmed by benzene and phenol adsorption experiments onto catalyst surface by GC. With benzene/H2O2 ratio of 1, the benzene conversion of 13.8% with phenol selectivity of 85.0% was achieved. It is noteworthy that no any products are obtained using manganese pyrophosphate as catalyst in the oxidation of phenol in CH3CN solvent.

Surface modification of poly(L-lactic acid) to improve its cytocompatibility via assembly of polyelectrolytes and gelatin

Poly(L-lactide) (PLLA) surface was modified via aminolysis by poly(allylamine hydrochloride) (PAH) at high pH and subsequent electrostatic self-assembly of poly(sodium styrenesulfonate) (PSS) and PAH, and the process was monitored by X-ray photoelectron spectroscopy (XPS) and contact angle measurement. These modified PLLAs were then used as charged substrates for further incorporation of gelatin to improve their cytocompatibility. The amphoteric nature of the gelatin was exploited and the gelatin was adsorbed to the negatively charged PLLA/PSS and positively charged PLLA/PAH at pH = 3.4 and 7.4, respectively. XPS and water contact angle data indicated that the gelatin adsorption at pH = 3.4 resulted in much higher surface coverage by gelatin than at pH = 7.4. All the modified PLLA surfaces became more hydrophilic than the virgin PLLA. Chondrocyte culture was used to test the cell attachment, cell morphology and cell viability on the modified PLLA substrates.

Functionalization of an ethylene-propylene copolymer with allyl (3-isocyanate-4-tolyl) carbamate

An ethylene-propylene copolymer (EPM) was functionalized with an iso cyanate-bearing unsaturated monomer, allyl(3-isocyanate-4-tolyl) carbamate (TAI), with dicumyl peroxide as an initiator in a xylene solution. Fourier transform infrared (FTIR) was used to confirm the formation of EPM-g-TAI. The peak at 2273 cm(-1), characteristic of -NCO groups in EPM-g-TAI, revealed evidence of grafting. The grafting degree was determined with both chemical titration and FTIR. The grafting degree could be adjusted, and the maximum was over 6 wt % without any gelation. The molar mass distribution of EPM-g-TAI was narrower than that of EPM. The rheological behavior of both EPM-g-TAI and EPM was investigated with a rotational rheometer. The apparent viscosity of EPM-g-TAI was higher than that of EPM and increased with an increasing grafting degree of TAI. Surface analysis by contact-angle measurements showed that contact angles of EPM-g-TAI samples to a given polar liquid decreased with an increasing grafting degree of TAI. We also obtained the dispersion component of the surface free energy (gamma(S)(d)), the polar component of the surface free energy (gamma(S)(d)), and the total surface free energy (gamma(S) = gamma(S)(d) + gamma(S)(p)) of the grafted EPM. These parameters increased with the enhancement of the grafting degree, which gave us a quantitative estimation of the polar contribution of the grafted TAI to the total surface free energy of EPM-g-TAI.

Determination of surface pK(a) of SAM using an electrochemical titration method

A self-assembled monolayer (SAM) of 3-mercaptopropionic acid (HSCH2CH2COOH) was formed on a gold electrode. The effect of the charge of the end group on the electrochemical response of Fe(CN)(6)(3-) at the SAM modified electrode was studied by using cyclic voltammetry. At high pH, when the -COOH groups are dissociated, Fe(CN)(6)(3-) current is suppressed; as the solution pH is lowered, Fe(CN)(6)(3-) current increases. The electrochemical titration curve was obtained by correlating the currents to the different electrolyte pH values, from which the surface pK(a) was obtained to be 5.2+/-0.1. Furthermore, a calculation equation was presented to simulate the electrochemical titration. As comparison, the surface pK(a) was also measured by contact angle titration as 5.6+/-0.1. The surface pK(a) values determined by the two methods in our work are consistent and accurate.