Amphiphilic Nitroxide-Bearing Siloxane-Based Block Copolymer Coatings for Enhanced Marine Fouling Release.

The buildup of organic matter and organisms on surfaces exposed to marine environments, known as biofouling, is a disruptive and costly process affecting maritime operations. Previous research has identified some of the surface characteristics particularly suited to the creation of antifouling and fouling-release surfaces, but there remains room for improvement against both macrofouling and microfouling organisms. Characterization of their adhesives has shown that many rely on oxidative chemistries. In this work, we explore the incorporation of the stable radical 2,2,6,6-tetramethylpipiderin-1-oxyl (TEMPO) as a component in an amphiphilic block copolymer system to act as an inhibitor for marine cements, disrupting adhesion of macrofouling organisms. Using polystyrene-b-poly(dimethylsiloxane-r-vinylmethysiloxane) block copolymers, pendent vinyl groups were functionalized with TEMPO and poly(ethylene glycol) to construct an amphiphilic material with redox active character. The antifouling and fouling-release performance of these materials was investigated through settlement and removal assays of three model fouling organisms and correlated to surface structure and chemistry. Surfaces showed significant antifouling character and fouling-release performance was increased substantially toward barnacles by the incorporation of stable radicals, indicating their potential for marine antifouling applications.

Flexible and transparent Surface Enhanced Raman Scattering (SERS)-Active Ag NPs/PDMS composites for in-situ detection of food contaminants.

The fabrication of flexible and transparent Surface Enhanced Raman Scattering (SERS) substrates enabling fast, sensitive and on site detection is relevant for the practical application of SERS for real world analysis, such as food safety and organic pollutants monitoring. In this work novel Ag NPs/PDMS composites were fabricated and employed for the SERS detection of food contaminants directly on food surfaces. Ag NPs/PDMS composites were obtained by self-assembly of organic Ag nanoparticle solutions on flexible PDMS surfaces. Preliminary evaluation of the suitability of Ag NPs/PDMS probes for SERS analysis showed that composites were characterized by a SERS enhancement factor (EF) of 3.1 × 105, good stability and resistance to harsh conditions as well as good uniformity and batch to bach reproducibility. The "sticky" nature of Ag NPs/PDMS composites was exploited to "paste" them on irregular analytical surfaces, thus enabling the detection in situ of food contaminant crystal violet (CV) and pesticide thiram, respectively. Specifically, CV and thiram concentrations as low as 1 × 10-7 M and 1 × 10-5 M were measured on contaminated fish skin and orange peel, respectively. Furthermore, efficient SERS detection by micro-extraction of CV from fish skin and thiram from fruit surfaces was achieved, showing the analytical versatility of the fabricated SERS composites.

In Situ Polymerization Approach to Graphene-Oxide-Reinforced Silicone Composites for Superior Anticorrosive Coating.

Novel graphene-oxide-reinforced silicone composites (GOSC) are prepared by in situ polymerization of silanes and low concentrations (<0.15 wt%) of silylated GO (SGO). After modification, the distances of the SGO nanosheets are successfully increased from 0.72 to 0.87 nm. Compared with GO, the SGO shows better dispersibility in organic solvents as well as remarkably enhanced decomposition temperature (T d improved by 100 °C). After covalently grafting onto silicone resins via in situ polymerization, the obtained GOSC exhibits greatly enhanced thermal stability (T d up to 400 °C and T g improved by 3-5 °C), increased storage modulus, loss modulus, and complex viscosity. The morphology, microstructure, interfacial adhesion of the developed GOSC coatings were carefully investigated. The GOSC coatings on metal exhibit good transparency (up to 90%), hydrophobicity, and excellent anticorrosion capability. This work provides a new strategy for developing high performance graphene-based silicone composite materials.

Developing High Performance GaP/Si Heterojunction Solar Cells.

To improve the efficiency of Si-based solar cells beyond their Shockley-Queisser limit, the optimal path is to integrate them with III-V-based solar cells. In this work, we present high performance GaP/Si heterojunction solar cells with a high Si minority-carrier lifetime and high crystal quality of epitaxial GaP layers. It is shown that by applying phosphorus (P)-diffusion layers into the Si substrate and a SiNx layer, the Si minority-carrier lifetime can be well-maintained during the GaP growth in the molecular beam epitaxy (MBE). By controlling the growth conditions, the high crystal quality of GaP was grown on the P-rich Si surface. The film quality is characterized by atomic force microscopy and high-resolution x-ray diffraction. In addition, MoOx was implemented as a hole-selective contact that led to a significant increase in the short-circuit current density. The achieved high device performance of the GaP/Si heterojunction solar cells establishes a path for further enhancement of the performance of Si-based photovoltaic devices.

Thermo-responsive recoverable polymeric inhibitors for the resolution of racemic amino acids.

Novel polymeric inhibitors with lower critical solution temperatures in water were prepared and used to mediate the crystallization of racemic asparagine monohydrate, leading to chiral separation with 88.6 ee%. They could be recollected by simply elevating the temperature with a high yield of around 95% and reused without compromising the stereoselectivity and stability.

Custom 3D Printable Silicones with Tunable Stiffness.

Silicone elastomers have broad versatility within a variety of potential advanced materials applications, such as soft robotics, biomedical devices, and metamaterials. A series of custom 3D printable silicone inks with tunable stiffness is developed, formulated, and characterized. The silicone inks exhibit excellent rheological behavior for 3D printing, as observed from the printing of porous structures with controlled architectures. Herein, the capability to tune the stiffness of printable silicone materials via careful control over the chemistry, network formation, and crosslink density of the ink formulations in order to overcome the challenging interplay between ink development, post-processing, material properties, and performance is demonstrated.

Recent Developments in the Preparation of Silicones with Antimicrobial Properties.

This Focus Review describes state-of-the-art methods for the preparation of antimicrobial silicones. Given the diversity of antimicrobial activity and their mechanisms, the performance of these materials is highly dependent on the characteristics of the polymeric matrix. Therefore, different synthetic routes have been developed, such as 1) physical treatments, 2) chemical transformations, and 3) copolymerization. This classification is not exclusive, so some products belong to more than one class. Herein, we attempt to present a handy overview of the development of antimicrobial silicones, their most important application fields, the most relevant antimicrobial assays, and, as the title suggests, an overview of the most relevant preparation methods.

Unintentional PCB in chlorophenylsilanes as a source of contamination in environmental samples.

This paper discusses the concentrations and congener patterns of PCBs unintentionally present in chlorophenylsilanes. Chlorophenylsilanes are used in the production of silicone-based adhesives and phenyl silicones. The concentration of PCBs in adhesives was found to range from not-detectable concentrations to 40mg/kg. The concentrations of PCBs in trichlorophenylsilane, dichlorodiphenylsilane, chlorotriphenylsilane, and diphenylsilanediol were 0.00072-2.7, 6.5-1,500, 0.019-1.1, and 0.12-120mg/kg, respectively. Dichlorodiphenylsilane and diphenylsilanediol, in particular, had high PCB concentrations. The PCB concentration of some specimens exceeded the 50mg/kg limit set by the transportation regulations of the Stockholm Convention. In the adhesives and chlorophenylsilanes, mono- and di-chlorinated biphenyls were detected in high proportions. The congeners detected in dichlorinated biphenyls had a structure in which one chlorine atom was substituted at each of the two aryls of the biphenyl backbone. This indicated that the chlorobenzene used for synthesizing chlorophenylsilanes undergoes dimerization. The congener and homologue patterns of the adhesives containing PCBs were similar to dichlorodiphenylsilane and diphenylsilanediol. It was concluded that the production of the adhesives is based on these substances. In addition, these results indicate that silicone-based products may become a source of PCBs in the environment, leading to irregular PCB values in environmental analysis.

Formation of composite polyacrylamide and silicone substrates for independent control of stiffness and strain.

Cells that line major tissues in the body such as blood vessels, lungs and gastrointestinal tract experience deformation from mechanical strain with our heartbeat, breathing, and other daily activities. Tissues also remodel in both development and disease, changing their mechanical properties. Taken together, cells can experience vastly different mechanical cues resulting from the combination of these interdependent stimuli. To date, most studies of cellular mechanotransduction have been limited to assays in which variations in substrate stiffness and strain were not combined. Here, we address this technological gap by implementing a method that can simultaneously tune both substrate stiffness and mechanical strain. Substrate stiffness is controlled with different monomer and crosslinker ratios during polyacrylamide gel polymerization, and strain is transferred from the underlying silicone platform when stretched. We demonstrate this platform with polyacrylamide gels with elastic moduli at 6 kPa and 20 kPa in combination with two different silicone formulations. The gels remain attached with up to 50% applied strains. To validate strain transfer through the gels into cells, we employ particle-tracking methods and observe strain transmission via cell morphological changes.

Solution parameters for the fabrication of thinner silicone fibers by electrospinning.

Silicone fibers were synthesized by electrospinning, where 17 solvents with different chemical properties (boiling point, conductivity, viscosity, dielectric constant, and solubility parameter) were used to dissolve the silicone polymer for the formation of fibers through electrospinning. Previous reports on the miniaturization of fibers of polymers dissolved in a solvent suggested that the low viscosity and the high conductivity of the polymer solution were the key parameters to form thinner fibers when using a single solvent. Here we have found a powerful way to search for good solvents to reduce the fiber diameters as well as to dissolve the polymers. By considering different types of solvents, it was found that the solubility parameters conclusively determined the smallest fiber diameters of the silicone polymers. The solubility parameter of the silicone polymer should be lower than those of the solvents to make thinner fibers. The results have revealed the strong relationship between the diameters of the fibers and the solubility parameters of the solvents, and they indicate that the solubility parameter could be a good indicative parameter in selecting solvents during the fabrication of thinner fibers by electrospinning, especially for siloxane polymers.

Development of robust biocompatible silicone with high resistance to protein adsorption and bacterial adhesion.

A new biocompatible silicone comprising a carboxybetaine (CB) ester analogue, 3-methacryloxypropyltris(trimethylsiloxy)silane (TRIS) and an organic silicone macromer (bis-α,ω-(methacryloxypropyl) polydimethylsiloxane) has been developed using photo-polymerisation. Following interfacial hydrolysis of the CB ester, the resulting zwitterionic material became significantly more hydrophilic and exhibited high resistance to both non-specific protein adsorption and bacterial adhesion. Moreover, the stability of these non-fouling properties was dramatically improved by using a slow and controlled rate of ester hydrolysis of the original protective hydrophobic matrix. The subsequent ability to maintain the original optical and mechanical properties of the bare silicone following surface activation makes this material an ideal candidate for preparing contact lenses and other medical devices.

Biocatalytic synthesis of silicone polyesters.

The immobilized lipase B from Candida antarctica (CALB) was used to synthesize silicone polyesters. CALB routinely generated between 74-95% polytransesterification depending on the monomers that were used. Low molecular weight diols resulted in the highest rates of esterification. Rate constants were determined for the CALB catalyzed polytransesterifications at various reaction temperatures. The temperature dependence of the CALB-mediated polytransesterifications was examined. A lipase from C. rugosa was only successful in performing esterifications using carboxy-modified silicones that possessed alkyl chains greater than three methylene units between the carbonyl and the dimethylsiloxy groups. The proteases alpha-chymotrypsin and papain were not suitable enzymes for catalyzing any polytransesterification reactions.

A simple route to novel D spherosilicones; the first crystallographic structures of D(6) and D(8) cages.

The synthesis, characterisation and crystal structure of D(8) and D(6) cages from the corresponding bis(dialkoxy)methane is reported.

Interfacial activity of polymer-coated gold nanoparticles.

A systematic study of the interfacial activity of polymer-coated gold nanoparticles was performed with the use of a computer-controlled four-roll mill. The nanoparticle locality within the polymeric domains (bulk or interface) was controlled by means of a mixture of polymeric ligands grafted to the gold nanoparticle core. The bulk polymers were polybutadiene (PBd) and polydimethylsiloxane (PDMS). Monoterminated PDMS and PBd ligands were synthesized on the basis of the esterification of reactive groups (such as hydroxyl or amino groups) with lipoic acid anhydride. The formation of polymer-coated nanoparticles using these lipoic acid-functionalized polymers was confirmed via transmission electron microscopy (TEM), and their interfacial activity was manifested as a reduction of the interfacial tension and in the enhanced stability of thin films (as seen via the inhibition of coalescence). The nanoparticles showed an equal, if not superior, ability to reduce the interfacial tension when compared to previous studies on the effect of insoluble surfactants; however, these particles proved not to be as effective at inhibiting coalescence as their surfactant counterpart. We suggest that this effect may be caused by an increase in the attractive van der Waals forces created by the presence of metal-core nanoparticles. Experimental measurements using the four-roll mill allow us to explore the relationship between nanoparticle concentration at the interface and interfacial tension. In particular, we have found evidence that the interface concentration can be increased relative to the equilibrium value achieved by diffusion alone, and thus the interfacial tension can be systematically reduced if the interfacial area is increased temporarily via drop deformation or breakup followed by recoalescence.

Microstructure and macroscopic properties of bioactive CaO-SiO2-PDMS hybrids.

CaO-SiO2-PDMS (polydimethylsiloxane) hybrid materials were synthesized as crack-free monoliths presenting in vitro bioactivity, i.e. able to be coated with a calcium phosphate-rich layer after having been soaked in simulated body fluid (SBF). A wide physical-chemical characterization of these materials was carried out to relate their microscopic structure and macroscopic properties. The effect of PDMS and the amounts of water used for the tetraethoxysilane (TEOS) hydrolysis on the mechanical properties of hybrid materials was investigated by three-point bending tests. For a given amount of water, as PDMS content in hybrids increased, the elastic modulus decreased. Furthermore, keeping the PDMS content constant, when the amount of H2O decreased, the elastic modulus increased. Regarding in vitro bioactivity and mechanical properties, the hybrid material obtained with molar ratios H2O/TEOS = 2 and TEOS/PDMS = 3.5 proved to be the best candidate for either soft tissue substitution or metallic implant coating since the hybrid material would promote bond to bone formation, simultaneously dampening the mechanical charges.

Synthesis of silicone softener and its characteristics on cotton fabric.

This study was undertaken to examine the unresolved questions surrounding the influence of silicon softener on cotton fabrics. Results showed that the synthesized silicon softener was comparable with other tested conventional softener, According to present investigations the emulsions E1 and E2 is not economical and it is not evenly qualified and it become two phased after 24 h. But emulsion E3 was even and more economical. Moreover, it has high stability. In addition, measurement of kinetic and static friction show that the general effect of silicon softener on cotton cloth is the decrease of friction. Also, it was concluded that with increasing the add on percentage of softener, the crease of reflection angle did not change bending length and static and kinetic friction index significantly.

Silsesquioxane-based nanocomposite dendrimers with photo-luminescent and charge transport properties.

The synthesis and characterization of octavinylsilsesquioxane (OVS)-based nanocomposite dendrimers with luminescent and charge transport properties are reported. The nanocomposite dendrimers were prepared in high yield using mild Heck chemistry of mono-haloaromatic compounds with the peripheral vinylsilane groups of OVS. Attachment of 2-naphthalene, 2-(9,9-dimethyl)fluorene, and 2-(4-phenyl)-5-(1-naphthyl)-1,3,4-oxadiazole resulted in materials with blue-violet emission (360-380 nm) and photo-luminescent quantum efficiencies (PLQEs) from 1 to 26%. Blue-green emission was observed for attachment of 1-pyrene, 9-anthracene, and N1-(4-phenyl)-N1,N4,N4-triphenylbenzene-1,4-diamine with PLQEs ranging from 23 to 50%. Despite the planar characteristics of the organic dendrons, the nanocomposite dendrimers are completely amorphous and have high glass transition temperatures (Tg) ranging from 115 to 186 degrees C with decomposition temperatures (Td) exceeding 450 degrees C. Matrix-assisted laser desorption ionization-time of flight shows that unlike traditional Heck chemistry, haloaromatic compounds are adding twice across the vinylsilane groups. Finally, organic light emitting diodes using the aromatic amine-based dendrimer as hole injection layers show 55% improvement in device efficiency over traditional materials (5.16 vs. 3.24 cd A(-1)) with brightness levels exceeding 40,000 cd m(-2).

Biomimetic phosphorylcholine polymer grafting from polydimethylsiloxane surface using photo-induced polymerization.

The biomimetic synthetic phospholipid polymer containing a phosphorylcholine group, 2-methacryloyloxyethyl phosphorylcholine (MPC), has improved the surface property of biomaterials. Both hydrophilic and anti-biofouling surfaces were prepared on polydimethylsiloxane (PDMS) with MPC grafted by surface-initiated photo-induced radical polymerization. Benzophenone was used as the photoinitiator. The quantity of the adsorbed initiator on PDMS was determined by UV absorption and ellipsometry. The poly(MPC)-grafted PDMS surfaces were characterized by XPS, ATR-FTIR and static water contact angle (SCA) measurements. The SCA on PDMS decreased from 115 degrees to 25 degrees after the poly(MPC) grafting. The in vitro single protein adsorption on the poly(MPC)-grafted PDMS decreased 50-75% compared to the unmodified PDMS. The surface friction of the poly(MPC)-grafted PDMS was lower than the unmodified PDMS under wet conditions. The oxygen permeability of the poly(MPC)-grafted PDMS was as high as the unmodified PDMS. The tensile property of PDMS was maintained at about 90% of the ultimate stress and strain after the poly(MPC) grafting. The surface-modified PDMS is expected to be a novel medical elastomer which possesses an excellent surface hydrophilicity, anti-biofouling property, oxygen permeability and tensile property.

"Sweet silicones": biocatalytic reactions to form organosilicon carbohydrate macromers.

Immobilized lipase B from Candida antarctica (Novozyme 435) catalyzed the regioselective formation of ester bonds between organosilicon carboxylic diacids and a C1-O-alkylated sugar under mild reaction conditions (i.e., low temperature, neutral pH, solventless). Specifically, the acid-functionalized organosilicones reacted with the primary hydroxyl group at the C6 position of alpha,beta-ethyl glucoside during the regioselective esterification. The pure organosilicon-sugar conjugates were prepared in a one-step reaction without protection-deprotection steps and without activation of the acid groups with the integrity of the siloxane bonds. [reaction: see text]

Sol-gel-based solid-phase microextraction and gas chromatography-mass spectrometry determination of dextromethorphan and dextrorphan in human plasma.

A novel solid-phase microextraction (SPME) method was developed for isolation of dextromethorphan (DM) and its main metabolite dextrorphan (DP) from human plasma followed by GC-MS determination. Three different polymers, poly(dimethylsiloxane) (PDMS), poly(ethylenepropyleneglycol) monobutyl ether (Ucon) and polyethylene glycol (PEG) were synthesized as coated fibers using sol-gel methodologies. DP was converted to its acetyl-derivative prior to extraction and subsequent determination. The porosity of coated fibers was examined by SEM technique. Effects of different parameters such as fiber coating type, extraction mode, agitation method, sample volume, extraction time, and desorption condition, were investigated and optimized. The method is rapid, simple, easy and inexpensive and offers high sensitivity and reproducibility. The limits of detection are 0.010 and 0.015 ng/ml for DM and DP, respectively. The precisions for both analytes are below 5% (n=5). The correlation coefficient was satisfactory (r(2)>0.99) for both DM and DP. Linear ranges were obtained from 0.03 ng/ml to 2 microg/ml for DM and from 0.05 ng/ml to 2 microg/ml for DP.