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Background and Aims Vasoactive intestinal peptide (VIP) is a neuropeptide involved in the regulation of feeding behavior and circadian rhythms, metabolism, and immunity. Previous studies revealed the homeostatic effects of VIP signaling on the gut microbiota. VIP-deficient mice demonstrate a gut microbiota dysbiosis characterized by reduced α-diversity and decreased relative abundance (RA) of Gram-positive Firmicutes. However, the mechanism by which VIP signaling affects changes in the microbiota is unknown. Methods To investigate the role of the two cognate G protein-coupled receptors for VIP (VPAC1 and VPAC2), in VIP-mediated homeostasis of the microbiota, fecal samples from VPAC1- and VPAC2-deficient, heterozygous, and wild-type littermate mice were assessed via targeted amplicon sequencing. Their microbiota profiles were additionally compared to microbiota from VIP-deficient, heterozygous, and wild-type littermates, where genotype-dependent changes in the composition and predicted function of each cohort were compared. Results While the wild-type mice in each line differed in α-diversity and β-diversity, consistent changes in both metrics were observed in VIP-deficient and VPAC1-deficient mice. This includes a dramatic reduction in α-diversity, increased RA of Proteobacteria and Bacteroidetes, and decreased RA of Lachnospiraceae, Ruminococcaceae, Muribaculaceae, and Rikenellaceae. Specific amplicon sequence variants (ASVs) and predicted functions found to differ significantly based on VIP or VPAC1 genotype were concordant in their directions of change. Multi-platform predicted functional profiling suggested a defective VIP-VPAC1 axis was associated with reduced amino acid degradation along with reduced quinol and quinone biosynthesis. Furthermore, alterations in predicted functions include increased sugar degradation, nitrate reduction, and fatty acid biosynthetic pathways, among other changes. Conclusions We conclude that VIP signaling through VPAC1 is critical for the maintenance of normal function of the gut microbiota.

Background The COVID-19 pandemic has disproportionately affected racial and ethnic minority groups. The Fulton County Board of Health (FCBOH) sought to promote COVID-19 health equity by partnering with Community Organized Relief Effort (CORE) and Community-Based Organizations (CBOs) to address access barriers and increase vaccine acceptance in Black and Latinx residents. These priority populations were identified using data from the Social Vulnerability Index, the COVID-19 Community Vulnerability Index, and local data regarding COVID-19 positivity and death rates. Methods With support from the Centers for Disease Control, FCBOH partnered with CORE to deploy mobile units that provided free at-home vaccination services to Fulton County residents. CORE promoted their services in zip codes identified as having higher proportions of Black and Latinx residents. Additionally, CORE partnered with three CBOs that represented and had pre-existing relationships with our target populations. These CBOs promoted CORE’s at-home services to their constituents. CORE also provided vaccination and health education services at community outreach events hosted by the CBOs as well as at clinics operated by the CBOs. Results Between the months of September 2021 and March 2022, our programs were able to provide a total of 897 vaccinations - 510 (57%) at community events, 330 (37%) through at-home services, and 54 (6%) in community-based clinics. Among the 714 vaccinations for which race and ethnicity information were available, 348 (49%) were delivered to Black individuals and 326 (46%) vaccines were administered to Latinx individuals. Uptake of vaccines for Black and Latinx individuals was highest at community events (54% and 88%, respectively), followed by at-home services (35% and 12%, respectively). Conclusion At-home vaccination services and partnerships with local CBOs can support a higher proportion of COVID-19 vaccinations administered to populations most at-risk. Notably, community events were the most effective settings for administering vaccines to these populations. Utilizing these methods can help overcome barriers to accessing healthcare and ultimately reduce COVID-19 health disparities in underserved minority communities. Disclosures All Authors: No reported disclosures.

Hypertrophic cardiomyopathy (HCM) is the most common genetic cardiovascular disease, affecting 1 in 500 people. It’s a disease with hypertrophic myocytes in disarray, leading to either diffuse or focal ventricular wall thickening and associated with the development of fibrosis. The penetrance and presentation of the disease spans a wide spectrum. The most concerning sequalae is the occurrence of sudden cardiac death (SCD) in young patients. Besides SCD, HCM is associated with left ventricular outflow tract obstruction, systolic anterior motion of the mitral valve, diastolic heart failure, atrial fibrillation, cardiac ischemia, and end-stage systolic heart failure. The goals of treatment for acute symptoms include volume replacement, vasoconstrictors, and controlling tachycardia. Long-term treatment is centered around negative inotropes, negative chronotropes, and invasive interventions to reduce obstruction.

Point-of-care ultrasound of the optic nerve sheath diameter (ONSD) to diagnose increased intracranial pressure (ICP) is of great interest in various clinical scenarios. Yet, the lack of examination standardization has made clinical utility difficult. We compare three ultrasound ocular plane views (inferior, sagittal, and transverse), which are currently used in the literature to evaluate their consistency. Comparisons for each view to magnetic resonance imaging (MRI) measurements were also made. Fifty-one patients with recent MRI of the brain, but without clinical or radiological signs of elevated ICP, were selected to undergo ocular sonography via three ultrasound planes (inferior, sagittal, and transverse). Optic nerve sheath was measured in each ultrasound view as well with MRI. Image quality scores were assigned for the ultrasound views in different orientations. The three ocular plane views were analyzed for correlation. In addition, correlation of the three ocular ultrasound views with MRI was also performed. Correlation analysis showed a wide variability in the correlation between different ultrasound views with magnitude range of 0.1 to 0.8 and directions being both positive and negative. There was a difference in image quality scores between the ultrasound views. The inferior and transverse orientations were superior to the sagittal orientation in achieving high image quality. Comparison to MRI measurements did not demonstrate a significant correlation. Our findings suggest that absolute measurements should not be compared across different ultrasound orientations given the wide variability in the correlation between the ultrasound views used to assess the optic nerve sheath. The inferior and transverse ultrasound views are the most likely to yield high-quality images, although the specific view, for the best image, in an individual patient can vary. We would caution against absolute values of ONSD to indicate increased ICP, as it may be view dependent.

An approach to the design of polyurethane coatings having amphiphilic/zwitterionic surfaces via a self-stratification approach has been explored for marine non-fouling applications. Zwitterionic materials such as poly(sulfobetaine methacrylate) poly(SBMA), are used as non-fouling materials due to their protein resistance properties. ABA-type triblock copolymers, poly(SBMA)-block-PDMS-block-poly(SBMA), having PDMS as the central block and poly(SBMA) as the flanking blocks with secondary amines at the junction points were synthesized using ring opening equilibration polymerization (ROEP), Michael addition and atom transfer radical polymerization (ATRP). A series of triblocks were synthesized and incorporated into a polyurethane coating system and were evaluated for water contact angle (WCA), surface energy (SE) and pseudobarnacle adhesion (PB). The fouling-release (FR) performance of the coatings was evaluated in the laboratory using a suite of representative marine organisms. The coatings showed excellent FR performance toward the bacterium Halomonas pacifica and the diatom (microalga) Navicula incerta while the bacterium Cellulophaga lytica and sporelings of the green macroalga Ulva linza showed a relatively higher affinity for amphiphilic coating surfaces when compared to a series of standard control coatings.

Miconazole is an imidazole used for treatment of fungal infections that exhibits poor solubility in polar solvents (e.g., aqueous solutions). Microneedles, small-scale lancet-shaped devices that are commonly used for delivery of pharmacologic agents and vaccines, were made out of an acid anhydride copolymer using visible light dynamic mask micro-stereolithography/micromolding and loaded with miconazole using a piezoelectric inkjet printer. The miconazole-coated microneedles showed biodegradation and antifungal activity against the organism Candida albicans (ATCC 90028) on Sabouraud dextrose agar using an in vitro agar plating method. The results of this study demonstrate that piezoelectric inkjet printing may be used load microneedles and other drug delivery devices with pharmacologic agents. Miconazole-loaded microneedles prepared by the visible light dynamic mask micro-stereolithography–micromolding–piezoelectric inkjet printing approach have potential use in transdermal treatment of cutaneous fungal infections.

The effect of incorporation of silicone oils into a siloxane-polyurethane fouling-release coatings system was explored. Incorporation of phenylmethyl silicone oil has been shown to improve the fouling-release performance of silicone-based fouling-release coatings through increased interfacial slippage. The extent of improvement is highly dependent upon the type and composition of silicone oil used. The siloxane-polyurethane (SiPU) coating system is a tough fouling-release solution, which combines the mechanical durability of polyurethane while maintaining comparable fouling-release performance with regard to commercial standards. To further improve the fouling-release performance of the siloxane-PU coating system, the use of phenylmethyl silicones oils was studied. Coatings formulations were prepared incorporating phenylmethyl silicone oils having a range of compositions and viscosities. Contact angle and surface energy measurements were conducted to evaluate the surface wettability of the coatings. X-ray photoelectron spectroscopy (XPS) depth profiling experiments demonstrated self-stratification of silicone oil along with siloxane to the coating-air interface. Several coating formulations displayed improved or comparable fouling-release performance to commercial standards during laboratory biological assay tests for microalgae (Navicula incerta), macroalgae (Ulva linza), adult barnacles (Balanus amphitrite syn. Amphibalanus amphitrite), and mussels (Geukensia demissa). Selected silicone-oil-modified siloxane-PU coatings also demonstrated comparable fouling-release performance in field immersion trials. In general, modifying the siloxane-PU fouling-release coatings with a small amount (1-5 wt % basis) of phenylmethyl silicone oil resulted in improved performance in several laboratory biological assays and in long-term field immersion assessments.

A series of eight novel siloxane-polyurethane fouling-release (FR) coatings were assessed for their FR performance in both the laboratory and in the field. Laboratory analysis included adhesion assessments of bacteria, microalgae, macroalgal spores, adult barnacles and pseudobarnacles using high-throughput screening techniques, while field evaluations were conducted in accordance with standardized testing methods at three different ocean testing sites over the course of six-months exposure. The data collected were subjected to statistical analysis in order to identify potential correlations. In general, there was good agreement between the laboratory screening assays and the field assessments, with both regimes clearly distinguishing the siloxane-polyurethane compositions comprising monofunctional poly(dimethyl siloxane) (PDMS) (m-PDMS) as possessing superior, broad-spectrum FR properties compared to those prepared with difunctional PDMS (d-PDMS). Of the seven laboratory screening techniques, the Cellulophaga lytica biofilm retraction and reattached barnacle (Amphibalanus amphitrite) adhesion assays were shown to be the most predictive of broad-spectrum field performance.

The use of the phenomenon of self-stratification to design polyurethane coatings having amphiphilic surfaces was explored. A novel hydrophobic siloxane polymer having orthogonal carboxylic acid groups was used to create the amphiphilic surface. The acid functional siloxane polymers were synthesized using ring opening equilibration polymerization (ROEP) of two cyclic siloxane monomers and thiol-ene click chemistry was used to introduce pendant carboxylic acid groups. The acid functional siloxane polymers were then used to prepare acid functional siloxane–polyurethane (PDMS-A) coatings. The coatings were characterized for their surface properties using water contact angle (WCA), confocal raman microscopy (CRM), and attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. The characterization revealed the presence of the acid functional siloxane polymer at the coatings’ surface due to self-stratification. WCA data indicated the coatings became more hydrophilic after immersion in water and artificial seawater (ASW), indicating the presence of the carboxylic acid groups at the surface. The PDMS-A coatings showed excellent fouling-release performance towards microalgae and good release performance towards bacteria. However, macroalga and adult barnacles showed better removal from hydrophobic PDMS-containing coatings compared to the amphiphilic PDMS-A coatings.

Strategically designed amphiphilic invertible polymers (AIPs) are capable of (i) self-assembling into invertible micellar assemblies (IMAs) in response to changes in polarity of environment, polymer concentration, and structure, (ii) accommodating (solubilizing) substances that are otherwise insoluble in water, and (iii) inverting their molecular conformation in response to changes in the polarity of the local environment. The unique ability of AIPs to invert the molecular conformation depending on the polarity of the environment can be a decisive factor in establishing the novel stimuli-responsive mechanism of solubilized drug release that is induced just in response to a change in the polarity of the environment. The IMA capability to solubilize lipophilic drugs and deliver and release the cargo molecules by conformational inversion of polymer macromolecules in response to a change of the polarity of the environment was demonstrated by loading IMA with a phytochemical drug, curcumin. It was demonstrated that four sets of micellar vehicles based on different AIPs were capable of delivering the curcumin from water to an organic medium (1-octanol) by means of unique mechanism: AIP conformational inversion in response to changing polarity from polar to nonpolar. The IMAs are shown to be nontoxic against human cells up to a concentration of 10 mg/L. On the other hand, the curcumin-loaded IMAs are cytotoxic to breast carcinoma cells at this concentration, which confirms the potential of IMA-based vehicles in controlled delivery of poorly water-soluble drug candidates and release by means of this novel stimuli-responsive mechanism.

Nanoporous alumina membranes, also known as anodized aluminum oxide membranes, are being investigated for use in treatment of burn injuries and other skin wounds. In this study, atomic layer deposition was used for coating the surfaces of nanoporous alumina membranes with zinc oxide. Agar diffusion assays were used to show activity of zinc oxide-coated nanoporous alumina membranes against several bacteria found on the skin surface, including Bacillus subtilis, Escherichia coli, Staphylococcus aureus, and Staphylococcus epidermidis. On the other hand, zinc oxide-coated nanoporous alumina membranes did not show activity against Pseudomonas aeruginosa, Enterococcus faecalis, and Candida albicans. These results suggest that zinc oxide-coated nanoporous alumina membranes have activity against some Gram-positive and Gram-negative bacteria that are associated with skin colonization and skin infection.

Five non-biocidal xerogel coatings were compared to two commercial non-biocidal coatings and a silicone standard with respect to antifouling (AF)/fouling-release (FR) characteristics. The formation and release of biofilm of the marine bacterium Cellulophaga lytica, the attachment and release of the microalga Navicula incerta, and the fraction removal and critical removal stress of reattached adult barnacles of Amphibalanus amphitrite were evaluated in laboratory assays. Correlations of AF/FR performance with surface characteristics such as wettability, surface energy, elastic modulus, and surface roughness were examined. Several of the xerogel coating compositions performed well against both microfouling organisms while the commercial coatings performed less well toward the removal of microalgae. Reattached barnacle adhesion as measured by critical removal stress was significantly lower on the commercial coatings when compared to the xerogel coatings. However, two xerogel compositions showed release of 89–100% of reattached barnacles. These two formulations were also tested in the field and showed similar results.

Modifications have been made to the previously described adult barnacle laboratory reattachment method to enhance and improve the overall utility of this technique for rapidly assessing the efficacy of novel fouling-release marine coating technologies. These modifications include the use of an immobilization template to secure barnacles onto the coating surfaces during the underwater reattachment process, the development of a semi-automated push-off device to enable consistent and reproducible force gauge measurements and the implementation of a software tool to measure the diameter of barnacle base plates for adhesion strength calculations. A series of experimental siloxane–polyurethane and control coatings were evaluated with both the original and improved laboratory reattachment methodologies. Significantly higher adhesion strengths were obtained on these coatings using the improved reattachment method. Furthermore, only the improved reattachment method was able to discern significant differences in the performance of the siloxane–polyurethane coatings based on differences in compositional components. In this regard, the siloxane–polyurethane coatings containing the poly-caprolactone end groups attached to the poly(dimethylsiloxane) (PDMS) backbone exhibited significantly higher reattached barnacle adhesion strengths than the aminopropyl-terminated PDMS containing coatings. It was also shown that the utilization of barnacles with 5–6 mm base plate diameters, rather than 7–8 mm diameters, significantly enhanced the strength or tenacity of adhesion to the surface of the control coatings. The results of the improved laboratory reattachment evaluation of experimental siloxane–polyurethane and control coatings were in good agreement with barnacle adhesion measurements obtained for the same coatings with static ocean immersion testing in the field.

The effects of formulation variables, such as type of polyol, solvent type and solvent content, and coating application method, on the surface properties of siloxane–polyurethane fouling-release coatings were explored. Fouling-release coatings allow the easy removal of marine organisms from a ship’s hull via the application of a shear force to the surface. Self-stratified siloxane–polyurethane coatings are a new approach to a tough fouling-release coating system. Combinatorial High Throughput Experimentation was employed to formulate and characterize 24 different siloxane–polyurethane coatings applied using drawdown and drop-casting methods. The resulting coatings were tested for surface energy using contact angle measurements. The fouling-release performance of the coatings was tested using a number of diverse marine organisms including bacteria (Halomonas pacifica and Cytophaga lytica), sporelings (young plants) of the green macroalga (Ulva linza), diatom ((microalga) Navicula incerta), and barnacle (Amphibalanus amphitrite). The performance of the majority of the coatings was found to be better than the silicone standards, Intersleek® and Silastic® T2. An increase in solvent content in the formulations increased the surface roughness of the coatings. Coatings made with polycaprolactone polyol appeared to be somewhat rougher compared to coatings made with the acrylic polyol. The adhesion strength of sporelings of Ulva increased with an increase in solvent content and increase in surface roughness. The adhesion strengths of Ulva sporelings, C. lytica, and N. incerta were independent of application method (cast or drawdown) in contrast to H. pacifica adhesion, which was dependent on the application method.

Siloxane–polyurethane paints were formulated and characterized for coating properties and performance as fouling-release (FR) marine coatings. Paints were formulated at 20 and 30 pigment volume concentrations with titanium dioxide, and aminopropyl-terminated poly(dimethylsiloxane) (APT-PDMS) loadings were varied from 0 to 30% based on binder mass. The coatings were characterized for water contact angle, surface energy (SE), gloss, and pseudobarnacle (PB) adhesion. The assessment of the FR performance compared with polyurethane (PU) and silicone standards through the use of laboratory biological assays was also performed. Biofilm retention and adhesion were conducted with the marine bacterium Cellulophaga lytica, and the microalgae diatom Navicula incerta. Live adult barnacle reattachment using Amphibalanus amphitrite was also performed. The pigmented coatings were found to have properties and FR performance similar to those prepared without pigment. However, a higher loading of PDMS was required, in some cases, to obtain the same properties as coatings prepared without pigment. These coatings rely on a self-stratification mechanism to bring the PDMS to the coating surface. The slight reduction in water contact angle (WCA) and increase in pseudobarnacle release force with pigmentation suggests that pigmentation slowed or interfered with the self-stratification mechanism. However, increasing the PDMS loading is an apparent method for overcoming this issue, allowing for coatings having similar properties as those of clear coatings and FR performance similar to those of silicone standard coatings.

Microneedles are small-scale needle-like projections that may be used for transdermal delivery of pharmacologic agents, including protein-containing and nucleic acid-containing agents. Commercial translation of polymeric microneedles would benefit from the use of facile and cost effective fabrication methods. In this study, visible light dynamic mask microstereolithography, a rapid prototyping technique that utilizes digital light projection for selective polymerization of a liquid resin, was used for fabrication of solid microneedle array structures out of an acrylate-based polymer. Pulsed laser deposition was used to deposit silver and zinc oxide coatings on the surfaces of the visible light dynamic mask microstereolithography-fabricated microneedle array structures. Agar diffusion studies were used to demonstrate the antimicrobial activity of the coated microneedle array structures. This study indicates that light-based technologies, including visible light dynamic mask microstereolithography and pulsed laser deposition, may be used to fabricate microneedles with antimicrobial properties for treatment of local skin infections.

As part of ongoing efforts aimed at the development of extensive structure−property relationships for moisture-curable polysiloxane coatings containing tethered quaternary ammonium salt (QAS) moieties for potential application as environmental friendly coatings to combat marine biofouling, a combinatorial/high-throughput (C/HT) study was conducted that was focused on four different compositional variables. The coatings that were investigated were derived from solution blends of a silanol-terminated polydimethylsiloxane (HO-PDMS-OH), QAS-functional alkoxysilane, and methyltriacetoxysilane. The compositional variables investigated were alkoxysilane functionality of the QAS-functional silane, chain length of the monovalent alkyl group attached to the QAS nitrogen atom, concentration of the QAS-functional alkoxysilane, and molecular weight of the HO-PDMS-OH. Of these variables, the composition of the alkoxysilane functionality of the QAS-functional silane was a unique variable that had not been previously investigated. The antifouling (AF) and fouling-release (FR) characteristics of the 24 unique coating compositions were characterized using HT assays based on three different marine microorganisms, namely, the two bacteria, Cellulophaga lytica and Halomonas pacifica, and the diatom, Navicula incerta. Coatings surfaces were characterized by surface energy, water contact angle hysteresis, and atomic force microscopy (AFM). A wide variety of responses were obtained over the compositional space investigated. ANOVA analysis showed that the compositional variables and their interactions significantly influenced AF/FR behaviors toward individual marine microorganisms. It was also found that utilization of the ethoxysilane-functional QASs provided enhanced AF character compared to coatings based on methoxysilane-functional analogues. This was attributed to enhanced surface segregation of QAS groups at the coating-air interface and confirmed by phase images using AFM.

Marine biofouling of ship hulls has significant cost, performance and environmental implications. Due to environmental concerns associated with traditional antifouling paints that mitigate fouling with the use of biocides, increasing research and development efforts have been made on fouling-release (FR) coatings. FR coatings do not actively deter settlement of marine organisms, but, instead, mitigate biofouling by minimizing the strength of adhesion. Ideally, an FR coating will allow the fouling community to be removed by simply running the vessel at relatively high speed. Traditional methods for characterizing FR properties involve immersion of relatively large samples in the ocean and waiting months for enough fouling to occur to enable reliable measurements to be made. To greatly enhance research and development relative to FR coatings, a combinatorial/high-throughput workflow was developed that includes a suite of FR laboratory assays involving marine bacteria, microalgae, and live, adult barnacles. ...

An array of quaternary ammonium functionalized-polyhedral oligomeric silsesquioxane (Q-POSS) compounds with different alkyl chain lengths and counter ions were synthesized using a two-step process. First, octasilane POSS was functionalized with dimethylamino groups by hydrosilylation with allyldimethylamine. Next, partial quaternization of the tertiaryamino-functional POSS was achieved using an alkyl halide to produce the Q-POSS. Alkyl chain length of the Q-POSS compounds varied from –C12H25 to –C18H37 and the counter ions varied between chlorine, bromine, and iodine. Moisture-cured polysiloxane coatings were prepared by dispersing Q-POSS molecules into a solution blend of silanol-terminated polydimethylsiloxane, methylacetoxysilane, and a catalyst. To evaluate the utility of the Q-POSS molecules as a broad-spectrum antimicrobial additive, the antimicrobial activity of the coatings toward the Gram-negative bacterium, Escherichia coli, the Gram-positive bacterium, Staphylococcus aureus, and the opportunistic fungal pathogen, Candida albicans, was determined using an agar plating method. The results obtained showed that both the composition of the Q-POSS and the composition of the polysiloxane matrix affected antimicrobial properties. Compositions were identified that inhibited the growth of all three microorganisms on the coating surface. Surface Raman spectroscopic analysis was performed on selected set of coatings to understand the relative concentration of Q-POSS molecules at the coating surface.

An array of quaternary ammonium-functionalized POSS (Q-POSS) compounds were synthesized and their antimicrobial properties toward the Gram-negative bacterium, Escherichia coli, and the Gram-positive bacterium, Staphylococcus aureus, determined in aqueous solution. Using Q-POSS compositions that exhibited broad spectrum antimicrobial activity in solution, the utility of the Q-POSS compounds as an antimicrobial additive for polysiloxane coatings was determined. The results of the investigation showed that Q-POSSs possessing a relatively low extent of quaternization and longer alkyl chain lengths provided the highest antimicrobial activity in solution. For polysiloxane coatings containing Q-POSS molecules as an antimicrobial additive, coating surface energy, surface morphology, and antimicrobial properties were found to be strongly dependent on Q-POSS composition. Coatings based on Q-POSSs possessing the lowest extent of quaternization displayed antimicrobial activity while analogous coatings produced using Q-POSSs possessing the highest extent of quaternization showed no antimicrobial activity. The lack of antimicrobial activity exhibited by coatings possessing Q-POSSs with a relatively high extent of quaternization was attributed to agglomeration of Q-POSS molecules through the formation of intermolecular interactions involving the quaternary ammonium moieties. Agglomeration would be expected to reduce diffusivity and inhibit interaction of the Q-POSS molecules with microbial cells.

Novel, environmentally friendly antimicrobial coatings containing tethered biocide moieties derived from the ubiquitous biocide, triclosan, were synthesized and characterized using a high-throughput workflow. Triclosan was first modified with an acrylate functionality and, subsequently, copolymerized with hydroxyethyl acrylate and butyl acrylate using conventional free radical polymerization to form an array of acrylic polyol terpolymers. The polyols were characterized using nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and gel permeation chromatography. Arrays of urethane coatings were produced from the array of acrylic polyol terpolymers and, subsequently, characterized using parallel dynamic mechanical thermal analysis, surface energy measurements, and various biological assays. The results of the biological assays showed that the coatings were effective toward inhibiting Staphylococcus epidermidis biofilm retention without leaching triclosan or other toxic components from the coating. The level of antimicrobial activity was found to increase with the content of triclosan moieties incorporated into the coating matrix. These results indicate that triclosan moieties tethered to a polymer matrix can impart antimicrobial properties via a contact-active, nonleaching (i.e., environmentally friendly) mechanism. Since S. epidermidis is one of the primary microorganisms associated with infection and failure of implanted medical devices, such as prosthetic heart valves, urinary catheters, and a variety of orthopedic implants, these coatings may have good potential for commercialization in some of these applications.

Polymer surface properties are controlled by the molecular surface structures. Sum frequency generation (SFG) vibrational spectroscopy has been demonstrated to be a powerful technique to study polymer surface structures at the molecular level in different chemical environments. In this research, SFG has been used to study the surface segregation of biocide moieties derived from triclosan (TCS) and tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (C-14 QAS) that have been covalently bound to a poly(dimethylsiloxane) (PDMS) matrix. PDMS materials are being developed as coatings to control biofouling. This SFG study indicated that TCS-moieties segregate to the surface when the bulk concentration of TCS-moieties exceeds 8.75% by weight. Surface segregation of C-14 QAS moieties was detected after 5% by weight incorporation into a PDMS matrix. SFG results were found to correlate well with antifouling activity, providing a molecular interpretation of such results. This research showed that SFG can aid in the development of coatings for controlling biofouling by elucidating the chemical structure of the coating surface.

Release mechanisms of barnacles (Amphibalanus amphitrite or Balanus amphitrite) reattached to platinum-cured silicone coatings were studied as a function of coating thickness (210-770 microm), elastic modulus (0.08-1.3 MPa), and shear rate (2-22 microm s(-1)). It was found that the shear stress of the reattached, live barnacles necessary to remove from the silicone coatings was controlled by the combined term (E/t)(0.5) of the elastic modulus (E) and thickness (t). As the ratio of the elastic modulus to coating thickness decreased, the barnacles were more readily removed from the silicone coatings, showing a similar release behavior to pseudobarnacles (epoxy glue). The barnacle mean shear stress ranged from 0.017 to 0.055 MPa whereas the pseudobarnacle mean shear stress ranged from 0.022 to 0.095 MPa.

BACKGROUND: UV-curable coatings are promising candidates for environmentally friendly marine fouling-release coatings. Cationic UV-curable epoxy-siloxane release coatings show good release performance but suffer from poor coating mechanical properties. A difunctional oxetane monomer, DOX, was co-photopolymerized with an epoxy-siloxane oligomer at loading levels from 10 to 40 wt% to obtain toughened fouling-release coatings. RESULTS: The DOX-toughened coatings showed enhanced cationic photopolymerization activity, solvent resistance and modulus. DOX-toughened coatings (10 and 20 wt%) exhibited higher impact resistance. The DOX-toughened coatings showed no leachate toxicity and the coatings were hydrophobic and non-toxic to biofilm growth when analyzed with marine bacteria and algae. In general, 10 and 20 wt% DOX-toughened coatings exhibited better marine bacteria and algae fouling-release performance among the DOX-toughened coatings. Pseudo-barnacle shear release stress for the DOX-toughened coatings increased with increasing DOX content. Live barnacle reattachment assay showed that 10 and 20 wt% DOX-toughened coatings had comparable barnacle removal stress to commercial silicone reference coatings. CONCLUSIONS: DOX-toughened (10 and 20 wt%) UV-curable epoxy-siloxane coatings exhibited enhanced mechanical properties and better overall marine fouling-release performance among the toughened UV-curable release coatings studied. Copyright © 2008 Society of Chemical Industry

The concept of tethering quaternary ammonium salts (QASs) to a crosslinked polysiloxane matrix to produce a hybrid antifouling/fouling-release coating was investigated. A statistical experimental design was used to determine the effect of QAS concentration on biocidal activity toward a marine bacterium, Cellulophaga lytica (C. lytica). In addition to measuring biocidal activity, coating film quality as well as stability upon water immersion were evaluated. The results of the study showed that biocidal activity was strongly dependent on QAS concentration. For addition-curable coatings, the presence of 4 wt% QAS moieties resulted in approximately 50% reduction in C. lytica biofilm retention without any leachate toxicity. Attempts to increase the level of QAS moieties to increase biocidal activity resulted in coating delamination from the substrate and unacceptable film quality upon artificial seawater immersion due to excessive swelling. As a result, a moisture-curable system based on tethered QASs was investigated since moisture curing allows for higher crosslink densities to be achieved which would be expected to minimize swelling upon artificial seawater immersion. The moisture-curable coating developed showed enhanced stability upon artificial seawater immersion, greater than 80% reduction in C. lytica biofilm retention, and greater than 90% reduction in biofilm growth for the marine algae, Navicula incerta.

Polysiloxane coatings containing chemically-bound ("tethered") quaternary ammonium salt (QAS) moieties were investigated for potential application as environmental-friendly coatings to control marine biofouling. A combinatorial/high-throughput approach was applied to the investigation to enable multiple variables to be probed simultaneously and efficiently. The variables investigated for the moisture-curable coatings included QAS composition, ie alkyl chain length, and concentration as well as silanol-terminated polysiloxane molecular weight. A total of 75 compositionally unique coatings were prepared and characterized using surface characterization techniques and biological assays. Biological assays were based on two different marine microorganisms, a bacterium, Cellulophaga lytica and a diatom, Navicula incerta, as well as a macrofouling alga, Ulva. The results of the study showed that all three variables influenced coating surface properties as well as antifouling (AF) and fouling-release (FR) characteristics. The incorporation of QAS moieties into a polysiloxane matrix generally resulted in an increase in coating surface hydrophobicity. Characterization of coating surface morphology revealed a heterogeneous, two-phase morphology for many of the coatings investigated. A correlation was found between water contact angle and coating surface roughness, with the contact angle increasing with increasing surface roughness. Coatings based on the QAS moiety containing the longest alkyl chain (18 carbons) displayed the highest micro-roughness and, thus, the most hydrophobic surfaces. With regard to AF and FR properties, coatings based on the 18 carbon QAS moieties were very effective at inhibiting C. lytica biofilm formation and enabling easy removal of Ulva sporelings (young plants) while coatings based on the 14 carbon QAS moities were very effective at inhibiting biofilm growth of N. incerta.

A combinatorial workflow has been produced for the development of novel, environmental-friendly marine coatings. A particularly challenging aspect of the workflow development was the selection and development of high-throughput screening methods that allow for some degree of prediction of coating performance in the aquatic environment of interest. The high-throughput screening methods currently in place include measurements of surface energy, viscoelastic properties, pseudobarnacle adhesion, and a suite of biological assays based on various marine organisms. An experiment involving a series of fouling-release coatings was used to correlate high-throughput screening data to data obtained from ocean site immersion testing. The results of the experiment showed that both bacterial biofilm surface coverage and storage modulus at 30 °C showed a good correlation with barnacle adhesion strength and a fair correlation with fouling rating, but surface energy and pseudobarnacle adhesion did not correlate with the results from ocean site testing.

Crosslinked siloxane–polyurethane coatings were designed, synthesized, formulated, applied, and characterized using combinatorial high-throughput experimentation and eight coatings were selected as candidates for further characterization. First, 72 novel hydroxyalkyl carbamate and dihydroxyalkyl carbamate-terminated poly(dimethylsiloxane) (PDMS) oligomers and their carbamate-linked block copolymers with poly(e-caprolactone) (PCL) were synthesized using a high-throughput synthesis system. These PDMS oligomers and block copolymers were characterized for their molecular weight using high-throughput Gel Permeation Chromatography (Rapid-GPC). The 72 oligomers were then incorporated into siloxane–polyurethane formulations at four different levels resulting in 288 coatings. After initial screening of these 288 coatings, eight coatings were selected for further characterization. Differential scanning calorimetry, dynamic mechanical analysis, X-ray photoelectron spectroscopy and surface energy analysis demonstrate the presence of PDMS on the surface with a polyurethane underlayer. Pseudo-barnacle adhesion and the attachment strength of reattached live barnacles (Balanus amphitrite) were in good agreement. Out of the eight coatings that were down-selected, two coatings performed well in algal (Ulva), bacterial (Cytophaga lytica, Halomonas pacifica), and barnacle (Balanus amphitrite) laboratory screening assays and are potential candidates for ocean testing.

High throughput combinatorial characterization was performed on thermosetting siloxane–urethane coatings in order to find a correlation between the characterization techniques, surface topography, and adhesion strength of barnacles. A series of coatings having microtopographical surfaces with different domain sizes were prepared based on a thermosetting siloxane–urethane system. This microtopography was formed spontaneously during the film-formation process. These surfaces were characterized by atomic force microscopy (AFM), surface energy, dynamic contact angle, and pseudo barnacle pull-off adhesion and were compared to pure polyurethane (PU) and silicone rubber control. Surface energy and dynamic contact angles were measured by an automated surface energy measurement system and pull-off adhesion values were obtained from a high throughput pull-off adhesion measurement unit. The results were compared with the adhesion strength of barnacles.

In order to facilitate a semi-high throughput approach to the evaluation of novel fouling-release coatings, a 'spinjet' apparatus has been constructed. The apparatus delivers a jet of water of controlled, variable pressure into the wells of 24-well plates in order to facilitate measurement of the strength of adhesion of algae growing on the base of the wells. Two algae, namely, sporelings (young plants) of the green macroalga Ulva and a diatom (Navicula), were selected as test organisms because of their opposing responses to silicone fouling-release coatings. The percentage removal of algal biofilm was positively correlated with the impact pressure for both organisms growing on all the coating types. Ulva sporelings were removed from silicone elastomers at low impact pressures in contrast to Navicula cells which were strongly attached to this type of coating. The data obtained for the 24-well plates correlated with those obtained for the same coatings applied to microscope slides. The data show that the 24-well plate format is suitable for semi-high throughput screening of the adhesion strength of algae.

A high-throughput bacterial biofilm retention screening method has been augmented to facilitate the rapid analysis and down-selection of fouling-release coatings for identification of promising candidates. Coatings were cast in modified 24-well tissue culture plates and inoculated with the marine bacterium Cytophaga lytica for attachment and biofilm growth. Biofilms retained after rinsing with deionised water were dried at ambient laboratory conditions. During the drying process, retained biofilms retracted through a surface de-wetting phenomenon on the hydrophobic silicone surfaces. The retracted biofilms were stained with crystal violet, imaged, and analysed for percentage coverage. Two sets of experimental fouling-release coatings were analysed with the high-throughput biofilm retention and retraction assay (HTBRRA). The first set consisted of a series of model polysiloxane coatings that were systematically varied with respect to ratios of low and high MW silanol-terminated PDMS, level of cross-linker, and amount of silicone oil. The second set consisted of cross-linked PDMS-polyurethane coatings varied with respect to the MW of the PDMS and end group functionality. For the model polysiloxane coatings, HTBRRA results were compared to data obtained from field immersion testing at the Indian River Lagoon at the Florida Institute of Technology. The percentage coverage calculations of retracted biofilms correlated well to barnacle adhesion strength in the field (R(2)=0.82) and accurately identified the best and poorest performing coating compositions. For the cross-linked PDMS-polyurethane coatings, the HTBRRA results were compared to combinatorial pseudobarnacle pull-off adhesion data and good agreement in performance was observed. Details of the developed assay and its implications in the rapid discovery of new fouling-release coatings are discussed.

A series of polysulfone and polyacrylate-based zwitterionic coatings were prepared on epoxy-primed aluminum substrata and characterized for their antifouling (AF) and fouling-release (FR) properties towards marine bacteria, microalgae and barnacles. The zwitterionic polymer coatings provided minimal resistance against bacterial biofilm retention and microalgal cell attachment, but facilitated good removal of attached microbial biomass by exposure to water-jet apparatus generated hydrodynamic shearing forces. Increasing the ion content of the coatings improved the AF properties, but required a stronger adhesive bond to the epoxy-primed aluminum substratum to prevent coating swelling and dissolution. Grafted poly(sulfobetaine) (gpSBMA), the most promising zwitterionic coating identified from microfouling evaluations, enabled the removal of four out of five barnacles reattached to its surface without incurring damage to their baseplates. This significant result indicated that gpSBMA relied predominately on its surface chemistry for its FR properties since it was very thin (~1-2 µm) relative to commercial coating standards (>200 µm).

High-throughput methods were used to prepare and characterize the fouling-release (FR) properties of an array of amphiphilic polysiloxane-based coatings possessing systematic variations in composition. The coatings were derived from a silanol-terminated polydimethylsiloxane, a silanol-terminated polytrifluorpropylmethylsiloxane (CF3-PDMS), 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane (TMS-PEG), methyltriacetoxysilane and hexamethyldisilazane-treated fumed silica. The variables investigated were the concentration of TMS-PEG and the concentration of CF3-PDMS. In general, it was found that the TMS-PEG and the CF3-PDMS had a synergist effect on FR properties with these properties being enhanced by combining both compounds into the coating formulations. In addition, reattached adult barnacles removed from coatings possessing both TMS-PEG and relatively high levels of CF3-PDMS displayed atypical base-plate morphologies. The majority of the barnacles removed from these coatings exhibited a cupped or domed base-plate as compared to the flat base-plate observed for the control coating that did not contain TMS-PEG or CF3-PDMS. Coating surface analysis using water contact angle measurements indicated that the presence of CF3-PDMS facilitated migration of TMS-PEG to the coating/air interface during the film formation/curing process. In general, coatings containing both TMS-PEG and relatively high levels of CF3-PDMS possessed excellent FR properties.

Atopic dermatitis is the most common chronic inflammatory skin disease and is a major cause of morbidity and suffering. This review examines its differing prevalence worldwide, its aetiology, and genetics.

A series of patients undergoing component reconstruction of midline abdominal wall separations was analyzed to assess the effects of comorbidities and biological implant reinforcements on outcomes. Thirty-nine patients were identified as fitting the technical definition of component repairs and having at least 12 months of documented follow-up. This group of procedures had a 67% primary healing rate, 18% and 13% rate of major and minor complications, respectively, and a total of 90% successful reconstructions after secondary procedures. Variables assessed for outcome influences included etiology of the abdominal wall separation, obesity, diabetes, hypertension, and biological implant reinforcements, including absorbable mesh and biological implants. None of these factors significantly influenced outcome, although first time repairs and reinforced repairs had suggestively higher success rates. This data suggest that comorbidities do not influence outcomes of component abdominal wall repairs, and assessments of the problem and ongoing technical refinements of the procedure should be studied further.

In our series, 15 patients underwent 21 procedures for wide resection of axillary hidradenitis with coverage by posteriorly based Limberg transposition flaps. Twenty flaps (95%) healed without axillary contracture. One failed flap required skin graft coverage. Transposition flap coverage in these patients was a reliable, single-stage reconstruction allowing prompt arm movement.

A 2½-year-old previously well Afro-Caribbean girl presented with a 1-week history of fever and a generalised non-healing, painful and itchy ulceration on the body 3 weeks after acute varicella infection. On examination, she had multiple punched-out ulcers on her torso measuring 0.5–2 cm in diameter associated with central necrosis (figure 1). She had a normal white cell count and inflammatory markers. Her varicella …

HIV-specific Elispot responses were investigated in 57 antiretroviral therapy-naive children, of median age 9.9 years. CD8(+) T-cell responses were detected in 96% children; Nef was the immunodominant protein. Responses broadened over time, but there was no association between magnitude, breadth or specificity of response and viraemia. Gag-specific CD4(+) T-cell responses, detectable in 26% children, correlated inversely with viraemia (R = -0.43, P < 0.001), suggesting that preservation of this cell population may be an important goal of therapeutic/vaccine strategies.

Siloxane-polyurethane fouling-release (FR) coatings based on aminopropyl terminated poly(dimethylsiloxane) (PDMS) macromers were prepared and characterized for FR performance via laboratory biological assays. These systems rely on self-stratification, resulting in a coating with a siloxane-rich surface and polyurethane bulk. Previously, these coating systems have used PDMS with multiple functional groups which react into the polyurethane bulk. Here, aminopropyl terminated PDMS macromers were prepared, where a single amine group anchors the PDMS in the coating. Coatings were prepared with four molecular weights (1000, 5000, 10,000, and 15,000 g mol⁻¹) and two levels of PDMS (5% and 10%). High water contact angles and low surface energies were observed for the coatings before and after water immersion, along with low pseudobarnacle removal forces. Laboratory bioassays showed reduced biofilm retention of marine bacteria, good removal of diatoms from coatings with low molecular weight PDMS, high removal of algal sporelings (young plants), and low removal forces of live barnacles.

Assessment and down-selection of non-biocidal coatings that prevent the adhesion of fouling organisms in the marine environment requires a hierarchy of laboratory methods to reduce the number of experimental coatings for field testing. Automated image-based methods are described that facilitate rapid, quantitative biological screening of coatings generated through combinatorial polymer chemistry. Algorithms are described that measure the coverage of bacterial and algal biofilms on coatings prepared in 24-well plates and on array panels, respectively. The data are used to calculate adhesion strength of organisms on experimental coatings. The results complement a number of physical and mechanical methods developed to screen large numbers of samples.

A total of 400 clinical Streptococcus pneumoniae strains from patients with respiratory diseases were collected from January 2002 to December 2005. In this study, an increased prevalence of penicillin-nonsusceptible S. pneumoniae (PNSP) from 63% in 2002-2003 to 69% in 2004-2005 was found. During 2004-2005, 56% were erythromycin-nonsusceptible S. pneumoniae (ENSP) and 54% were both PNSP and ENSP. The PNSP, ENSP and PNSP+ENSP groups showed similar trends, ie, sensitive to amoxicillin/clavulanate (range 97.2-98.5%), levofloxacin (range 90.7-92.4%), ceftriaxone (range 87.1-89.4%), and ofloxacin (range 64.8-66.1%). Lower levels of susceptibility were detected for azithromycin, clarithromycin, cefdinir, cefprozil, clindamycin, co-trimoxazole, chloramphenicol and tetracycline in penicillin and erythromycin-nonsusceptible strains. Of the macrolide-resistant S. pneumoniae, 55% of strains exhibited the M phenotype and 45% the constitutive MLS(B) phenotype. No pneumococci with the inducible MLS(B) phenotype were detected in Thailand.

Large numbers of coatings can be generated very quickly using a combinatorial high-throughput approach. Rapid screening assays are typically required to adequately evaluate and down select coating candidates to identify promising compositions. An automated, spinning water jet apparatus was developed to rapidly characterize the adhesion strength of marine organisms to coating surfaces. Coating arrays are cast in multiwell plates and subjected to a jet of water of controlled pressure and duration. Array plates are manipulated by a robotic arm to facilitate accurate and repeatable water jet treatments. Jet pressures of 40-688 kPa can be generated and precisely maintained by computer control. A five axis robotic arm selects plates from three plate stacking hotels yielding a total of 39 plates or 936 individual coating samples for each experimental run. All robotic instructions, process parameters, and data are stored and controlled by the computer. The large plate handling capacity offered by the robotic system enables the analysis of a wide variety of coatings for "fouling-release" properties. A brief example demonstrating the capability of the automated water jet apparatus to evaluate marine bacterial adhesion to coating surfaces is provided.

The authors recently reported on the development of a novel multiwell plate screening method for the high-throughput assessment of bacterial biofilm retention on surfaces. Two series of biocide containing coatings were prepared to assess the ability of the developed assay to adequately discern differences in antifouling performance: i) a commercially available poly(methyl methacrylate) (PMMA) and silicone elastomer (DC) physically blended with an organic antifouling biocide Sea-Nine 211 (SN211) (4,5-dichloro-2-n-octyl-3(2H)-isothiazolone), and ii) a silanol-terminated polydimethylsiloxane (PDMS-OH) reacted with an alkoxy silane-modified polyethylenimine containing bound ammonium salt groups (PEI-AmCl). Three marine bacteria were utilised to evaluate the SN211 blended coatings (Pseudoalteromonas atlantica ATCC 19262, Cobetia marina ATCC 25374, Halomonas pacifica ATCC 27122) and the marine bacterium Cytophaga lytica was utilised to evaluate the PEI-AmCl/PDMS-OH coatings. The SN211 blended coatings showed a general trend of decreasing biofilm retention as the concentration of SN211 increased in both PMMA and DC. HPLC analysis revealed that reduction in biofilm retention was positively correlated with the amount of SN211 released into the growth medium over the length of the bacterial incubation. When compared to PMMA, DC consistently showed an equal or greater percent reduction in biofilm retention as the level of SN211 loading increased, although at lower loading concentrations. Evaluations of the PEI-AmCl/PDMS-OH coatings with C. lytica showed that all PEI-AmCl loading concentrations significantly reduced biofilm retention (p0.0001) by a surface contact phenomenon. The high-throughput bacterial biofilm growth and retention assay has been shown to be useful as an effective primary screening tool for the rapid assessment of antifouling materials.