Plasmonic effects of au/ag bimetallic multispiked nanoparticles for photovoltaic applications.

In recent years, there has been considerable interest in the use of plasmons, that is, free electron oscillations in conductors, to boost the performance of both organic and inorganic thin film solar cells. This has been driven by the possibility of employing thin active layers in solar cells in order to reduce materials costs, and is enabled by significant advances in fabrication technology. The ability of surface plasmons in metallic nanostructures to guide and confine light in the nanometer scale has opened up new design possibilities for solar cell devices. Here, we report the synthesis and characterization of highly monodisperse, reasonably stable, multipode Au/Ag bimetallic nanostructures using an inorganic additive as a ligand for photovoltaic applications. A promising surface enhanced Raman scattering (SERS) effect has been observed for the synthesized bimetallic Au/Ag multispiked nanoparticles, which compare favorably well with their Au and Ag spherical nanoparticle counterparts. The synthesized plasmonic nanostructures were incorporated on the rear surface of an ultrathin planar c-silicon/organic polymer hybrid solar cell, and the overall effect on photovoltaic performance was investigated. A promising enhancement in solar cell performance parameters, including both the open circuit voltage (VOC) and short circuit current density (JSC), has been observed by employing the aforementioned bimetallic multispiked nanoparticles on the rear surface of solar cell devices. A power conversion efficiency (PCE) value as high as 7.70% has been measured in a hybrid device with Au/Ag multispiked nanoparticles on the rear surface of an ultrathin, crystalline silicon (c-Si) membrane (∼ 12 µm). This value compares well to the measured PCE value of 6.72% for a similar device without nanoparticles. The experimental observations support the hope for a sizable PCE increase, due to plasmon effects, in thin-film, c-Si solar cells in the near future.

Ultrathin, flexible organic-inorganic hybrid solar cells based on silicon nanowires and PEDOT:PSS.

Recently, free-standing, ultrathin, single-crystal silicon (c-Si) membranes have attracted considerable attention as a suitable material for low-cost, mechanically flexible electronics. In this paper, we report a promising ultrathin, flexible, hybrid solar cell based on silicon nanowire (SiNW) arrays and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The free-standing, ultrathin c-Si membranes of different thicknesses were produced by KOH etching of double-side-polished silicon wafers for various etching times. The processed free-standing silicon membranes were observed to be mechanically flexible, and in spite of their relatively small thickness, the samples tolerated the different steps of solar cell fabrication, including surface nanotexturization, spin-casting, dielectric film deposition, and metallization. However, in terms of the optical performance, ultrathin c-Si membranes suffer from noticeable transmission losses, especially in the long-wavelength region. We describe the experimental performance of a promising light-trapping scheme in the aforementioned ultrathin c-Si membranes of thicknesses as small as 5.7 µm employing front-surface random SiNW texturization in combination with a back-surface distribution of silver (Ag) nanoparticles (NPs). We report the enhancement of both the short-circuit current density (JSC) and the open-circuit voltage (VOC) that has been achieved in the described devices. Such enhancement is attributable to the plasmonic backscattering effect of the back-surface Ag NPs, which led to an overall 10% increase in the power conversion efficiency (PCE) of the devices compared to similar structures without Ag NPs. A PCE in excess of 6.62% has been achieved in the described devices having a c-Si membrane of thickness 8.6 µm. The described device technology could prove crucial in achieving an efficient, low-cost, mechanically flexible photovoltaic device in the near future.

High efficiency hybrid silicon nanopillar-polymer solar cells.

Recently, inorganic/organic hybrid solar cells have been considered as a viable alternative for low-cost photovoltaic devices because the Schottky junction between inorganic and organic materials can be formed employing low temperature processing methods. We present an efficient hybrid solar cell based on highly ordered silicon nanopillars (SiNPs) and poly(3,4-ethylene-dioxythiophene):polystyrenesulfonate (PEDOT:PSS). The proposed device is formed by spin coating the organic polymer PEDOT:PSS on a SiNP array fabricated using metal assisted electroless chemical etching process. The characteristics of the hybrid solar cells are investigated as a function of SiNP height. A maximum power conversion efficiency (PCE) of 9.65% has been achieved for an optimized SiNP array hybrid solar cell with nanopillar height of 400 nm, despite the absence of a back surface field enhancement. The effect of an ultrathin atomic layer deposition (ALD), grown aluminum oxide (Al2O3), as a passivation layer (recombination barrier) has also been studied for the enhanced electrical performance of the device. With the inclusion of the ultrathin ALD deposited Al2O3 between the SiNP array textured surface and the PEDOT:PSS layer, the PCE of the fabricated device was observed to increase to 10.56%, which is ∼10% greater than the corresponding device without the Al2O3 layer. The device described herein is considered to be promising toward the realization of a low-cost, high-efficiency inorganic/organic hybrid solar cell.

Development of an animal model to investigate optimal laparoscopic trocar site fascial closure.

BACKGROUND: The rate of hernia formation after closure of 10-12 mm laparoscopic trocar sites is grossly under-reported. Using an animal model, we have developed a method to assess trocar site fascial dehiscence and the strength of different methods of fascial closure. MATERIALS AND METHODS: Pigs (n = 9; 17 ± 2.5 lbs) underwent placement of 12 mm Hasson trocars with pneumoperitoneum maintained for 1 h. Three closure techniques (Figure-of-eight; simple interrupted; pulley) were compared with no fascial closure and to native fascia at five randomly allocated abdominal wall midline locations. Necropsy was performed on the fourth postoperative d. Statistical comparisons of tensile strength and breaking strength based on closure type and trocar location were made using ANOVA with Tukey's tests. RESULTS: The mean (SD) force (Newtons) required for fascial disruption varied significantly with closure type [Native Fascia 170 (39), Figure-of-eight 169 (31), Pulley 167 (59), Simple Interrupted 151 (27), No Closure 108 (28)]; P = 0.007. The mean force required for fascial disruption was significantly increased for Native Fascia, Figure-of-eight, and Pulley relative to No Closure (P = 0.013, P = 0.015, P = 0.023, respectively). The mean (SD) force (in Newtons) required for fascial disruption also varied significantly with location of trocar [subxiphoid 181 (43), supraumbilical 151 (23), Umbilical 146 (23), infraumbilical 168 (62), suprapubic 120 (38)]; P = 0.03. The mean force for subxiphoid location was significantly increased relative to the suprapubic location (P = 0.021). CONCLUSIONS: We have developed a novel assessment model that reliably detects differences in fascial integrity after laparoscopic trocar placement and closure. This model will allow for further testing of various trocars and closure techniques, and facilitate hernia prevention strategies.

Computational, electrochemical, and spectroscopic, studies of acetycholinesterase covalently attached to carbon nanotubes.

This manuscript describes results related to the characterization of electrodes modified with a composite of acetylcholinesterase covalently bound to carbon nanotubes (CNT). The characterization was performed by computational methods and complemented by cyclic voltammetry, infrared spectroscopy, and electrochemical impedance spectroscopy. In-silico simulations enabled the identification of the binding site and the calculation of the interaction energy. Besides complementing the computational studies, experimental results obtained by cyclic voltammetry showed that the addition of CNT to the surface of electrodes yielded significant increases in effective area and greatly facilitated the electron transfer reactions. These results are also in agreement with impedance spectroscopy data, which indicated a high apparent rate constant, even after the immobilization of the enzyme. These results lend new information about the physical and chemical properties of biointerfaces at the molecular level, specifically about the mechanism and consequences of the interaction of a model enzyme with CNT.

Unmanned platform for long-range remote analysis of volatile compounds in air samples.

This paper describes a long-range remotely controlled CE system built on an all-terrain vehicle. A four-stroke engine and a set of 12-V batteries were used to provide power to a series of subsystems that include drivers, communication, computers, and a capillary electrophoresis module. This dedicated instrument allows air sampling using a polypropylene porous tube, coupled to a flow system that transports the sample to the inlet of a fused-silica capillary. A hybrid approach was used for the construction of the analytical subsystem combining a conventional fused-silica capillary (used for separation) and a laser machined microfluidic block, made of PMMA. A solid-state cooling approach was also integrated in the CE module to enable controlling the temperature and therefore increasing the useful range of the robot. Although ultimately intended for detection of chemical warfare agents, the proposed system was used to analyze a series of volatile organic acids. As such, the system allowed the separation and detection of formic, acetic, and propionic acids with signal-to-noise ratios of 414, 150, and 115, respectively, after sampling by only 30 s and performing an electrokinetic injection during 2.0 s at 1.0 kV.

Drug delivery from gold and titanium surfaces using self-assembled monolayers.

Currently available drug-eluting stents (DES) use polymers for coating and releasing drugs. Increasing evidence suggests that inflammatory and hypersensitive reactions are caused by such polymer coatings. This study focused on developing new techniques for delivering drugs directly from metal implant surfaces. Hydroxyl-terminated self-assembled monolayers (SAMs) were coated on Au and Ti surfaces. Therapeutic self-assembled monolayers (TSAMs) were prepared by chemically attaching the model drug, flufenamic acid, to SAM coated metal surfaces. Three different methods of esterification (acid chloride esterification, dry heat esterification, and direct esterification) were explored to attach flufenamic acid to SAMs. TSAMs were characterized using X-ray photoelectron spectroscopy, fluorescence microscopy, atomic force microscopy, and contact angle goniometry. These techniques collectively confirmed the attachment of drug onto SAM coated metal surfaces. In vitro drug release was investigated by immersing TSAM coated metal specimens in tris-buffered saline (TBS) at 37 degrees C for 28 days. TBS was analyzed at 1, 3, 7, 14, 21, and 28 days for the amount of drug eluted using high performance liquid chromatography. Large data scatter was observed for the release profiles of TSAMs prepared by acid chloride esterification. TSAMs prepared by dry heat and direct esterification methods showed an initial burst release of the drug followed by a sustained slow release for up to 2 weeks. Thus, this study suggests the potential for using self-assembled monolayers as an alternate system for delivering drugs from coronary stents and other metal implants.

Stability of self-assembled monolayers on titanium and gold.

Methyl- and hydroxyl-terminated phosphonic acid self-assembled monolayers (SAMs) were coated on Ti from aqueous solution. Dodecyl phosphate and dodecyltrichlorosilane SAMs were also coated on Ti using solution-phase deposition. The stability of SAMs on Ti was investigated in Tris-buffered saline (TBS) at 37 degrees C using X-ray photoelectron spectroscopy, contact angle goniometry, and atomic force microscopy. For comparison purposes, a hydroxyl-terminated thiol SAM was coated on Au, and its stability was also investigated under similar conditions. In TBS, a significant proportion of phosphonic acid or phosphate molecules were desorbed from the Ti surface within 1 day, while the trichlorosilane SAM on Ti or thiol SAM on Au was stable for up to 7 days under similar conditions. The stability of hydroxyl-terminated phosphonic acid SAM coated Ti and thiol SAM coated Au was investigated in ambient air and ultraviolet (UV) light. In ambient air, the phosphonic acid SAM on Ti was stable for up to 14 days, while the thiol SAM on Au was not stable for 1 day. Under UV-radiation exposure, the alkyl chains of the phosphonic acid SAM were decomposed, leaving only the phosphonate groups on the Ti surface after 12 h. Under similar conditions, decomposition of alkyl chains of the thiol SAM was observed on the Au surface accompanied by oxidation of thiolates.

Drug delivery from therapeutic self-assembled monolayers (T-SAMs) on 316L stainless steel.

Delivery of therapeutic agents from self-assembled monolayers (SAMs) on 316L stainless steel (SS) has been demonstrated as a viable method to deliver drugs for localized coronary artery stent application. SAMs are highly-ordered, nano-sized molecular coatings, adding 1-10 nm thickness to a surface. Hydroxyl terminated alkanethiol SAMs of 11-mercapto-1-undecanol (-OH SAM) were formed on 316L SS with 48 hr immersion in ethanolic solutions. Attachment of ibuprofen (a model drug) to the functional SAMs was carried out in toluene for 5 hrs at 60 degrees C using Novozume-435 as a biocatalyst. SAM formation and subsequent attachment of ibuprofen was characterized collectively using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and contact angle (CA) measure-ments. The quantitative in vitro release of ibuprofen into a "physiological" buffer solution was characterized using reverse phase HPLC. Drug release kinetics showed that 14.1 microg of ibuprofen eluted over a period of 35 days with 2.7microg being eluted in the first day and the remaining being eluted over a period of 35 days. The drug release kinetics showed an increase in ibuprofen elution that occurred during first 14 days (2.7microg in 1 day to 9.5 microg in 14 days), following which there was a decrease in the rate of elution. Thus, functional SAMs on 316L SS could be used as tethers for drug attachment and could serve as a drug delivery mechanism from stainless steel implants such as coronary artery stents.

Surface modification of functional self-assembled monolayers on 316L stainless steel via lipase catalysis.

Lipase catalyzed esterification of therapeutic drugs to functional self-assembled monolayers (SAMs) on 316L stainless steel (SS) after assembly has been demonstrated. SAMs of 16-mercaptohexadecanoic acid (-COOH SAM) and 11-mercapto-1-undecanol (-OH SAM) were formed on 316L SS, and lipase catalysis was used to attach therapeutic drugs, perphenazine and ibuprofen, respectively, on these SAMs. The reaction was carried out in toluene at 60 degrees C for 5 h using Novozyme-435 as the biocatalyst. The FTIR spectra after surface modification of -OH SAMs showed the presence of the C=O stretching bands at 1745 cm(-1), which was absent in the FTIR spectra of -OH SAMs. Similarly, the FTIR spectra after the reaction of the -COOH SAM with perphenazine showed two peaks in the carbonyl region, a peak at 1764 cm(-1), which is the representative peak for the C=O stretching for esters. The second peak at 1681 cm(-1) is assigned to the C=O stretching of the remaining unreacted terminal COOH. XPS spectra after lipase catalysis with ibuprofen showed a photoelectron peak evolving at 288.5 eV which arises from the carbon (C=O) of the carboxylic acid of the drug (ibuprofen). Similarly for -COOH SAMs, after esterifiation we see a small, photoelectron peak evolving at 286.5 eV which corresponds to the C in the methylene groups adjacent to the oxygen (C-O), which should evolve only after the esterification of perphenazine with the -COOH SAM. Thus, lipase catalysis provides an alternate synthetic methodology for surface modification of functional SAMs after assembly.

Drug loading of nanoporous TiO2 films.

The loading of therapeutic amounts of drug on a nanoporous TiO(2) surface is described. This novel drug-loading scheme on a biocompatible surface, when employed on medical implants, will benefit patients who require the deployment of drug-eluting implants. Anticoagulants, analgesics and antibiotics can be considered on the associated implants for drug delivery during the time of maximal pain or risk for patients undergoing orthopedic procedures. Therefore, this scheme will maximize the chances of patient recovery.

The use of alkanethiol self-assembled monolayers on 316L stainless steel for coronary artery stent nanomedicine applications: an oxidative and in vitro stability study.

The use of self-assembled monolayers (SAMs) on medical devices offers a methodology for the incorporation of nanotechnology into medicine. SAMs are highly ordered nanosized molecular coatings, adding 1 to 10 nm thickness to a surface. This work is part of an overall goal to deliver therapeutic drugs from the surface of metal coronary stents using SAMs. In this study the oxidative and in vitro stability of functional alkylthiol SAMs on 316L stainless steel (SS) has been demonstrated. SAMs of 11-mercaptoundecanoic acid (-COOH SAM) and 11-mercapto-1-undecanol (-OH SAM) were formed on 316L SS. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and contact angle (CA) measurements collectively confirmed the formation of functional alkylthiol SAMs on 316L SS. Well-formed SAMs (CA: 82 deg +/- 9 deg) were achieved within 48 hours of immersion in ethanolic solutions, after which no significant improvement in CA was observed. The ratio of the thiolate peak (163.5 eV) to the oxidized sulfur (sulfonates) peak (166.5 eV) gives us an indication of the percentage SAMs that would bind to the metal and serve as a drug reservoir in vivo; which in turn represents the stability and viability of these SAMs, keeping in mind the cardiovascular application under consideration. Oxidative and in vitro stability studies showed that alkanethiol SAMs oxidized completely within 14 days. The SAMs tend to desorb and leave the metal surface after longer time periods (21 days) in phosphate-buffered saline (PBS) immersion, whereas for oxidative exposure the SAMs continue to remain on the metal surface in the form of sulfonates. Although the chemistry of bonding of alkylthiol with the 316L SS is not well understood, the nanosized alkylthiol SAMs demonstrate sufficient stability to justify further study on these systems for potential in vivo drug delivery in the chosen coronary artery stent applications.