Operando cathode activation with alkali metal cations for high current density operation of water-fed zero-gap carbon dioxide electrolyzers.

Continuous-flow electrolyzers allow CO2 reduction at industrially relevant rates, but long-term operation is still challenging. One reason for this is the formation of precipitates in the porous cathode from the alkaline electrolyte and the CO2 feed. Here we show that while precipitate formation is detrimental for the long-term stability, the presence of alkali metal cations at the cathode improves performance. To overcome this contradiction, we develop an operando activation and regeneration process, where the cathode of a zero-gap electrolyzer cell is periodically infused with alkali cation-containing solutions. This enables deionized water-fed electrolyzers to operate at a CO2 reduction rate matching that of those using alkaline electrolytes (CO partial current density of 420 ± 50 mA cm-2 for over 200 hours). We deconvolute the complex effects of activation and validate the concept with five different electrolytes and three different commercial membranes. Finally, we demonstrate the scalability of this approach on a multi-cell electrolyzer stack, with a 100 cm2 / cell active area.

Microstructuration of poly(3-hexylthiophene) leads to bifunctional superhydrophobic and photoreactive surfaces.

In this paper, we present the first report on an organic conducting polymer film, which alone exhibits both superhydrophobicity and visible light photoactivity. The microstructure of poly(3-hexylthiophene) was optimized using controlled precipitation until superhydrophobic behavior was achieved. Photocatalytic tests employing visible light irradiation proved that polymer degrades the ethanol test molecule.

Nonactivated titanium-dioxide nanoparticles promote the growth of Chlamydia trachomatis and decrease the antimicrobial activity of silver nanoparticles.

AIMS: Chlamydia trachomatis and herpes simplex virus (HSV) are the most prevalent bacterial and viral sexually transmitted infections. Due to the chronic nature of their infections, they are able to interact with titanium-dioxide (TiO2 ) nanoparticles (NPs) applied as food additives or drug delivery vehicles. The aim of this study was to describe the interactions of these two prevalent pathogens with the TiO2 NPs. METHODS AND RESULTS: Chlamydia trachomatis and HSV-2 were treated with nonactivated TiO2 NPs, silver NPs and silver decorated TiO2 NPs before infection of HeLa and Vero cells. Their intracellular growth was monitored by quantitative PCR. Unexpectedly, the TiO2 NPs (100 µg ml-1 ) increased the growth of C. trachomatis by approximately fourfold, while the HSV-2 replication was not affected. Addition of TiO2 to silver NPs decreased their antimicrobial activity against C. trachomatis up to 27·92-fold. CONCLUSION: In summary, nonactivated TiO2 NPs could increase the replication of C. trachomatis and decrease the antimicrobial activity of silver NPs. SIGNIFICANCE AND IMPACT OF THE STUDY: The food industry or drug delivery use of TiO2 NPs could enhance the growth of certain intracellular pathogens and potentially worsen disease symptoms, a feature that should be further investigated.

Comprehensive study on the structure of the BSA from extended-to aged form in wide (2-12) pH range.

In this work we studied the structure of the bovine serum albumin (BSA) and the protein-ligand interactions since researchers prefer to use them as carriers in drug delivery systems. Systematic study (between pH 2-12, in double distilled water and physiological salt solution) was carried out to determine the changes in the secondary and the tertiary structures of the BSA, the apparent molecular weight (Mw), the size (dLS) and the electrokinetic potential (ζ). At pH 7, the BSA has higher stability in the absence (ζ=-69mV, dLS=2.2nm, A2=1.4×10(-3)mlmol/g(2)) than in the presence of salt solution (ζ=-2.4mV, dLS=5.3nm, A2=-3.2×10(-4)mlmol/g(2)). The Mw strongly depends on the pH and the ionic strength (at pH 3 in the absence of salt, the Mw is 54.6kDa while in the presence of salt is 114kDa) which determines the geometry of the protein. The protein-ligand interactions were characterized by fluorescence (FL) and isothermal microcalorimetry (ITC) methods; these independent techniques provided similar thermodynamic parameters such as the binding constant (K) and the Gibbs free energy (ΔG).

Determination of binding capacity and adsorption enthalpy between Human Glutamate Receptor (GluR1) peptide fragments and kynurenic acid by surface plasmon resonance experiments. Part 2: Interaction of GluR1270-300 with KYNA.

In the course of our previous work, the interactions of two peptide fragments (GluR1201-230 and GluR1231-259) of human glutamate receptor (GluR1201-300) polypeptide with kynurenic acid (KYNA) were investigated by surface plasmon resonance (SPR) spectroscopy. Besides quantitation of the interactions, the enthalpies of binding of KYNA on certain peptide fragment-modified gold surfaces were also reported. In the present work, a third peptide fragment (GluR1270-300) of the glutamate receptor was synthesized and its interaction with KYNA was investigated by an SPR technique. This 31-membered peptide was chemically bonded onto a gold-coated SPR chip via a cysteine residue. The peptide-functionalized biosensor chip was analyzed by atomic force microscopy (AFM) and theoretical calculations were performed on the structure and dimensions of the peptide on the gold surface. In order to determine the isosteric heat of adsorption of the binding of KYNA on the peptide-functionalized gold thin film, SPR experiments were carried out between +10°C and +40°C. The results on the GluR1270-300-KYNA system were compared with the previously published binding parameters of the interactions of GluR1201-230 and GluR1231-259 with KYNA. The binding abilities of KYNA with all three peptide fragments immobilized on the gold surface were estimated by a molecular docking procedure and the binding free energies of these AMPA receptor subunits with KYNA were determined.

Bovine serum albumin-sodium alkyl sulfates bioconjugates as drug delivery systems.

Precipitation of bovine serum albumin (BSA) by anionic surfactants with alkyl chains of increasing lengths (octyl, decyl, dodecyl sulfates) was studied at room temperature, at pH 3.0, in isotonic sodium chloride solution. The particle size of albumin, the zeta potential, the surface charge and fluorescent properties of BSA-surfactant composites were investigated concerning addition of increasing amount of surfactant. The thermal stability of the systems was monitored by calorimetric analysis (DSC). The formation of the well-ordered structure in the self-assembly process in liquid phase was studied by XRD measurement. The structure of the precipitated BSA-surfactant nanocomposites was characterized by small-angle X-ray scattering (SAXS). Finally, ibuprofen (IBU) molecules were enclosed in BSA-surfactant bioconjugate systems and the release properties of the drug were investigated. It has been found out that, as a consequence to the increasing number of carbon atoms in the alkyl chains of the surfactant, the structure and the fluorescent properties of the aggregates formed can be controlled due to the increase in the hydrophobicity of BSA-surfactant composites. The bioconjugates are well applicable as carrier to realize controlled release of drug molecules.

BSA/polyelectrolyte core-shell nanoparticles for controlled release of encapsulated ibuprofen.

Bovine serum albumin (BSA) based core-shell nanoparticles were developed as carrier systems for drug transportation. At pH=3, the oppositely charged polyelectrolytes: poly(sodium-4-styrene)sulphonate (PSS) and the chitosan (Chit) bind to the positively charged protein via electrostatic interactions. We applied ibuprofen (IBU) as model molecule which has low solubility. The changes in the BSA's secondary structure during the steps of the synthesis were inspected by FT-IR measurements. The size and the zeta potential were determined by dynamic light scattering (DLS). The changes in the structure and in the size were investigated by small angle X-ray scattering (SAXS) too, for each composite. The release of the ibuprofen was studied by vertical diffusion cell (Franz cell) at pH 7.4 at 25 and 37.5°C. The structure of the core-shell nanoparticles have significantly changed as the pH has risen from 3.0 to 7.4. Kinetic models were used to describe the release mechanism. The experimental results demonstrated that the BSA has an ordered structure at pH=3 which will become random coil by adding ibuprofen. The first shell restores the ordered structure of the protein. The controlled release was carried out; the IBU release decreased by 40% in the case of two-layered composites compared with the "naked" BSA.

Variation in MR signal intensity across normal human knee cartilage.

Signal intensity (SI) of individual pixels on sagittal magnetic resonance (MR) images of normal human knee cartilage was quantified to investigate whether it was related to cartilage proteoglycan content. In five subjects, images were acquired with spin-echo sequences with a TR msec/TE msec of 1,000 or 700/20 and a three-dimensional gradient-echo (GRE) sequence (60/15). In a sixth subject, the GRE sequence alone was used with 15 degrees, 30 degrees, and 50 degrees flip angles. In all subjects, SI was maximal in pixel layers of the medial zone and minimal at both cartilage edges, resulting in the presence of a bell-shaped curve of interpixel (zonal) SI variation across the cartilage thickness. The magnitude of SI was dependent on the pulse sequence and flip angle, but the bell shape of the SI variation curve was independent of them. For example, in the medial tibial cartilage, the peak SI was highest with the 1,000/20 spin-echo sequence, intermediate with the 700/20 sequence, and lowest with the GRE sequence. The differences were statistically significant. The bell-shaped SI variation curve resembled the curve for zonal variation in cartilage proteoglycan content but not the curves for collagen or free water content. The physiologic basis for this resemblance and the potential usefulness of the findings for early diagnosis of diseases such as osteoarthritis are discussed.

In-vitro assessment of the behavior of magnetic resonance angiography in the presence of constrictions.

RATIONALE AND OBJECTIVES: Time-of-flight magnetic resonance angiography (TOF/MRA) is increasingly used to assess the nature and severity of stenotic blood vessels. Flow artifacts associated with high flows and/or narrow constrictions may confuse the interpretation of these studies. Accurate TOF/MRA evaluations demand an understanding of the nature of these flow effects. METHODS: A two-dimensional TOF pulse sequence was used to acquire images of five smoothly constricted phantoms at various flows. Analysis included assessment of phantom appearance and quantification of apparent constriction diameter and signal variations. RESULTS: Most notable flow phenomena were a cone-shaped region of high signal, a region of signal void, and signal preservation along the wall. When visible, constriction diameter was accurately measured. CONCLUSIONS: The behavior observed in TOF/MRA images can be understood by considering the contributing mechanisms of phase dispersion, turbulence, poststenotic flow eddies, flow reversal, and flow separation.

The comparative evaluation of three-dimensional magnetic resonance for carotid artery disease.

Conventional angiography is the current standard for the evaluation of carotid artery disease. The excellent resolution of this invasive study is offset by the potential for contrast-related, embolic, and puncture site complications. Three-dimensional magnetic resonance angiography may offer a noninvasive diagnostic alternative. We examined this possibility by performing both conventional angiography and three-dimensional magnetic resonance angiography in 13 patients. Cervical duplex scans were also obtained in these patients. Contiguous transverse cervical magnetic resonance images were acquired in a 1.5 tesla magnet, by use of a posterior neck coil and a gradient echo pulse sequence. These "raw" data were transferred to a real-time workstation where three-dimensional cervical arterial images were reformatted, magnified, and examined from multiple angles. Total study time from patient positioning to image generation was approximately 30 minutes. In all patients, on three-dimensional magnetic resonance angiography the common, external, and internal carotid arteries and distal vertebral arteries were easily discernable and correctly identified as patent, stenotic, or occluded. Three-dimensional magnetic resonance angiography was not accurate in detecting carotid ulcers. The degree of internal carotid artery stenosis measured from the three-dimensional magnetic resonance angiography studies correlated well with the internal carotid artery stenosis measured with conventional angiography (r = 0.866, r2 = 75.1%, p = less than or equal to 0.0001). This recent technologic advance represents significant progress toward achieving the goal of completely noninvasive vascular assessment in this patient population.

Interleaved magnetic resonance and ultrasound by electronic synchronization.

Increasing attention has been directed toward using magnetic resonance imaging (MRI) to assess blood flow velocity. Complete acceptance of this application requires validation of MRI-derived flow measurements against an accepted flow measurement technique such as Doppler ultrasound in an in vivo situation. To provide an accurate correlation in the presence of rapid changes in blood flow, the MR acquisition should be made nearly simultaneously with the ultrasonic measurements. Unfortunately, standard ultrasound equipment generates radio frequency signal which interferes with MRI. Near-simultaneous acquisition of MR data and ultrasonic blood flow data should be possible if the two measurements are properly synchronized. In the technique presented, ultrasound is made to peacefully coexist with MRI by gating the ultrasound so that it is disabled during the time of MR data acquisition. Phantom and animal experiments confirm the use of this procedure. Although we did not specifically test new fast-scan MR techniques, our technique is completely general and should work equally well with spin-echo as well as newer fast scanning MRI techniques.

Image processing on Macintosh II: a practical boundary finding algorithm for biomedical measurement.

With increasing research interest in displaying and analyzing biomedical images, a practical personal computer based off-line image processing software would be useful. This paper describes the implementation of an image processing work station on a Macintosh II which features a novel edge detection capability useful for biomedical measurement. The boundary finding algorithm is coded in Turbo Pascal, and operates at a speed comfortable for interactive operation. Depending on the complexity of the problem, it usually takes less than a minute for the measurement of an image. The edge detection algorithm has an built-in edge detector with decision-making capability, and can be efficiently controlled by a mouse. In this way, the local accuracy of an automatic edge detection operator, and the global accuracy of the human eye (through manual control of a mouse) are combined.

Magnetic resonance imaging of acute occlusive intestinal ischemia.

The mortality of acute superior mesenteric artery occlusion and mesenteric infarction remains high, in part because of the failure to identify the patients with the disorder. A reliable noninvasive diagnostic study may facilitate earlier definitive diagnosis and therapy. Proton magnetic resonance imaging may offer a noninvasive diagnostic alternative. We examined this possibility by using an experimental rabbit model of acute superior mesenteric artery occlusion in this study. Animals were scanned 1 hour after the ischemic insult. Relative intestinal wall signal intensity was increased in experimental (ischemic) animals when compared to sham operated controls on T2-weighted (4.35 +/- 0.5 vs 2.57 +/- 0.31, p less than 0.02) and proton spin density-weighted images (2.1 +/- 0.2 vs 1.4 +/- 0.21, p less than 0.05). Significant increases in image intensity were found on T2-weighted and proton spin density images when compared to control animals. Differences between groups could be further highlighted after the administration of a paramagnetic contrast agent gadolinium diethyltriamine pentacetic acid on T1-weighted images. The data from this preliminary study demonstrate that proton magnetic resonance imaging may be used to discriminate between ischemic and nonischemic small intestine. This noninvasive tool may someday become clinically useful to enhance our diagnostic capabilities when a diagnosis of acute superior mesenteric artery occlusion is being entertained.

Single-acquisition chemical-shift imaging of a binary system with use of stimulated echoes.

A method for separating binary chemical-shift components with a single image data acquisition by means of stimulated echoes is demonstrated. With a strategy analogous to the modified Dixon method, three stimulated echoes were acquired to form three complex images. In each of the images, the complex pixel intensities were imparted, by design of the pulse sequence, with a phase factor carrying chemical-shift or field inhomogeneity information. With these three images, true fat/water separation can be obtained in biologic tissues. Studies at high field strength (4.7 T) on a toluene phantom, a pseudo-binary chemical-shift system, were used to evaluate the applicability of the method. Its clinical feasibility was demonstrated on a healthy human subject in a 0.6-T whole-body imaging system.