Dialysate regeneration via urea photodecomposition with TiO2 nanowires at therapeutic rates.

BACKGROUND: The standard weekly treatment for end-stage renal disease patients is three 4-h-long hemodialysis sessions with each session c'onsuming over 120 L of clean dialysate, which prevents the development of portable or continuous ambulatory dialysis treatments. The regeneration of a small (~1 L) amount of dialysate would enable treatments that give conditions close to continuous hemostasis and improve patient quality of life through mobility. METHODS: Small-scale studies have shown that nanowires of TiO2 are highly efficient at photodecomposing urea into CO2 and N2 when using an applied bias and an air permeable cathode. To enable the demonstration of a dialysate regeneration system at therapeutically useful rates, a scalable microwave hydrothermal synthesis of single crystal TiO2 nanowires grown directly from conductive substrates was developed. These were incorporated into 1810 cm2 flow channel arrays. The regenerated dialysate samples were treated with activated carbon (2 min at 0.2 g/mL). RESULTS: The photodecomposition system achieved the therapeutic target of 14.2 g urea removal in 24 h. TiO2 electrode had a high urea removal photocurrent efficiency of 91%, with less than 1% of the decomposed urea generating NH4 + (1.04 µg/h/cm2 ), 3% generating NO3 - and 0.5% generating chlorine species. Activated carbon treatment could reduce total chlorine concentration from 0.15 to <0.02 mg/L. The regenerated dialysate showed significant cytotoxicity which could be removed by treatment with activated carbon. Additionally, a forward osmosis membrane with sufficient urea flux can cut off the mass transfer of the by-products back into the dialysate. CONCLUSION: Urea could be removed from spent dialysate at a therapeutic rate using a TiO2 based photooxidation unit, which can enable portable dialysis systems.

Strategies for optimizing urea removal to enable portable kidney dialysis: A reappraisal.

BACKGROUND: Portable hemodialysis has the potential to improve health outcomes and quality of life for patients with kidney failure at reduced costs. Urea removal, required for dialysate regeneration, is a central function of any existing/potential portable dialysis device. Urea in the spent dialysate coexists with non-urea uremic toxins, nutrients, and electrolytes, all of which will interfere with the urea removal efficiency, regardless of whether the underlying urea removal mechanism is based on urease conversion, direct urea adsorption, or oxidation. The aim of the current review is to identify the amount of the most prevalent chemicals being removed during a single dialysis session and evaluate the potential benefits of an urea-selective membrane for portable dialysis. METHODS: We have performed a literature search using Web of Science and PubMed databases to find available articles reporting (or be able to calculate from blood plasma concentration) > 5 mg of individually quantified solutes removed during thrice-weekly hemodialysis sessions. If multiple reports of the same solute were available, the reported values were averaged, and the geometric mean of standard deviations was taken. Further critical literature analysis of reported dialysate regeneration methods was performed using Web of Science and PubMed databases. RESULTS: On average, 46.0 g uremic retention solutes are removed in a single conventional dialysis session, out of which urea is only 23.6 g. For both urease- and sorbent-based urea removal mechanisms, amino acids, with 7.7 g removal per session, could potentially interfere with urea removal efficiency. Additionally for the oxidation-based urea removal system, plentiful nutrients such as glucose (24.0 g) will interfere with urea removal by competition. Using a nanofiltration membrane between dialysate and oxidation unit with a molecular weight cutoff (MWCO) of ~200 Da, 67.6 g of non-electrolyte species will be removed in a single dialysis session, out of which 44.0 g are non-urea molecules. If the membrane MWCO is further decreased to 120 Da, the mass of non-electrolyte non-urea species will drop to 9.3 g. Reverse osmosis membranes have been shown to be both effective at blocking the transport of non-urea species (creatinine for example with ~90% rejection ratio), and permissive for urea transport (~20% rejection ratio), making them a promising urea selective membrane to increase the efficiency of the oxidative urea removal system. CONCLUSIONS: Compiled are quantified solute removal amounts greater than 5 mg per session during conventional hemodialysis treatments, to act as a guide for portable dialysis system design. Analysis shows that multiple chemical species in the dialysate interfere with all proposed portable urea removal systems. This suggests the need for an additional protective dialysate loop coupled to urea removal system and an urea-selective membrane.

Micro- and nano-patterned conductive graphene-PEG hybrid scaffolds for cardiac tissue engineering.

A lack of electrical conductivity and structural organization in currently available biomaterial scaffolds limits their utility for generating physiologically representative models of functional cardiac tissue. Here we report on the development of scalable, graphene-functionalized topographies with anisotropic electrical conductivity for engineering the structural and functional phenotypes of macroscopic cardiac tissue constructs. Guided by anisotropic electroconductive and topographic cues, the tissue constructs displayed structural property enhancement in myofibrils and sarcomeres, and exhibited significant increases in the expression of cell-cell coupling and calcium handling proteins, as well as in action potential duration and peak calcium release.

Nanoscale surface potential variation correlates with local S/Se ratio in solution-processed CZTSSe solar cells.

Thin film solar cells made from Cu, Zn, Sn, and S/Se can be processed from solution to yield high-performing kesterite (CZTS or CZTSSe) photovoltaics. We present a microstructural study of solution-deposited CZTSSe films prepared by nanocrystal-based ink approaches using scanning probe microscopy (SPM) and scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). We correlate scanning Kelvin probe microscopy (SKPM) maps of local surface potential with SEM/EDS images of the exact same regions of the film, allowing us to relate observed variations in surface potential to local variations in stoichiometry. Specifically, we find a correlation between surface potential and the S/(S + Se) composition ratio. In particular, we find that regions with high S/(S + Se) ratios are often associated with regions of more negative surface potential and thus higher work function. The change in work function is larger than the expected change in the valence band position with these small changes in sulfur, and thus the data suggest an increase in acceptor-like defects with increasing sulfur. These findings provide new experimental insight into the microscopic relationships between composition, structure, and electronic properties in these promising photovoltaic materials.

Intensity-modulated scanning Kelvin probe microscopy for probing recombination in organic photovoltaics.

We study surface photovoltage decays on sub-millisecond time scales in organic solar cells using intensity-modulated scanning Kelvin probe microscopy (SKPM). Using polymer/fullerene (poly[N-9"-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]/[6,6]-phenyl C71-butyric acid methyl ester, PCDTBT/PC71BM) bulk heterojunction devices as a test case, we show that the decay lifetimes measured by SKPM depend on the intensity of the background illumination. We propose that this intensity dependence is related to the well-known carrier-density-dependent recombination kinetics in organic bulk heterojunction materials. We perform transient photovoltage (TPV) and charge extraction (CE) measurements on the PCDTBT/PC71BM blends to extract the carrier-density dependence of the recombination lifetime in our samples, and we find that the device TPV and CE data are in good agreement with the intensity and frequency dependence observed via SKPM. Finally, we demonstrate the capability of intensity-modulated SKPM to probe local recombination rates due to buried interfaces in organic photovoltaics (OPVs). We measure the differences in photovoltage decay lifetimes over regions of an OPV cell fabricated on an indium tin oxide electrode patterned with two different phosphonic acid monolayers known to affect carrier lifetime.

Correlating structure and photocurrent for composite semiconducting nanoparticles with contrast variation small-angle neutron scattering and photoconductive atomic force microscopy.

Aqueous dispersions of semiconducting nanoparticles have shown promise as a robust and scalable platform for the production of efficient polymer/fullerene active layers in organic photovoltaic applications. Semiconducting nanoparticles are a composite of both an n-type and p-type semiconductor contained within a single nanoparticle. In order to realize efficient organic solar cells from these materials, there is a need to understand how the size and internal distribution of materials within each nanoparticle contributes to photocurrent generation in a nanoparticle-derived device. Therefore, characterizing the internal distribution of conjugated polymer and fullerene within the dispersion is the first step to improving performance. To date, study of polymer/fullerene structure within these nanoparticles has been limited to microscopy techniques of deposited nanoparticles. In this work, we use contrast variation with small-angle neutron scattering to determine the internal distribution of poly(3-hexylthiophene) and [6,6]phenyl-C61-butyric acid methyl ester inside the composite nanoparticles as a function of formulation while in dispersion. On the basis of these measurements, we connect the formulation of these nanoparticles with their internal structure. Using electrostatic deposited monolayers of these nanoparticles, we characterize intrinsic charge generation using photoconductive atomic force microscopy and correlate this with structures determined from small-angle neutron scattering measurements. These techniques combined show that the best performing composite nanoparticles are those that have a uniform distribution of conjugated polymer and fullerene throughout the nanoparticle volume such that electrons and holes are easily transported out of the particle.

Morphology-dependent trap formation in bulk heterojunction photodiodes.

We show that local structural variation affects the rate of aging in nanostructured polymer solar cells by comparing time-resolved electrostatic force microscopy (trEFM) and conventional device measurements on model polymer blends. Specifically, we study photovoltaic devices made from 1:1 blends of the polyfluorene copolymers poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylene-diamine) (PFB) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT). We photooxidize these films in situ using 365, 405, and 455 nm illumination under ambient conditions, with the wavelengths chosen to preferentially excite the different components. During photooxidation, we observe a faster loss of photocurrent generation from F8BT-rich domains, leaving the PFB-rich phases to show higher photoresponse even at wavelengths absorbed predominantly by F8BT. We propose that this effect is due to the more rapid degradation of PFB hole-transport pathways in the F8BT-rich regions, resulting in a loss of percolation pathways for hole transport in the F8BT-rich phase.

Submicrosecond time resolution atomic force microscopy for probing nanoscale dynamics.

We propose, simulate, and experimentally validate a new mechanical detection method to analyze atomic force microscopy (AFM) cantilever motion that enables noncontact discrimination of transient events with ~100 ns temporal resolution without the need for custom AFM probes, specialized instrumentation, or expensive add-on hardware. As an example application, we use the method to screen thermally annealed poly(3-hexylthiophene):phenyl-C(61)-butyric acid methyl ester photovoltaic devices under realistic testing conditions over a technologically relevant performance window. We show that variations in device efficiency and nanoscale transient charging behavior are correlated, thereby linking local dynamics with device behavior. We anticipate that this method will find application in scanning probe experiments of dynamic local mechanical, electronic, magnetic, and biophysical phenomena.