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In this paper, we propose a lightweight wearable thermoelectric (TE) cooler with a rationally designed flexible heatsink. Heatsinks are commonly designed for use with stationary applications, and are consequently rigid and heavy. These traditional heatsinks are incompatible with wearable applications, which must be durable, mechanically flexible, and lightweight while maintaining performance. This paper presents a flexible heatsink based on a ternary composite of silicone elastomer, phase-change material, and graphite powder; this combination is needed to achieve high flexibility and durability as well as the optimum heat capacity and thermal conductivity. Those factors are key requirements for a heatsink to optimize the cooling performance of a TE cooler and maintain a longer cooling capacity. With our optimized ternary composite flexible heatsink, we achieved a cooling temperature of ∼5 K at 0.5 W input power and kept cooling for more than 5 h under ambient conditions. On-body testing of the wearable TE cooler with flexible heatsink was also performed to demonstrate potential applications in the real-world. Our work provides fundamental insights to designing wearable TE devices and paves the way for innovative solutions for on-body thermal management applications such as clothing, hats, seat cushions, and other portable devices.

Polyacetal electrolytes have been demonstrated as promising alternatives to liquid electrolytes and poly(ethylene oxide) (PEO) for rechargeable lithium-ion batteries; however, the relationship between polymer structure and ion motion is difficult to characterize. Here, we study structure-property trends in ion diffusion with respect to polymer composition for a systematic series of five polyacetals with varying ratios of ethylene oxide (EO) to methylene oxide (MO) units, denoted as P(xEO-yMO), and PEO. We first use 7Li and 19F pulsed-field-gradient NMR spectroscopy to measure cation and anion self-diffusion, respectively, in polymer/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt mixtures. At 90 °C, we observe modest changes in Li+ diffusivity across all polymer compositions, while anion (TFSI-) self-diffusion coefficients decrease significantly with increasing MO content. At a given reduced temperature (T - Tg), all polyacetal electrolytes exhibit faster Li+ self-diffusion than PEO. Intriguingly, P(EO-MO) and P(EO-2MO) also show slower TFSI- anion self-diffusion than PEO at a given reduced temperature. Molecular dynamics simulations reveal that shorter distances between acetal oxygen atoms (O-CH2-O) compared to ether oxygens (O-CH2-CH2-O) promote more diverse, often asymmetric, Li+ coordination environments. Raman spectra reveal that anion-rich ion clusters in P(EO-MO) and P(EO-2MO) lead to decreased anion diffusivity, which along with increased cation diffusivity, support the viability of polyacetals as high-performance polymer electrolytes.

Heteroatom substitution can favorably alter electronic transport in conductive polymers to improve their thermoelectric performance. This study reports the spectroscopic, structural, and thermoelectric properties of poly(3-(3′,7′-dimethyloctyl) chalcogenophenes) or P3RX doped with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), where the heteroatom [X = thiophene (T), selenophene (Se), tellurophene (Te)], the doping methodology, and extent of doping are systematically varied. Spectroscopic measurements reveal that while all P3RX polymers are appreciably doped, the doping mechanism is inherently different. Poly(3-hexylthiophene) (P3HT, used as a control) and poly(3-(3′,7′-dimethyloctyl)tellurophene) (P3RTe) are doped primarily via integer charge transfer (ICT), whereas poly(3-(3′,7′-dimethyloctyl)selenophene) (P3RSe) and poly(3-(3′,7′-dimethyloctyl)thiophene) (P3RT) are doped via charge transfer complex (CTC) mechanisms. Despite these differences, all polymers saturate with roughly the same number of F4TCNQ counterions (1 dopant per 4 to 6 heterocycles), reinforcing the idea that the extent of charge transfer varies with the doping mechanism. Grazing incidence wide-angle x-ray scattering measurements provide insight into the structural driving forces behind different doping mechanisms—P3RT and P3RSe have similar microstructures in which F4TCNQ intercalates between the π-stacked backbones resulting in CTC doping (localized carriers), while P3HT and P3RTe have microstructures in which F4TCNQ intercalates in the alkyl side chain region, giving rise to ICT doping (delocalized carriers). These structural and spectroscopic observations shed light on why P3HT and P3RTe obtain electrical conductivities ca. 3 S/cm, while P3RT and P3RSe have conductivities

Organic–inorganic hybrids offer great promise as solution-processable thermoelectric materials. However, they have struggled to surpass the performance of their rigid inorganic counterparts due, in part, to a lack of synthetic control and limited understanding of how inorganic nanostructure dimensions impact overall charge transport. While it has been hypothesized that length, diameter, and aspect ratio (AR) all impact electronic transport in hybrid nanowires, the field lacks clarity on the relative role of each. In this study, the experimental parameter of ligand molecular weight (MW) is investigated as a synthetic knob for modulating nanowire dimensions, as well as the deconvolution of nanowire length versus diameter impacts on electron transport. By increasing ligand MW, larger nanowire AR dispersions occur and an optimal power factor of ≈130 μWm−1 K−2 is achieved for a modest AR of 73. Power factors of this magnitude are thought to only be achievable in ultrahigh AR systems; representing a 183% increase in performance over literature reports with similar AR. Additionally, nanowire diameter is demonstrated to be a far more sensitive parameter for enhancing performance than modulating length. This study provides improved fundamental insight into rational synthetic design avenues for future enhancements in the performance of hybrid materials.

For the sake of water and energy conservation, development of latent heat cooling and thermal storage systems that minimize water consumption and operate with higher efficacy than their water-driven counterparts is a crucial task. Phase change materials (PCMs) present a potential solution, but their integration into real-world systems abounds with scientific challenges such as material toxicity, flammability, low thermal performance and lack of tunable phase-change temperatures. In this study we report on a first-in-class nanocomposite PCM that leverages non-flammable, non-toxic, high latent heat sugar alcohols (SAs) encapsulated within easy-to-synthesize zeolitic imidazolate framework (ZIF) crystals. We also outline a practical route for surface functionalization with hydrophilic and hydrophobic moieties. The SA@ZIF composites display suppressed phase-change temperatures which, together with alterable surface functionality, broadens their applicability to a plethora of working environments. Direct synthesis of the SA@ZIF composite generates nanoconfined SAs with phase-change temperatures as low as 19.8 °C and latent heats as high as 285 J g-1. This nanoconfinement-induced thermal phenomenon is conserved even after functionalization of the SA@ZIF crystal surface. We believe this study will lay the groundwork as a platform for next generation high performing, tunable PCMs to aid in the realization of waterless cooling systems.

Sodium borohydride (NaBH4) has been a material of interest for many years in developing metal boride complexes and shows a great deal of potential as a hydrogen storage material. Though many have used various additives as catalysts to weaken the bonds within NaBH4 to create a more energetically favorable material, very little is understood about how the borohydride interacts with and changes the additives being incorporated. This work uses ball milling to incorporate calcium chloride (CaCl2) into NaBH4. Using several x-ray techniques, thermogravimetric analysis, and Raman spectroscopy, this study shows not only that the salt diffuses into NaBH4 but describes how the borohydride changes the additive itself. In gaining a stronger understanding of what happens to the additives needed to weaken the borohydride bonds, future researchers may have an easier time selecting the appropriate additive to create a borohydride complex that will meet their needs.

Porous graphitic framework (PGF) is a two-dimensional (2D) material that has emerging energy applications. An archetype contains stacked 2D layers, the structure of which features a fully annulated aromatic skeleton with embedded heteroatoms and periodic pores. Due to the lack of a rational approach in establishing in-plane order under mild synthetic conditions, the structural integrity of PGF has remained elusive and ultimately limited its material performance. Here, we report the discovery of the unusual dynamic character of the C=N bonds in the aromatic pyrazine ring system under basic aqueous conditions, which enables the successful synthesis of a crystalline porous nitrogenous graphitic framework with remarkable in-plane order, as evidenced by powder X-ray diffraction studies and direct visualization using high-resolution transmission electron microscopy. The crystalline framework displays superior performance as a cathode material for lithium-ion batteries, outperforming the amorphous counterparts in terms of capacity and cycle stability. Insertion of well-defined, evenly spaced nanoscale pores into the two-dimensional (2D) layers of graphene invokes exciting properties due to the modulation of its electronic band gaps and surface functionalities. A bottom-up synthesis approach to such porous graphitic frameworks (PGFs) is appealing but also remains a great challenge. The current methods of building covalent organic frameworks rely on a small collection of thermodynamically reversible reactions. Such reactions are, however, inadequate in generating a fully annulated aromatic skeleton in PGFs. With the discovery of dynamic pyrazine formation, we succeeded in applying this linking chemistry to obtain a crystalline PGF material, which has displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries. We envision that the demonstrated success will open the door to a wide array of fully annulated 2D porous frameworks, which hold immense potential for clean energy applications. We report the unusual dynamic characteristics of the C=N bonds in the pyrazine ring promoted under basic aqueous conditions, which enables the successful synthesis of two-dimensional porous graphitic frameworks (PGFs) featuring fully annulated aromatic skeletons and periodic pores. The PGF displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries, far outperforming the amorphous counterparts in terms of capacity and cycle stability.

A high-performance, wearable thermoelectric generator (TEG) was fabricated with a highly aligned carbon nanotube (CNT) sheet. The aligned CNT sheet exhibits extraordinary electrical conductivity compared to disordered CNT sheets and also can be directly fabricated as a continuous TEG without metal electrode interconnects. This provides a significant reduction in contact resistance between TE legs and electrodes compared to traditional TEGs, resulting in higher power output. In addition, the continuity of the module without any disconnected parts provides high degrees of mechanical stability and durability. This robust and scalable approach to flexible TEG fabrication paves the way for CNT applications in lightweight, flexible, and wearable electronics.

Cu2Se thin films provide a promising route toward relatively safe, sustainable and solution processed thermoelectric (TE) modules in contrast to more expensive and toxic materials currently on the market such as Bi2Te3. Cu2Se is known in the TE community for its high performance at high temperature and has recently attracted attention from its large theoretically predicted figure of merit at room temperature. Unfortunately, one of the main limitations encountered so far in Cu2Se thin films is that the carrier concentrations are not optimized for TE operation after solution processing. In this work, we conduct a comprehensive study of the structural, optical, and TE properties of Cu2Se thin films and demonstrate that nonoptimized carrier concentrations in these films lead to observations of poor performance at room temperature. Through a simple soaking procedure in a Cu+ ion solution for only a few minutes, we demonstrate a 200-300% increase in power factor. This soaking process pushes the carrier concentration of the Cu2Se thin film toward its optimal value for TE operation and marks the highest TE performance for any solution processed Cu2Se thin film at room temperature thus far. If the performance can be further optimized at room temperature, Cu2Se thin films will be the material of choice to utilize in TE modules for powering miniature electronics and sensors, which has been an increasingly popular and rapidly expanding market.

Thermoelectric properties of conducting polymers typically suffer from molecular chain disordering, as charge transport is predominantly controlled by morphology. This is especially more problematic when counterions are introduced to tune the carrier concentration for optimal thermoelectric performance, which disturbs the morphology further. In this work, we introduce a new avenue for enhancing thermoelectric properties without needing to regulate the morphology, namely, by controlling the coulombic interaction between polarons and counterions. We perform in situ de-doping thermoelectric experiments over 3 orders of magnitude change in electrical conductivity of three distinct thermoelectric polymers, namely, poly(3-hexylthiophene-2,5-diyl) (P3HT), poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2- b ]thiophene] (PBTTT-C 12 ), and poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole- alt -5,5-(2,5-di(thien-2-yl)thieno[3,2- b ]thiophene)] (OD-PDPP2T-TT) conjugated polymers, followed by grazing-incidence wide-angle X-ray scattering (GIWAXS) to study their respective morphologies. We demonstrate a 9-fold enhancement in the thermoelectric power factor in OD-PDPP2T-TT compared to PBTTT-C 12 and link it to the coulombic screening of charge carriers, including in the optimally doped regime. We support this hypothesis using Boltzmann transport equations and show that, in both P3HT and PBTTT-C 12 , as the polymer is doped, impurity scattering remains the dominant scattering mechanism, while in OD-PDPP2T-TT, the scattering mechanism changes from impurity to acoustic phonon limited, resulting in more effective screening of ionized counterions. Our results provide an additional knob to enhance the fundamental understanding of thermoelectric physics of conducting polymers and provide a pathway to achieve higher performance in the field of organic thermoelectrics.

Inorganic-organic hybrids, such as Te-PEDOT:PSS core/shell nanowires, have emerged as a class of promising thermoelectric materials with combined attributes of mechanical flexibility and low cost. However, the poorly understood structure-property relationship calls for further investigation for performance enhancement. Here, through precise treatments of focused electron beam irradiation and thermal annealing on individual Te-PEDOT:PSS nanowires, new, nonchemical mechanisms are introduced to specifically engineer the organic phase, and the measured results provide an unprecedented piece of evidence, confirming the dominant role of organic shell in charge transport. Paired with the Kang-Snyder model and molecular dynamics simulations, this work provides mechanistic insights in terms of heating-enabled morphological ordering of the polymer chains. The measured results show that thermal annealing on the 42 nm nanowire results in a ZT value of 0.78 at 450 K. Through leveraging the interfacial self-assembly of the organic phase to construct a high electrical conductivity domain, this work lays out a clear framework for the development of next-generation soft thermoelectrics.

This study investigates the charge-transport properties of poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly(ProDOT- alt -biEDOT) (PE 2 ) films doped with a set of iron(III)-based dopants and as a function of dopant concentration. X-ray photoelectron spectroscopy measurements show that doping P3HT with 12 mM iron(III) solutions leads to similar extents of oxidation, independent of the dopant anion; however, the electrical conductivities and Seebeck coefficients vary significantly (5 S cm -1 and + 82 μV K -1 with tosylate and 56 S cm -1 and +31 μV K -1 with perchlorate). In contrast, PE 2 thermoelectric transport properties vary less with respect to the iron(III) anion chemistry, which is attributed to PE 2 having a lower onset of oxidation than P3HT. Consequentially, PE 2 doped with 12 mM iron(III) perchlorate obtained an electrical conductivity of 315 S cm -1 and a Seebeck coefficient of + 7 μV K -1 . Modeling these thermoelectric properties with the semilocalized transport (SLoT) model suggests that tosylate-doped P3HT remains mostly in the localized transport regime, attributed to more disorder in the microstructure. In contrast perchlorate-doped P3HT and PE 2 films exhibited thermally deactivated electrical conductivities and metal-like transport at high doping levels over limited temperature ranges. Finally, the SLoT model suggests that PE 2 has the potential to be more electrically conductive than P3HT due to PE 2 's ability to achieve higher extents of oxidation and larger shifts in the reduced Fermi energy levels.

Two-dimensional (2D) anatase titanium dioxide (TiO 2 ) is expected to exhibit different properties as compared to anatase nanocrystallites, due to its highly reactive exposed facets. However, access to 2D anatase TiO 2 is limited by the non-layered nature of the bulk crystal, which does not allow use of top-down chemical exfoliation. Large efforts have been dedicated to the growth of 2D anatase TiO 2 with high reactive facets by bottom-up approaches, which relies on the use of harmful chemical reagents. Here, we demonstrate a novel fluorine-free strategy based on topochemical conversion of 2D 1T-TiS 2 for the production of single crystalline 2D anatase TiO 2 , exposing the {001} facet on the top and bottom and {100} at the sides of the nanosheet. The exposure of these faces, with no additional defects or doping, gives rise to a significant activity enhancement in the hydrogen evolution reaction, as compared to commercially available Degussa P25 TiO 2 nanoparticles. Because of the strong potential of TiO 2 in many energy-based applications, our topochemical approach offers a low cost, green and mass scalable route for production of highly crystalline anatase TiO 2 with well controlled and highly reactive exposed facets., Competing Interests: Thee are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Limiting emissions of climate-warming methane from oil and gas (O&G) is a major opportunity for short-term climate benefits. We deploy a basin-wide airborne survey of O&G extraction and transportation activities in the New Mexico Permian Basin, spanning 35 923 km 2 , 26 292 active wells, and over 15 000 km of natural gas pipelines using an independently validated hyperspectral methane point source detection and quantification system. The airborne survey repeatedly visited over 90% of the active wells in the survey region throughout October 2018 to January 2020, totaling approximately 98 000 well site visits. We estimate total O&G methane emissions in this area at 194 (+72/-68, 95% CI) metric tonnes per hour (t/h), or 9.4% (+3.5%/-3.3%) of gross gas production. 50% of observed emissions come from large emission sources with persistence-averaged emission rates over 308 kg/h. The fact that a large sample size is required to characterize the heavy tail of the distribution emphasizes the importance of capturing low-probability, high-consequence events through basin-wide surveys when estimating regional O&G methane emissions.

The sky is a natural heat sink that has been extensively used for passive radiative cooling of households. A lot of focus has been on maximizing the radiative cooling power of roof coating in the hot daytime using static, cooling-optimized material properties. However, the resultant overcooling in cold night or winter times exacerbates the heating cost, especially in climates where heating dominates energy consumption. We approached thermal regulation from an all-season perspective by developing a mechanically flexible coating that adapts its thermal emittance to different ambient temperatures. The fabricated temperature-adaptive radiative coating (TARC) optimally absorbs the solar energy and automatically switches thermal emittance from 0.20 for ambient temperatures lower than 15°C to 0.90 for temperatures above 30°C, driven by a photonically amplified metal-insulator transition. Simulations show that this system outperforms existing roof coatings for energy saving in most climates, especially those with substantial seasonal variations.

Background: Working memory decline has been associated with normal aging. The frontal brain structure responsible for this decline is primarily located in the prefrontal cortex (PFC). Our previous neuroimaging study demonstrated a significant change in functional connectivity between the left dorsolateral PFC (DLPFC) and left ventrolateral PFC (VLPFC) when applying 2 mA tDCS in MRI scanner during an N-Back task. These regions were part of the working memory network. The present study is the first study that utilizes individualized finite element models derived from older adults' MRI to predict significant changes of functional connectivity observed from an acute tDCS application., Methods: Individualized head models from 15 healthy older adults (mean age = 71.3 years) were constructed to create current density maps. Each head model was segmented into 11 tissue types: white matter, gray matter, CSF, muscle, blood vessels, fat, eyes, air, skin, cancellous, and cortical bone. Electrodes were segmented from T1-weighted images and added to the models. Computed median and maximum current density values in the left DLPFC and left VLPFC regions of interest (ROIs) were correlated with beta values as functional connectivity metrics measured in different timepoint (baseline, during stimulation) and stimulation condition (active and sham)., Main Results: Positive significant correlations (R 2  = 0.523 for max J, R 2  = 0.367 for median J, p < 0.05) were found between the beta values and computed current densities in the left DLPFC ROIs for active stimulation, but no significant correlation was found during sham stimulation. We found no significant correlation between connectivity and current densities computed in the left VLPFC for both active and sham stimulation., Conclusions: The amount of current within the left DLPFC ROIs was found positively correlated with changes in functional connectivity between left DLPFC and left VLPFC during active 2 mA stimulation. Future work may include expansion of number of participants to further test the accuracy of tDCS models used to predict tDCS-induced functional connectivity changes within the working memory network., Competing Interests: Declaration of competing interest We wish to confirm that there are no known conflicts of interest associated with this publication and there has been no significant financial support for this work that could have influenced its outcome. We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. We further confirm that the order of authors listed in the manuscript has been approved by all of us. We confirm that we have given due consideration to the protection of intellectual property associated with this work and that there are no impediments to publication, including the timing of publication, with respect to intellectual property. In so doing we confirm that we have followed the regulations of our institutions concerning intellectual property. We further confirm that any aspect of the work covered in this manuscript that has involved either experimental animals or human patients has been conducted with the ethical approval of all relevant bodies and that such approvals are acknowledged within the manuscript. We understand that the Corresponding Author is the sole contact for the Editorial process (including Editorial Manager and direct communications with the office). He/she is responsible for communicating with the other authors about progress, submissions of revisions and final approval of proofs. We confirm that we have provided a current, correct email address which is accessible by the Corresponding Author and which has been configured to accept email from: aprinda.indahlas@phhp.ufl.edu., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Organic-inorganic hybrids have recently emerged as a class of high-performing thermoelectric materials that are lightweight and mechanically flexible. However, the fundamental electrical and thermal transport in these materials has remained elusive due to the heterogeneity of bulk, polycrystalline, thin films reported thus far. Here, we systematically investigate a model hybrid comprising a single core/shell nanowire of Te-PEDOT:PSS. We show that as the nanowire diameter is reduced, the electrical conductivity increases and the thermal conductivity decreases, while the Seebeck coefficient remains nearly constant-this collectively results in a figure of merit, ZT , of 0.54 at 400 K. The origin of the decoupling of charge and heat transport lies in the fact that electrical transport occurs through the organic shell, while thermal transport is driven by the inorganic core. This study establishes design principles for high-performing thermoelectrics that leverage the unique interactions occurring at the interfaces of hybrid nanowires., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Thermoelectric devices possess enormous potential to reshape the global energy landscape by converting waste heat into electricity, yet their commercial implementation has been limited by their high cost to output power ratio. No single "champion" thermoelectric material exists due to a broad range of material-dependent thermal and electrical property optimization challenges. While the advent of nanostructuring provided a general design paradigm for reducing material thermal conductivities, there exists no analogous strategy for homogeneous, precise doping of materials. Here, we demonstrate a nanoscale interface-engineering approach that harnesses the large chemically accessible surface areas of nanomaterials to yield massive, finely-controlled, and stable changes in the Seebeck coefficient, switching a poor nonconventional p-type thermoelectric material, tellurium, into a robust n-type material exhibiting stable properties over months of testing. These remodeled, n-type nanowires display extremely high power factors (~500 µW m -1 K -2 ) that are orders of magnitude higher than their bulk p-type counterparts.

It remains difficult to understand the surface of solid acid catalysts at the molecular level, despite their importance for industrial catalytic applications. A sulfated zirconium-based metal-organic framework, MOF-808-SO 4 , was previously shown to be a strong solid Brønsted acid material. In this report, we probe the origin of its acidity through an array of spectroscopic, crystallographic and computational characterization techniques. The strongest Brønsted acid site is shown to consist of a specific arrangement of adsorbed water and sulfate moieties on the zirconium clusters. When a water molecule adsorbs to one zirconium atom, it participates in a hydrogen bond with a sulfate moiety that is chelated to a neighbouring zirconium atom; this motif, in turn, results in the presence of a strongly acidic proton. On dehydration, the material loses its acidity. The hydrated sulfated MOF exhibits a good catalytic performance for the dimerization of isobutene (2-methyl-1-propene), and achieves a 100% selectivity for C8 products with a good conversion efficiency.

Mystery surrounds the transition from gas-phase hydrocarbon precursors to terrestrial soot and interstellar dust, which are carbonaceous particles formed under similar conditions. Although polycyclic aromatic hydrocarbons (PAHs) are known precursors to high-temperature carbonaceous-particle formation, the molecular pathways that initiate particle formation are unknown. We present experimental and theoretical evidence for rapid molecular clustering-reaction pathways involving radicals with extended conjugation. These radicals react with other hydrocarbon species to form covalently bound complexes that promote further growth and clustering by regenerating resonance-stabilized radicals through low-barrier hydrogen-abstraction and hydrogen-ejection reactions. Such radical-chain reaction pathways may lead to covalently bound clusters of PAHs and other hydrocarbons that would otherwise be too small to condense at high temperatures, thus providing the key mechanistic steps for rapid particle formation and surface growth by hydrocarbon chemisorption., (Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Thermoelectric power generation can play a key role in a sustainable energy future by converting waste heat from power plants and other industrial processes into usable electrical power. Current thermoelectric devices, however, require energy intensive manufacturing processes such as alloying and spark plasma sintering. Here, we describe the fabrication of a p-type thermoelectric material, copper selenide (Cu 2 Se), utilizing solution-processing and thermal annealing to produce a thin film that achieves a figure of merit, ZT, which is as high as its traditionally processed counterpart, a value of 0.14 at room temperature. This is the first report of a fully solution-processed nanomaterial achieving performance equivalent to its bulk form and represents a general strategy to reduce the energy required to manufacture advanced energy conversion and harvesting materials.

Unlabelled: This work demonstrates the first method for controlled growth of heterostructures within hybrid organic/inorganic nanocomposite thermoelectrics. Using a facile, aqueous technique, semimetal-alloy nanointerfaces are patterned within a hybrid thermoelectric system consisting of tellurium (Te) nanowires and the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (, Pedot: PSS). Specifically, this method is used to grow nanoscale islands of Cu1.75Te alloy subphases within hybrid, Pedot: PSS-Te nanowires. This technique is shown to provide tunability of thermoelectric and electronic properties, providing up to 22% enhancement of the system's power factor in the low-doping regime, consistent with preferential scattering of low energy carriers. This work provides an exciting platform for rational design of multiphase nanocomposites and highlights the potential for engineering of carrier filtering within hybrid thermoelectrics via introduction of interfaces with controlled structural and energetic properties.

Reverse shoulder arthroplasty (RSA) has revolutionized treatment of arthritis and rotator cuff insufficiency and is performed using implants with either a medial or a lateral center of rotation. We conducted a study of the outcomes and the effect of surgeon learning after the first 60 consecutive lateral-center-of-rotation RSAs implanted by a single surgeon unaffiliated with the design team for this particular reverse shoulder prosthesis. At minimum 2-year followup, mean improvements in active forward elevation, abduction, and external rotation were 69°, 55°, and 23°, respectively; mean active internal rotation improved significantly as well (P < .001 for all). Mean Simple Shoulder Test (SST) scores improved from 1.8 (range, 0-6) to 6.9 (range, 0-12) (P < .0001), and mean final American Shoulder and Elbow Surgeons score was 72 (range, 27-100). Final radiographs showed scapular notching in 5 shoulders (11%). Gains in SST scores, active forward elevation, and active abduction were lower for the first 15 cases than for the next 45 cases, and 5 of the 8 reoperations were performed after the first 15 cases. Overall improvements in active motion and self-assessed shoulder function in this series are comparable to those previously reported by the design team. Experience with RSA appears to influence efficacy, but the learning curve may not be as steep as previously reported.

A chemicurrent is a flux of fast (kinetic energy approximately > 0.5-1.3 eV) metal electrons caused by moderately exothermic (1-3 eV) chemical reactions over high work function (4-6 eV) metal surfaces. In this report, the relation between chemicurrent and surface chemistry is elucidated with a combination of top-down phenomenology and bottom-up atomic-scale modeling. Examination of catalytic CO oxidation, an example which exhibits a chemicurrent, reveals 3 constituents of this relation: The localization of some conduction electrons to the surface via a reduction reaction, 0.5 O(2) + deltae(-) --> O(delta(-)) (Red); the delocalization of some surface electrons into a conduction band in an oxidation reaction, O(delta(-)) + CO --> CO(2)(delta-) --> CO(2) + deltae(-) (Ox); and relaxation without charge transfer (Rel). Juxtaposition of Red, Ox, and Rel produces a daunting variety of metal electronic excitations, but only those that originate from CO(2) reactive desorption are long-range and fast enough to dominate the chemicurrent. The chemicurrent yield depends on the universality class of the desorption process and the distribution of the desorption thresholds. This analysis implies a power-law relation with exponent 2.66 between the chemicurrent and the heat of adsorption, which is consistent with experimental findings for a range of systems. This picture also applies to other oxidation-reduction reactions over high work function metal surfaces.

Research that utilizes human subjects is a large and growing enterprise. Tens of millions of individuals have already participated as subjects in one or more research protocols, and millions more participate each year. Government and industry combined spend billions annually to support as many as 20,000 research studies, many of which are individually large and complex enterprises in their own right.These numbers are, if anything, likely to increase even further. Besides the growth in research, two other trends are apparent. First, research-related litigation is on the rise and appears likely to become even more widespread. Sparked at least in part by recent widely publicized instances of harm befalling research subjects, plaintiffs' attorneys are suing both more often and more creatively. Related to this is the second trend: public trust in research is declining and, as a result, at least some types of research are struggling to find adequate numbers of human subjects.As a result of these trends, exposure to potential liability and public perception are both increasingly important. Concomitant with all of this research is the discovery and generation of tremendous quantities of data specific to individual subjects, including--but not limited to--genetic information. Much of this data is irrelevant to subjects' interests because it lacks predictive value, has uncertain meaning, or is otherwise uninformative. Some, however, is different--some of the personal data learned during the course of research with human subjects bears directly on individuals' health. Despite the fact that much individual data has already been generated and that both the quantity and the quality of data generated seem likely to increase, there is a lack of clear guidance for researchers regarding whether and when such information should be divulged to the subjects on whom it bears.In this environment, the potential exists for litigation alleging that a researcher was negligent for failure to disclose to a subject an individual research finding of medical significance. Such litigation would raise a heretofore-unanswered question: should a researcher have a legal duty to disclose medically significant individual research findings to a subject?

Determining the haplotypes in a diploid individual is a major technical challenge in genetic studies of human complex traits. Here we report a method of molecular haplotyping by directly imaging multiple polymorphic sites on individual DNA molecules simultaneously. DNA fragments amplified by long-range PCR were labeled with fluorescent dyes at each polymorphic site using a modified gap-filled padlock probe ligation approach. The labeled DNA molecules were then stretched into linear form on a functionalized glass surface and imaged with multicolor total internal reflection fluorescence (TIRF) microscopy. By determining the colors and positions of the fluorescent labels with respect to the backbone at polymorphic sites, the haplotype can be inferred accurately, in a manner similar to reading a barcode, even when the DNA fragments are not fully labeled. The feasibility of this technology is demonstrated by the determination of the haplotype of a 9.3-kbp DNA fragment containing four SNPs.

The removal of gutta-percha from root-filled teeth is required for re-treatment of failed endodontic treatment and to prepare a space for placement of a post. Complete removal of filling material and sealer is a requirement for success. A review was undertaken of the current literature on methods of gutta-percha and sealer removal. Clinical recommendations based on current evidence are included. A combination of methods may be required to remove filling materials effectively.

Aim: To compare the area occupied by gutta-percha, sealer, or void in standardized .06 tapered prepared simulated curved canals and in mesio-buccal canals of extracted maxillary first molars filled with a single .06 gutta-percha point and sealer or lateral condensation of multiple .02 gutta-percha points and sealer., Methodology: Simulated canals in resin blocks with either a 30 degrees curve and radius of 10.5 mm (n = 20) or a 58 degrees curve and 4.7 mm radius (n = 20) and curved mesio-buccal canals of extracted maxillary first molars (n = 20) were prepared using .06 ProFiles in a variable tip crown-down sequence to an apical size 35 at 0.5 mm from the canal terminus or apical foramen. Ten 30 degrees and 58 degrees curved resin canals and 10 canals in the extracted teeth group were obturated with .02 taper gutta-percha cones and AH 26 sealer using lateral condensation. The time required to obturate was recorded. The remaining canals were obturated with a single .06 taper gutta-percha cone and AH 26 sealer. Excess gutta-percha was removed from the specimens using heat and the warm mass vertically condensed. Horizontal sections were cut at 0.5, 1.5, 2.5, 4.5, 7.5 and 11.5 mm from the canal terminus or apical foramen. Colour photographs were taken using an Olympus 35 mm camera attached to a stereomicroscope set at x40 magnification, and then digitized using a flatbed scanner. The cross-sectional area of the canal contents was analysed using Adobe PhotoShop. The percentage of gutta-percha, sealer or voids to the total root canal area were derived and data analysed using unpaired Student's t-test and the Mann-Whitney U-test., Results: In the 30 degrees curved canals the levels had between 94 and 100% of the area filled with gutta-percha with no significant difference (P > 0.05) between the lateral condensation and single cone techniques. In the 58 degrees curved canals the levels had 92-99% of the area filled with gutta-percha, with the single cone technique having significantly (P < 0.05) more gutta-percha fill at the 2.5 mm level only. In the mesio-buccal canals of the teeth the levels had between 72 and 96% of the area filled with gutta-percha with no significant difference (P > 0.05) between the lateral condensation and single cone technique. The time for obturation was significantly (P < 0.05) greater for lateral condensation compared with the single cone technique in all groups., Conclusions: The .06 taper single cone technique was comparable with lateral condensation in the amount of gutta-percha occupying a prepared .06 tapered canal. The .06 single cone technique was faster than lateral condensation.

The fate of carbon tetrachloride (CT) during phytoremediation with poplar was assessed by examining the transpiration of CT from leaves, diffusion from soil, tree trunks, and surface roots, and accumulation of chloride ion in soil and plant tissues. Feedwater containing 12-15 mg/L CT was added to the field test beds planted with poplar, and over 99% of the CT was removed. No significant amount of CT was transpired or diffused into the air, and no significant amount of CT-chlorine accumulated in the tree tissues. Chloride ion accumulated in the soil accounted for all of the CT-chlorine removed. When soils from the root zones were compared to unvegetated soils, microbial mineralization of CT was not enhanced in soils from the root zones as compared to unvegetated soils. Thus, we conclude that uptake and dechlorination of CT by plant tissues is likely the primary mechanism for phytoremediation by poplar.

Prior to root canal treatment at least one undistorted radiograph is required to assess canal morphology. The apical extent of instrumentation and the final root filling have a role in treatment success, and are primarily determined radiographically. Electronic apex locators reduce the number of radiographs required and assist where radiographic methods create difficulty. They may also indicate cases where the apical foramen is some distance from the radiographic apex. Other roles include the detection of root canal perforation. A review of the literature focussed first on the subject of electronic apex location. A second review used the names of apex location devices. From the combined searches, 113 pertinent articles in English were found. This paper reviews the development, action, use and types of electronic apex locators.

Conventional light microscopy is limited in its resolving power by the Rayleigh limit to length scales on the order of 200 nm. On the other hand, spectroscopic techniques such as fluorescence resonance energy transfer cannot be used to measure distances >10 nm, leaving a "gap" in the ability of optical techniques to measure distances on the 10- to 100-nm scale. We have previously demonstrated the ability to localize single dye molecules to a precision of 1.5 nm with subsecond time resolution. Here we locate the position of two dyes and determine their separation with 5-nm precision, using the quantal photobleaching behavior of single fluorescent dye molecules. By fitting images both before and after photobleaching of one of the dyes, we may localize both dyes simultaneously and compute their separation. Hence, we have circumvented the Rayleigh limit and achieved nanometer-scale resolution. Specifically, we demonstrate the technique by measuring the distance between single fluorophores separated by 10-20 nm via attachment to the ends of double-stranded DNA molecules immobilized on a surface. In addition to bridging the gap in optical resolution, this technique may be useful for biophysical or genomic applications, including the generation of super-high-density maps of single-nucleotide polymorphisms.

Ethylene dibromide (EDB; dibromoethane) and trichloroethylene (TCE) are hazardous environmental pollutants. The use of plants to treat polluted sites and groundwater, termed phytoremediation, requires plants that can both effectively remove the pollutant as well as grow in the climatic region of the site. In this paper, we report that the tropical leguminous tree, Leuceana leucocephala var. K636, is able to take up and metabolize EDB and TCE. The plants were grown in sterile hydroponic solution without its symbiont, Rhizobium. EDB and TCE were both metabolized by the plant, as indicated by the formation of bromide ion from EDB and trichloroethanol from TCE. Each plant organ was independently capable of debromination of EDB. L. leucocephala is being used to treat perched groundwater as part of a remedial alternative to address an accidental EDB spill in Hawaii. Bromide levels of plant tissues from the trees grown in the phytoremediation treatment cells at the Hawaii Site were elevated, indicating uptake and degradation of brominated compounds in the trees. This report is the first evidence of a tropical tree effectively metabolizing these common organic pollutants.

Trichloroethylene (TCE) is one of the most prevalent environmental contaminants, and it poses an expensive remediation problem. Phytoremediation has been investigated as a potential tool for the removal of TCE from ground water and soil, and has shown promise in preliminary trials. However, the fate of TCE in plants is largely unknown. Radiolabel studies showed that once taken up and transformed, most of the TCE is incorporated into plant tissue as a non-volatile, un-extractable residue. We describe here an assay for TCE transformation by poplar suspension cells. Using this assay, it was shown that two different activities contribute to the fixation of TCE by poplar cells, one associated with cell walls and insoluble residues, the other associated with a high molecular weight, heat labile fraction of the cell extract. It appears that plant enzymes catalyze some of the transformations.

P450 2E1 is an important mammalian liver enzyme known to metabolize a wide range of compounds including several common environmental pollutants. The medicinal plant, Atropa belladonna, was transformed with Agrobacterium rhizogenes containing a binary vector with rabbit P450 2E1 in either the sense or antisense orientation. The resulting "hairy roots" were isolated and grown in liquid medium. Production of P450 2E1 protein was verified in the roots containing the 2E1 gene in the sense orientation. Transgenic and control root cultures were dosed with the environmental pollutant, trichloroethylene (TCE), and were analyzed for the TCE metabolites, chloral and trichloroethanol. The root cultures expressing the mammalian P450 2E1 had increased levels of the metabolites compared to the levels in the control roots. This method represents a quick way to screen transformants for expression of foreign genes before regeneration of whole plants, and also as a possible source of foreign protein for purification., (Copyright 2002 John Wiley & Sons, Inc. Biotechnol Bioeng 77: 462-466, 2002; DOI 10.1002/bit.10151)

The biochemical mechanism of carbon tetrachloride transformation by poplar cells was investigated using an axenic poplar cell culture. After one-day incubations of poplar cells under aerobic conditions, about 1.5% of dosed carbon tetrachloride was transformed to carbon dioxide, about 0.001% to chloroform and about 3% of the carbon was bound to insoluble poplar cellular materials. The production of carbon dioxide increased under aerobic conditions while the formation of chloroform and cell binding of carbon tetrachloride-carbon was enhanced under anaerobic conditions. Both carbon dioxide production and cell binding were significantly inhibited by a general inhibitor of cytochrome P-450 activity (carbon monoxide) and by specific P-450 2E1 inhibitors (chlorzoxazone, isoniazid, 4-methylpyrazole and 1-phenylimidazole). However, no inhibitory effects were observed when the cells were incubated in the presence of lignin peroxidase inhibitors (NaVO3 and 3-amino-1,2,4-triazole). These results suggest that an enzyme similar to mammalian cytochrome P450-2E1 is involved in the metabolism of carbon tetrachloride by poplar cells. This study demonstrates an environmental biodegradative process for carbon tetrachloride that operates under aerobic conditions.

The 5.67-megabase genome of the plant pathogen Agrobacterium tumefaciens C58 consists of a circular chromosome, a linear chromosome, and two plasmids. Extensive orthology and nucleotide colinearity between the genomes of A. tumefaciens and the plant symbiont Sinorhizobium meliloti suggest a recent evolutionary divergence. Their similarities include metabolic, transport, and regulatory systems that promote survival in the highly competitive rhizosphere; differences are apparent in their genome structure and virulence gene complement. Availability of the A. tumefaciens sequence will facilitate investigations into the molecular basis of pathogenesis and the evolutionary divergence of pathogenic and symbiotic lifestyles.

Trichloroethylene (TCE) is a widespread and persistent environmental contaminant. Recently, plants, poplar trees in particular, have been investigated as a tool to remove TCE from soil and groundwater. The metabolism of TCE in plants is being investigated for two reasons: one, plant uptake and metabolism represent an important aspect of the environmental fate of the contaminant; two, metabolism pattern and metabolite identification will help assess the applicability of phytoremediation. It was previously shown that TCE metabolites in plants are similar to ones that result from cytochrome P450-mediated oxidation in mammals: trichloroethanol, trichloroacetate and dichloroacetate. Our measurements indicate that one of these metabolites, trichloroethanol, is further glycosylated in tobacco and poplar. The glycoside was detected in all tissues (roots, stems and leaves) in comparable levels, and was at least 10 fold more abundant than free trichloroethanol. The glycoside in tobacco was identified as the ss-D-glucoside of trichloroethanol by comparison of the mass spectra and the chromatographic retention time of its acetylation product to that of the synthesized standard. Trichloroethanol and its glucoside did not persist in plant tissue once plants are removed from TCE contaminated water, indicating further metabolism.

Chlorinated solvents, especially trichloroethylene (TCE), are the most widespread groundwater contaminants in the United States. Existing methods of pumping and treating are expensive and laborious. Phytoremediation, the use of plants for remediation of soil and groundwater pollution, is less expensive and has low maintenance; however, it requires large land areas and there are a limited number of suitable plants that are known to combine adaptation to a particular environment with efficient metabolism of the contaminant. In this work, we have engineered plants with a profound increase in metabolism of the most common contaminant, TCE, by introducing the mammalian cytochrome P450 2E1. This enzyme oxidizes a wide range of important pollutants, including TCE, ethylene dibromide, carbon tetrachloride, chloroform, and vinyl chloride. The transgenic plants had a dramatic enhancement in metabolism of TCE of up to 640-fold as compared with null vector control plants. The transgenic plants also showed an increased uptake and debromination of ethylene dibromide. Therefore, transgenic plants with this enzyme could be used for more efficient remediation of many sites contaminated with halogenated hydrocarbons.

Agrobacterium tumefaciens induces tumours on plants by transferring a nucleoprotein complex, the T-complex, from the bacterium to the plant cell. The T-complex consists of a single-stranded DNA (ssDNA) segment, the T-DNA, and VirD2, an endonuclease covalently attached to the 5' end of the T-DNA. A type IV secretion system encoded by the virB operon and virD4 is required for the entry of the T-complex and VirE2, a ssDNA-binding protein, into plant cells. The VirE1 protein is specifically required for the export of the VirE2 protein, as demonstrated by extracellular complementation and tumour formation. In this report, using a yeast two-hybrid system, we demonstrated that the VirE1 and VirE2 proteins interact and confirmed this interaction by in vitro binding assays. Although VirE2 is a ssDNA-binding protein, addition of ssDNA into the binding buffer did not interfere with the interaction of VirE1 and VirE2. VirE2 also interacts with itself, but the interaction between VirE1 and VirE2 is stronger than the VirE2 self-interaction, as measured in a lacZ reporter gene assay. In addition, the interaction of VirE2 with itself is inhibited by VirE1, indicating that VirE2 binds VirE1 preferentially. Analysis of various virE2 deletions indicated that the VirE1 interaction domain of VirE2 overlaps the VirE2 self-interaction domain. Incubation of extracts from Escherichia coli overexpressing His-VirE1 with the extracts of E. coli overexpressing His-VirE2 increased the yield of His-VirE2 in the soluble fraction. In a similar purified protein solubility assay, His-VirE1 increased the amount of His-VirE2 partitioning into the soluble fraction. In Agrobacterium, VirE2 was undetectable in the soluble protein fraction unless VirE1 was co-expressed. When urea was added to solubilize any large protein aggregates, a low level of VirE2 was detected. These results indicate that VirE1 prevents VirE2 from aggregating, enhances the stability of VirE2 and, perhaps, maintains VirE2 in an export-competent state. Analysis of the deduced amino acid sequence of the VirE1 protein revealed that the VirE1 protein shares a number of properties with molecular chaperones that are involved in the transport of specific proteins into animal and plant cells using type III secretion systems. We suggest that VirE1 functions as a specific molecular chaperone for VirE2, the first such chaperone linked to the presumed type IV secretion system.

Agrobacterium tumefaciens induces crown gall tumors on plants by transferring a nucleoprotein complex, the T-complex, from the bacterium to the plant cell. The T-complex consists of T-DNA, a single-stranded DNA segment of the tumor-inducing plasmid, VirD2, an endonuclease covalently bound to the 5' end of the T-DNA, and perhaps VirE2, a single-stranded DNA binding protein. The yeast two-hybrid system was used to screen for proteins interacting with VirD2 and VirE2 to identify components in Arabidopsis thaliana that interact with the T-complex. Three VirD2- and two VirE2-interacting proteins were identified. Here we characterize the interactions of VirD2 with two isoforms of Arabidopsis cyclophilins identified by using this analysis. The VirD2 domain interacting with the cyclophilins is distinct from the endonuclease, omega, and the nuclear localization signal domains. The VirD2-cyclophilin interaction is disrupted in vitro by cyclosporin A, which also inhibits Agrobacterium-mediated transformation of Arabidopsis and tobacco. These data strongly suggest that host cyclophilins play a role in T-DNA transfer.