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Polarized transient X-ray absorption near-edge structure (XANES) was used to probe the excited-state structure of a photostable B12 antivitamin (Coβ-2-(2,4-difluorophenyl)-ethynylcobalamin, F2PhEtyCbl). A drop-on-demand delivery system synchronized to the LCLS X-ray free electron laser pulses was implemented and used to measure the XANES difference spectrum 12 ps following excitation, exposing only ∼45 μL of sample. Unlike cyanocobalamin (CNCbl), where the Co-C bond expands 15-20%, the excited state of F2PhEtyCbl is characterized by little change in the Co-C bond, suggesting that the acetylide linkage raises the barrier for expansion of the Co-C bond. In contrast, the lower axial Co-NDMB bond is elongated in the excited state of F2PhEtyCbl by ca. 10% or more, comparable to the 10% elongation observed for Co-NDMB in CNCbl.

Caribbean whiptail and southern stingrays are large-bodied mesopredators, occupying shallow, nearshore ecosystems of The Bahamas, yet virtually nothing is known of their diet or potential resource competition. We used stomach content analysis via gastric lavage and stable isotope analysis to investigate the diet of 94 Caribbean whiptail rays Styracura schmardae and 112 southern stingrays Hypanus americanus across 3 locations in the central Bahamas. Gastric lavage was used to identify prey consumed and compared to stable isotope analysis of δ15N, δ13C and δ34S of barb, muscle, blood and skin, representing different temporal integration periods. Both species appeared to consume a majority of crustaceans and annelids, although δ13C values suggested that Caribbean whiptail rays have larger isotopic niche space across isotopes sampled (potentially broader diet) than southern stingrays, ranging from 5.82-3.43‰2, and a greater variance in δ13C. This suggests Caribbean whiptail rays potentially feed on prey from either a wider geographic range or from different habitats. Caribbean whiptail and southern stingrays are known to spatio-temporally overlap, and their isotopic niche overlapped by 35.6%. This study represents the first integrated diet estimate for southern stingrays obtained using multiple techniques, and the first ever diet assessment in Caribbean whiptail rays. These data are critical for conservation of coastal ray species and management of coastal and nearshore environments throughout the region.

We have used transient absorption spectroscopy in the UV-visible and X-ray regions to characterize the excited state of CarH, a protein photoreceptor that uses a form of B

7 pags., 5 figs., We have used transient absorption spectroscopy in the UV-visible and X-ray regions to characterize the excited state of CarH, a protein photoreceptor that uses a form of B12, adenosylcobalamin (AdoCbl), to sense light. With visible excitation, a nanosecond-lifetime photoactive excited state is formed with unit quantum yield. The time-resolved X-ray absorption near edge structure difference spectrum of this state demonstrates that the excited state of AdoCbl in CarH undergoes only modest structural expansion around the central cobalt, a behavior similar to that observed for methylcobalamin rather than for AdoCbl free in solution. We propose a new mechanism for CarH photoreactivity involving formation of a triplet excited state. This allows the sensor to operate with high quantum efficiency and without formation of potentially dangerous side products. By stabilizing the excited electronic state, CarH controls reactivity of AdoCbl and enables slow reactions that yield nonreactive products and bypass bond homolysis and reactive radical species formation., This work was supported by grants from the National Science Foundation NSF-CHE 1464584 and NSFCHE 1836435 to R.J.S., NSF-CHE 1565795 to K.J.K., NSFCHE 1608553 and NSF-CHE-1904759 to E.N.G.M., and NSF-CHE 1945174 to M.K.; from the Agencia Estatal de Investigación (AEI)-Spain and the European Regional Development Fund (FEDER) grants PGC2018-094635-BC21 (to M.E.-A.) and PGC2018-094635-B-C22 (to S.P.); and from the Fundacion Seneca (Murcia)-Spain grant 20992/PI/ ́ 18 (to M.E.-A.). Portions of this work were carried out in the Laboratory for Ultrafast Multidimensional Optical Spectroscopy (LUMOS) supported by NSF-CHE 1428479. Use of the Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515.

Polarized transient X-ray absorption near-edge structure (XANES) was used to probe the excited-state structure of a photostable B

We use picosecond time-resolved polarized X-ray absorption near-edge structure (XANES) measurements to probe the structure of the long-lived photoexcited state of methylcobalamin (MeCbl) and the cob(II)alamin photoproduct formed following photoexcitation of adenosylcobalamin (AdoCbl, coenzyme B12). For MeCbl, we used 520 nm excitation and a time delay of 100 ps to avoid the formation of cob(II)alamin. We find only small spectral changes in the equatorial and axial directions, which we interpret as arising from small (

Laser annealing can reduce the annealing time required to form Cu(In,Ga)(S,Se)2 (CIGSe) thin films for use in thin film photovoltaics to a single second timescale, if not faster. In this work, we use microstructural characterization coupled with modeling of the optical and thermal properties to understand the laser annealing of three types of electrodeposited precursor stacks for the CIGSe parent compound CuInSe2. The precursor films are: stacked elemental layers Cu/In/Se, stacked binary selenides In2Se3/Cu2−xSe, and a single layer of coelectrodeposited Cu–In–Se. Conceptually, these stacks are ordered in terms of decreasing stored chemical and interfacial potential free energy, consideration of which predicts that the formation of large grained CuInSe2 from the stacked elemental layers would be the most exothermic and thus most rapid process. However we find that microstructural details of the electrodeposited films such as void fraction present in the stacked binary selenides dramatically alter the heat and mass flow. Additionally, modeling of the optical absorption within the elemental stacked precursor suggests extremely localized heating at the In/Se interface resulting in significant Se loss. Despite its lower chemical potential energy, the coelectrodeposited CuInSe2 precursor's more uniform optical absorption of near-bandgap light coupled with its compact, low void fraction microstructure of nano-sized grains results in the most optimal recrystallization and compositional homogenization via interdiffusion. Furthermore this annealed layer formed a working device with a short circuit current density of 23 mA cm−2. This combined modeling and experimental investigation underscores the need to consider practical micro- and nanostructure-dependent properties as well as the optical absorption and not simply thermodynamics when designing accelerated two step deposition and annealing processes for compound semiconductors.

One industrially relevant fabrication method for CuInSe2 absorber layers begins with electrodeposition, which is highly resource efficient and easily up-scalable, followed by a high temperature annealing step. Commonly a furnace is used for annealing, although it is possible to reduce the duration of this step by 2–3 orders of magnitude using laser heating. Past work demonstrated that rastering a 1064 nm, continuous wave, neodymium-doped yttrium aluminium garnet laser beam over an electrodeposited precursor film with 1 s dwell time, promoted CuInSe2 formation, grain growth, and gave a photovoltaic device with 1.6% power conversion efficiency. However, this device showed inhomogeneous current collection correlating approximately to the Gaussian flux profile of the laser beam. This work demonstrates how deviations in the incident laser flux on the precursor lead to local temperature variation in the film. The temperature affects the rates of atomic diffusion, grain growth and chemical reactions, with the hottest region having the largest crystallites and a stoichiometric and constant composition through the film depth. Spatially resolved photoluminescence yield shows a positive correlation to the temperature profile caused by the Gaussian flux. It is expected that with a homogeneous laser beam flux, spatial variations in absorber layer properties would be eliminated, leading to uniform device properties.

Cu(In,Ga)Se2 (CIGSe) is a polycrystalline absorber layer in thin film solar cells with solar conversion efficiencies exceeding 20%. High temperature annealing for periods of minutes to hours is currently required to convert amorphous or nanocrystalline precursor material into high quality Cu(In,Ga)Se2 absorber layers. In this work, we perform the critical annealing step, using a 1064 nm laser, on electrodeposited precursor layers containing Cu, In, and Se, for times of 0.3–60 s thus synthesizing CuInSe2 absorber layers. An annealing time of 1 s is found to be sufficient to remove elemental concentration gradients in the bulk of the layer and to increase the average implied crystallite size (crystal coherence length, as determined by X-ray diffraction, XRD). Therefore the rate-determining step in producing higher quality layers with short annealing times is the rate of grain growth and not atomic diffusion. Optoelectronic analysis of the absorber layers revealed p-type doping with improved radiative recomb...

CuInSe2 (CISe) is a prototype material for the I–III–VI chalcopyrites such as Cu(In,Ga)(S,Se)2 used as absorber layers in thin film photovoltaic cells. Carefully-controlled pulsed-laser annealing (PLA) is a unique annealing process that has been demonstrated to improve the device performance of chalcopyrite solar cells. Here, we investigate the changes in defect populations after PLA of electrochemically-deposited CISe thin films previously furnace annealed in selenium vapor. The films were irradiated in the sub-melting regime at fluences inducing temperatures up to 840 ± 100 K. Deep-level transient spectroscopy on Schottky diodes reveals that the activation energy of the dominant majority carrier trap changes non-monotonically from 215 ± 10 meV for the reference sample, to 330 ± 10 meV for samples irradiated at 20 and 30 mJ/cm2, and then back to 215 ± 10 meV for samples irradiated at 40 mJ/cm2. A hypothesis involving competing processes of diffusion of Cu and laser-induced generation of In vacancies may explain this behavior.

In this unpublished memoir, written in the early 1990s, the late Dana Meadows reflects on the history of The Limits to Growth, including its origins, conclusions, and the reactions it generated. This memoir had been condensed and edited by Dennis Meadows. Copyright © 2007 John Wiley & Sons, Ltd.

Many natural resource-based commodity systems exhibit a trio of undesirable behaviors—price instability, resource unsustainability, and inequity among people along the commodity chain. In this article we share findings from a modeling project that focuses primarily on the second problem, unsustainability, in the forest products economy and forest ecosystem of the Northeastern United States. The model shows the structural potential for lumber industry capacity to overshoot the timber resource of the regional forest. Many of the policies commonly advocated in response to resource shortage, such as boosting mill efficiencies and eliminating log exports, appear unlikely to solve the problem. We identify several policies with the potential to help sustain both the industry and resource base. We also share insights on how to design a modeling and intervention process when addressing policy problems for which no single organization has direct responsibility. Finally, we consider ways to navigate through three prevalent “defensive routines”—denial, resignation, and despair—that are often barriers to constructive discussion on how to address potential limits to growth. Copyright © 2002 John Wiley & Sons, Ltd.

One method for producing CuInSe 2 (CISe) absorber layers is electrodeposition followed by annealing. Replacing the commonly used furnace annealing step with a laser can reduce annealing times by 2–3 orders of magnitude: from 30 minutes to 1 s. However, laser processing has, to date, not resulted in absorber layers which can form functioning final devices. One reason is due to Se loss during annealing even on these short timescales. We show how this Se loss is reduced by using a background partial pressure of Se (P Se ) during annealing. Higher P Se results in increased grain size and drastically increased photoluminescence yield. The introduction of an elevated P Se in the laser annealing chamber enabled the fabrication of the first known CuInSe 2 photovoltaic device using electrodeposition followed by laser annealing which gave 1.6% efficiency.

To determine the attitudes of general dental practitioners toward aspects of change in undergraduate dental education.Descriptive postal survey using a cross-sectional random sample of general dental practitioners administered in 1997.689 general dental practitioners practising in five regions of England with close proximity to a dental school selected by a one in two stratified random sample.Response rate: 70%. The questionnaire was both valid and reliable with an internal consistency reliability coefficient of 0.84. Responses identified strong support for preparing dental students for the wider role of the dentist and an emphasis toward self-directed learning. Other themes emerging from the investigation included support for learning to work as part of a dental team and for students to have experience of general dental practice early on in the undergraduate course.These responses have implications for curriculum design, syllabus, teaching methods, resources and staff development for dental schools in the UK.

For the production of high efficiency thin film, Cu(In,Ga)Se2 solar cells, absorber layers with grain sizes of a few hundred nanometers and without detrimental secondary phases are favored. Co-electrodeposition offers a low-cost and material efficient synthesis route, where, in a single step, films containing CuInSe2 are formed. However, the material is nanocrystalline, constitutes multiple phases and has poor photovoltaic properties 1. Therefore a subsequent annealing step is required to produce absorber layers suitable for use in photovoltaic devices. Laser annealing has been demonstrated to improve crystallinity, stimulate atomic diffusion and develop opto-electronic properties when compared to the precursor 2. In this work, high resolution X-ray diffraction was used in order to assess the presence of secondary phases in the absorber layer. All diffractograms of laser annealed films exhibited an additional, unknown peak, measurable through the full depth of the material which is independent of precursor composition, annealing time or laser flux. Evaluation of literature on codeposited CuInSe2, combined with Rietveld refinement suggests a number of possible identities for this peak. The candidates in order of most likely to least likely are structural defects, In2Se3, and CuIn3Se5. We consider the impact that each of these would have on a device formed via this process and thus its success as a new manufacturing route for CuInSe2 solar cells.

In order to upscale the production of thin film solar cells a cost effective and simple synthesis technique is required. Keeping this in mind we have investigated the effect of electrochemical deposition (ED) and inherently low thermal budget rapid thermal annealing (RTA) processing of CuInSe 2 in sulfur atmosphere. X-ray diffraction ( -2 ) scans indicate increased grain size and improved crystallinity after RTA of ED films. Scanning electron microscopy images (SEM) suggest changes in surface morphol ogy after sulfur incorporation. Raman spectroscopy results and temperature dependent conductivity measurements are also discussed in the paper. CuIn(S,Se) 2 , electrochemical deposition and rapid thermal annealing 1. INTRODUCTION Thin film solar cell is a fast growing sector of solar cell industry with its major advantages of potential cost reduction and scalability. These advantages over the present high throughput crystalline Si technology will bring the cost per watt of solar energy at grid parity. Of the relatively less defect sensitive photovoltaic (PV) materials for thin film solar cells, materials with chalcogenide and kesterite structure are considered strong contenders. CuInSe

In this report we investigate the effects of pulsed laser annealing (PLA) on both as-electrodeposited (ED) and electrodeposited-furnace annealed (EDA) CuInSe 2 (CIS) samples by varying the laser fluence (J/cm2) and number of pulses. Results for as-ED samples indicate that liquid CIS-phase formation during PLA with 248 nm laser is to be avoided as liquid CIS dewets on Mo [1] as well as MoSe 2 . In the case of EDA-PLA samples, scanning electron microscopy (SEM) images suggest no apparent change in surface morphology but photoluminescence (PL) indicates change in PL yield and FWHM after PLA processing, a possible indication of annealing of defect states. The effects of PLA on defects are further explored using deep level transient spectroscopy (DLTS).

Le scenario d'une crise tant economique qu'ecologique est demontre par une simulation informatique de la croissance mondiale

All of the communication technologies explored have a number of characteristics in common, including how their adoption spreads from a small group of highly interested users to the general public, what the effects of these technologies are upon the people who use them, and how these technologies affect each other. Theoretical approaches are useful in understanding the origins of the information-based economy in which we now live, why some technologies take off while others fail, the impacts and effects of technologies, and the economics of the communication technology marketplace. Information about an innovation is communicated through different channels. Mass media is good for awareness knowledge. Interpersonal channels are also an important means of communication about innovations. These interactions generally involve subjective evaluations of the innovation. For a technology’s adoption to move from innovators to the early adopters the technology must show a major new benefit.

The 1990s promise to usher in a new era of formal and informal disclosure. Through the “formal” disclosure process, shareholders and institutional investors have and will continue to assume a more active role in corporate governance. Moreover, corporate management must also be wary of its increased liability for “informal” disclosure of material, nonpublic information. Now, more than ever, corporate management must be cognizant of the importance of formal and informal disclosure. This article examines both formal and informal corporate disclosures under current law.

The effect of spastic cerebral palsy on in vivo gastrocnemius muscle fascicle length is not clear. Similarity of fascicle lengths in children with diplegia and typically developing children, but shortening of fascicle lengths in the paretic legs of children with hemiplegia compared with the non-paretic legs, are both reported. In the former case, comparisons were made between fascicle lengths normalized to leg length, whereas in the latter case, absolute fascicle lengths were compared. The inherent assumptions when normalizing fascicle length (measured via ultrasonography) were not validated, raising the possibility that inappropriate normalization contributed to the controversy. We used statistical methods to control the potential confounding effect of leg length on fascicle length, and tested the feasibility of the normalization method for a group of 18 children with diplegia (nine males, nine females; mean age 8y 7mo [SD 3y 11mo], range 2-15y; Gross Motor Function Classification System levels II and III) and 50 typically developing children (20 males, 30 females; mean age 9y 1mo [SD 2y 4mo], range 4-14y). Children with diplegia, as a group, had shorter absolute and normalized fascicle lengths (p

It has been generally accepted that mechanical stimulation is an important factor in the promotion of formation of bone. Fracture-healing consists of periosteal bridging of the fracture, which achieves stability, and proliferation of endosteal bone to fill the defects between the ends of the bone. To evaluate the effect of weight-bearing on bone-healing, an operatively created defect in the tibial cortex was chosen as an experimental model. In one set of dogs (Group 1), a bilateral defect in the tibial cortex was created and weight-bearing was permitted on one tibia but not on the opposite one. In Group 2, a bilateral defect in the tibial cortex was made and weight-bearing was allowed on both tibiae. A third group of dogs of similar age (Group 3) had no tibial defects. Quantitative histomorphometry was used to measure formation and porosity of bone. Weight-bearing was measured with both static and dynamic techniques. Significantly less woven bone formed in the defects in the non-weight-bearing tibiae than in the weight-bearing tibiae. This appeared to be due to a disuse response in the underloaded tibiae, in which less bone formed, rather than to the formation of more bone in the weight-bearing tibiae. The data suggest that weight-bearing is a permissive factor, not a stimulus, for formation of woven bone in a tibial defect. Clinical Relevance: This animal model supports the concept that lack of weight-bearing decreases the amount of woven bone that is formed in a healing tibial defect. The results of this study indicate that weight-bearing increases the formation of bone in fracture-healing.(ABSTRACT TRUNCATED AT 250 WORDS)

Background: The aim of this study was to investigate the architectural alterations of skeletal muscle following hemiplegic cerebral palsy. If associated with functional and clinical measures of disability, information on muscle architecture could then be used as an objective tool in the assessment of motor disability in these patients. Methods: Ultrasonography was used to assess in vivo the gastrocnemius muscle architecture in the paretic and non-paretic legs of eight children with cerebral palsy. Findings: Fascicle length and muscle thickness at the resting ankle position were reduced in the paretic compared to the non-paretic legs by up to 18% and 20%, respectively (P < 0.05), indicating a loss of both in-series and in-parallel sarcomeres in the affected muscles. However, pennation angle was similar (P > 0.05) in the two legs. Interpretation: The present results indicate that paresis in hemiplegic cerebral palsy may affect the geometry of skeletal muscle. Further studies are required to examine the relation between muscle architecture, severity of motor disability, and treatment.

In the late 1980s, the treatment of primary anal cancer in the UK moved away from surgical treatment to nonsurgical treatment. This was partly due to the first UK trial in the disease [1], now known as ACT I. By the early 1990s, the results of the UK trial and separate trials run by the European Organisation for Research and Treatment of Cancer (EORTC) and Radiation Therapy Oncology Group (RTOG) were available [2,3]. ACT I was the largest of the three trials and, like the EORTC trial, compared radiotherapy with the same radiotherapy plus 5-fluorouracil (5-FU) and mitomycin C (MMC) during the first and final week of the first radiotherapy course. The trial established chemoradiation as the treatment of choice for most patients with the disease. Subsequently, similar trials in other squamous cell carcinomas showed improved survival for patients receiving both treatment modalities synchronously.

Chemoradiotherapy is the standard treatment for most patients with epidermoid anal cancer. Pre-treatment staging is based on size for T1-T3 lesions and clinical and radiological assessment of adjacent organ invasion for T4 lesions. For patients with residual or recurrent carcinoma, anorectal excision offers the best chance of oncological salvage. Pathological staging systems for anorectal excision specimens were validated at the time when surgical treatment was first line therapy. A validated staging system is necessary for salvage surgical excision specimens following an attempt to cure by radiotherapy and chemotherapy for the purpose of prognosis and further treatment planning.

We review prior and on-going works in using laser annealing (LA) techniques in the development of chalcogenide-based [CdTe and Cu(In,Ga)(S,Se)2] solar cells. LA can achieve unique processing regimes as the wavelength and pulse duration can be chosen to selectively heat particular layers of a thin film solar cell or even particular regions within a single layer. Pulsed LA, in particular, can achieve non-steady-state conditions that allow for stoichiometry control by preferential evaporation, which has been utilized in CdTe solar cells to create Ohmic back contacts. Pulsed lasers have also been used with Cu(In,Ga)(S,Se)2 to improve device performance by surface-defect annealing as well as bulk deep-defect annealing. Continuous-wave LA shows promise for use as a replacement for furnace annealing as it almost instantaneously supplies heat to the absorbing film without wasting time or energy to bring the much thicker substrate to temperature. Optimizing and utilizing such a technology would allow production lines to increase throughput and thus manufacturing capacity. Lasers have also been used to create potentially low-cost chalcogenide thin films from precursors, which is also reviewed.