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We investigate the spin relaxation of Ho single atom magnets on MgO/Ag(100) as a function of temperature and magnetic field. We find that the spin relaxation is thermally activated at low field, while it remains larger than 1000 s up to 30 K and 8 T. This behavior contrasts with that of single molecule magnets and bulk paramagnetic impurities, which relax faster at high field. Combining our results with density functional theory, we rationalize this unconventional behavior by showing that local vibrations activate a two-phonon Raman process with a relaxation rate that peaks near zero field and is suppressed at high field. Our work shows the importance of these excitations in the relaxation of axially coordinated magnetic atoms.
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We have experimentally determined the lateral registry and geometric structure of free-base porphine (2H-P) and copper-metalated porphine (Cu-P) adsorbed on Cu(111), by means of energy-scanned photoelectron diffraction (PhD), and compared the experimental results to density functional theory (DFT) calculations that included van der Waals corrections within the Tkatchenko-Scheffler approach. Both 2H-P and Cu-P adsorb with their center above a surface bridge site. Consistency is obtained between the experimental and DFT-predicted structural models, with a characteristic change in the corrugation of the four N atoms of the molecule's macrocycle following metalation. Interestingly, comparison with previously published data for cobalt porphine adsorbed on the same surface evidences a distinct increase in the average height of the N atoms above the surface through the series 2H-P, Cu-P, and cobalt porphine. Such an increase strikingly anti-correlates the DFT-predicted adsorption strength, with 2H-P having the smallest adsorption height despite the weakest calculated adsorption energy. In addition, our findings suggest that for these macrocyclic compounds, substrate-to-molecule charge transfer and adsorption strength may not be univocally correlated.
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A permanent magnet retains a substantial fraction of its saturation magnetization in the absence of an external magnetic field. Realizing magnetic remanence in a single atom allows for storing and processing information in the smallest unit of matter. We show that individual holmium (Ho) atoms adsorbed on ultrathin MgO(100) layers on Ag(100) exhibit magnetic remanence up to a temperature of 30 kelvin and a relaxation time of 1500 seconds at 10 kelvin. This extraordinary stability is achieved by the realization of a symmetry-protected magnetic ground state and by decoupling the Ho spin from the underlying metal by a tunnel barrier.
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We report on the adsorption and self-metalation of a prototypic tetrapyrrole compound, the free-base porphine (2H-P), on the Cu(111) surface. Our multitechnique study combines scanning tunneling microscopy (STM) results with near-edge X-ray absorption fine-structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) data whose interpretation is supported by density functional theory calculations. In the first layer in contact with the copper substrate the molecules adsorb coplanar with the surface as shown by angle-resolved NEXAFS measurements. The quenching of the first resonance in the magic angle spectra of both carbon and nitrogen regions indicates a substantial electron transfer from the substrate to the LUMO of the molecule. The stepwise annealing of a bilayer of 2H-P molecules sequentially transforms the XP and NEXAFS signatures of the nitrogen regions into those indicative of the coordinated nitrogen species of the metalated copper porphine (Cu-P), i.e., we observe a temperature-induced self-metalation of the system. Pre- and post-metalation species are clearly discriminable by STM, corroborating the spectroscopic results. Similar to the free-base porphine, the Cu-P adsorbs flat in the first layer without distortion of the macrocycle. Additionally, the electron transfer from the copper surface to the molecule is preserved upon metalation. This behavior contrasts the self-metalation of tetraphenylporphyrin (2H-TPP) on Cu(111), where both the molecular conformation and the interaction with the substrate are strongly affected by the metalation process.
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The bonding and the temperature-driven metalation of 2H-tetraphenylporphyrin (2H-TPP) on the Cu(111) surface under ultrahigh vacuum conditions were investigated by a combination of x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy with density functional theory calculations. Thin films were prepared by organic molecular beam epitaxy and subsequent annealing. Our systematic study provides an understanding of the changes of the spectroscopic signature during adsorption and metalation. Specifically, we achieved a detailed peak assignment of the 2H-TPP multilayer data of the C1s and the N1s region. After annealing to 420 K both XPS and NEXAFS show the signatures of a metalloporphyrin, which indicates self-metalation at the porphyrin-substrate interface, resulting in Cu-TPP. Furthermore, for 2H-TPP monolayer samples we show how the strong influence of the copper surface is reflected in the spectroscopic signatures. Adsorption results in a strongly deformed macrocycle and a quenching of the first NEXAFS resonance in the nitrogen edge suggesting electron transfer into the LUMO. For Cu-TPP the spectroscopic data indicate a reduced interaction of first-layer molecules with the substrate as demonstrated by the relaxed macrocycle geometry.
Assuntos
Cobre/química , Compostos Organometálicos/síntese química , Porfirinas/química , Compostos Organometálicos/química , Teoria Quântica , Espectrofotometria , Propriedades de Superfície , Temperatura , Espectroscopia por Absorção de Raios X , Raios XRESUMO
An adaptive feedback control system is presented which employs a computational model of bioheat transfer in living tissue to guide, in real-time, laser treatments of prostate cancer monitored by magnetic resonance thermal imaging. The system is built on what can be referred to as cyberinfrastructure-a complex structure of high-speed network, large-scale parallel computing devices, laser optics, imaging, visualizations, inverse-analysis algorithms, mesh generation, and control systems that guide laser therapy to optimally control the ablation of cancerous tissue. The computational system has been successfully tested on in vivo, canine prostate. Over the course of an 18 min laser-induced thermal therapy performed at M.D. Anderson Cancer Center (MDACC) in Houston, Texas, the computational models were calibrated to intra-operative real-time thermal imaging treatment data and the calibrated models controlled the bioheat transfer to within 5 degrees C of the predetermined treatment plan. The computational arena is in Austin, Texas and managed at the Institute for Computational Engineering and Sciences (ICES). The system is designed to control the bioheat transfer remotely while simultaneously providing real-time remote visualization of the on-going treatment. Post-operative histology of the canine prostate reveal that the damage region was within the targeted 1.2 cm diameter treatment objective.
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Engenharia Biomédica/métodos , Terapia a Laser , Neoplasias da Próstata/terapia , Algoritmos , Animais , Calibragem , Biologia Computacional/métodos , Simulação por Computador , Sistemas Computacionais , Cães , Retroalimentação , Previsões , Temperatura Alta , Humanos , Hipertermia Induzida , Processamento de Imagem Assistida por Computador , Imageamento por Ressonância Magnética/métodos , Masculino , Modelos Biológicos , Imagens de Fantasmas , Reprodutibilidade dos Testes , Software , Terapia Assistida por ComputadorRESUMO
Elevating the temperature of cancerous cells is known to increase their susceptibility to subsequent radiation or chemotherapy treatments, and in the case in which a tumor exists as a well-defined region, higher intensity heat sources may be used to ablate the tissue. These facts are the basis for hyperthermia based cancer treatments. Of the many available modalities for delivering the heat source, the application of a laser heat source under the guidance of real-time treatment data has the potential to provide unprecedented control over the outcome of the treatment process [7, 18]. The goals of this work are to provide a precise mathematical framework for the real-time finite element solution of the problems of calibration, optimal heat source control, and goal-oriented error estimation applied to the equations of bioheat transfer and demonstrate that current finite element technology, parallel computer architecture, data transfer infrastructure, and thermal imaging modalities are capable of inducing a precise computer controlled temperature field within the biological domain.
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An optical-DSC system was designed, built, tested, calibrated and verified to incorporate into a single device the capability for simultaneous optical cryomicroscopy and differential scanning calorimetry (DSC). This instrument can be used to obtain both visual and thermal data for an individual specimen subjected to a defined freezing and thawing protocol with very little compromise in quality or range of data available in comparison with dedicated single instruments. Temperature and caloric calibrations were performed based on phase transition states in water, n-dodecane and n-decane. The instrument has proven effective for process analysis in living cells and in foodstuffs.
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This article presents a method to view a dynamic ice interface along the axis of ice growth using a laser-scanning microscope. A deep liquid volume is chilled from below so that ice growth is directed upward toward the microscope objective. The interface is made visible by rejection of fluorescent dye from the solid phase into the liquid. Images of the interface morphology in water with solutes of interest to cryobiology illustrate the imaging capability. These images are processed to quantify the lamellar structure of the ice interface. The optical-axis cryostage provides advantages over horizontal arrangements because (1) immersion objectives enhance, rather than disturb, the desired thermal gradient, and (2) features in the ice interface are not confined within a narrow capillary tube or microscope slide. This arrangement loses some of the thermal control found in planar freezing stages, and the dynamic, refractive interface presents challenges to confocal microscopy.
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Gelo , Água , Biologia/métodos , Ação Capilar , Congelamento , Microscopia Eletrônica de Varredura/métodosRESUMO
Biphasic transport of water and dimethyl sulfoxide (Me(2)SO), a common cryoprotective agent (CPA), in algal cells was induced and measured on a cryoperfusion stage. A two-step experimental protocol provided data for the volumetric response of Chlorococcum (C.) texanum to impermeable and permeable solutes. First, the cells were exposed to a 500-mOsm sucrose solution, causing immediate shrinkage of the cell to a minimum equilibrium volume. Then an isoosmotic 200-mOsm/300-mOsm CPA/sucrose solution was introduced to the cells, resulting in increased cell volume to a new equilibrium state. Experiments were conducted at temperatures between -3 and 23 degrees C. Cell volumes were measured off-line by computer analysis of video images. A network thermodynamic model was fit to the transient volume data to determine permeabilities of C. texanum to water and Me(2)SO over the full temperature range, and results were calculated with two numeric methods. Biphasic transport was found to be slower at colder temperatures, with water entering the cell faster than Me(2)SO. Experimental results were also compared with data from similar experiments using methanol (MeOH) as the CPA. MeOH influx was calculated to be a magnitude larger than that of water. Additionally, MeOH permeability was at least three orders of magnitude greater than Me(2)SO permeability, and the difference in these solute permeabilities increased as temperature decreased.
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Clorófitas/metabolismo , Crioprotetores/farmacocinética , Dimetil Sulfóxido/farmacocinética , Transporte Biológico Ativo , Clorófitas/citologia , Criopreservação/métodos , Microscopia/instrumentação , Modelos Biológicos , Osmose , Permeabilidade , Temperatura , Termodinâmica , Água/metabolismoRESUMO
The Wissler human thermoregulation model was augmented to incorporate simulation of a space suit thermal control system that includes interaction with a liquid cooled garment (LCG) and ventilation gas flow through the suit. The model was utilized in the design process of an automatic controller intended to maintain thermal neutrality of an exercising subject wearing a liquid cooling garment. An experimental apparatus was designed and built to test the efficacy of specific physiological state measurements to provide feedback data for input to the automatic control algorithm. Control of the coolant inlet temperature to the LCG was based on evaluation of transient physiological parameters that describe the thermal state of the subject, including metabolic rate, skin temperatures, and core temperature. Experimental evaluation of the control algorithm function was accomplished in an environmental chamber under conditions that simulated the thermal environment of a space suit and transient metabolic work loads typical of astronaut extravehicular activity (EVA). The model was also applied to analyze experiments to evaluate performance of the automatic control system in maintaining thermal comfort during extensive transient metabolic profiles for a range of environmental temperatures. Finally, the model was used to predict the efficacy of the LCG thermal controller for providing thermal comfort for a variety of regiments that may be encountered in future space missions. Simulations with the Wissler model accurately predicted the thermal interaction between the subject and LCG for a wide range of metabolic profiles and environmental conditions and matched the function of the automatic temperature controller for inlet cooling water to the LCG.
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Regulação da Temperatura Corporal/fisiologia , Modelos Biológicos , Voo Espacial/instrumentação , Trajes Espaciais , Algoritmos , Temperatura Corporal/fisiologia , Calibragem , Meato Acústico Externo/fisiologia , Metabolismo Energético/fisiologia , Ambiente Controlado , Desenho de Equipamento , Humanos , Temperatura Cutânea/fisiologia , Simulação de Ambiente Espacial , TermômetrosRESUMO
BACKGROUND: Thermal control in the EVA spacesuit requires attention from the astronaut which is not always desirable or feasible. Improvements in thermal control involve implementation of an automatic thermal control system operating independently of the knowledge of the working astronaut. METHODS: A control system was designed, developed, and tested to automatically maintain a subject's thermal neutrality while wearing a liquid cooling garment (LCG). Measurement of CO2 production as an indication of metabolic rate was used as a signal to initiate the control response. Mean body temperature, computed as a function of ear canal temperature and mean skin temperature, provided feedback to account for the thermal state of subjects as they were being cooled by the LCG. The control algorithm was tested on nine subjects, six males and three females, who performed a varying 90-min metabolic profile using an arm cranking ergometer. A total of 27 tests, three for each subject, were conducted in a thermal chamber at three different environmental temperatures: 10 degrees C, 18.3 degrees C and 26.7 degrees C. RESULTS AND CONCLUSIONS: Evaluation of subjective comfort rating and quantitative energy storage indicates good performance of the controller in maintaining thermal neutrality for the subject over a wide range of environmental and transient metabolic states. Measurements of metabolic rate effectively initiated controller response, and feedback of mean body temperature to the controller proved very capable of accounting for various steady-state environmental conditions and inter-subject variability.
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Medicina Aeroespacial , Regulação da Temperatura Corporal , Trajes Espaciais , Adulto , Algoritmos , Desenho de Equipamento , Feminino , Humanos , Masculino , Pessoa de Meia-IdadeRESUMO
This article presents a brief description of a set of equations by which the thermal burn process may be modeled, a formulation of the differential equations into a finite-difference format, and a simple method of solution using a standard commercial spreadsheet software application. A companion article provides a discussion of results that can be obtained with the modeling techniques presented here. A short version of the spreadsheet program is available from the author.
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Queimaduras , Software , Análise de Elementos Finitos , Humanos , Microcomputadores , Modelos BiológicosRESUMO
A network thermodynamic model has been devised to describe the coupled movement of water and a permeable additive within a kidney during perfusion under the combined action of diffusive, hydrodynamic, and mechanical processes. The model has been validated by simulating perfusions with Me2SO, glycerol, and sucrose and comparing predicted weight and vascular resistance with experimental results obtained by Pegg (1993). The flows of CPA, water, colloid, and cellular impermeants are governed by a combination of the individual osmotic potential and pressure differences between compartments of the kidney, the viscoelastic behavior of the tissue, and the momentum transferred between the flows. The model developed in this study presents an analytical tool for understanding the dynamics of the perfused kidney system and for modifying perfusion protocols to minimize the changes in cell volume, internal pressure build-up, and increases in vascular resistance that currently present barriers to the successful perfusion of organs.
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Simulação por Computador , Crioprotetores/farmacocinética , Rim/metabolismo , Modelos Biológicos , Animais , Dimetil Sulfóxido/farmacocinética , Elasticidade , Glicerol/farmacocinética , Rim/anatomia & histologia , Redes Neurais de Computação , Tamanho do Órgão , Osmose , Permeabilidade , Coelhos , Sacarose/farmacocinética , Termodinâmica , Resistência VascularRESUMO
Thermal injury in living tissues is commonly modeled as a rate process in which cell death is interpreted to occur as a function of a single kinetic process. Experimental data indicate that multiple rate processes govern the manifestation of injury and that these processes may act over a broad spectrum of time domains. Injury is typically computed as a dimensionless function (omega) of the temperature time history via an Arrhenius relationship to which numerical values are assigned based on defined threshold levels of damage. However, important issues central to calculation and interpretation of the omega function remain to be defined. These issues include the following: how is temperature identified in time and space within a tissue exposed to thermal stress; what is the biophysical and physiological meaning of a quantitative value for omega; how can omega be quantified in an experimental system; how should omega be scaled between graded levels of injury; and what are the differences in injury kinetics between unit volume- and unit surface area-governed processes of energy deposition into tissue to cause thermal stress? This paper addresses these issues with the goal of defining a more rigorous and comprehensive standard for modeling thermal injury in tissues.
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Queimaduras/fisiopatologia , Animais , Queimaduras/classificação , Queimaduras/patologia , Temperatura Alta , Humanos , Modelos BiológicosRESUMO
Mathematic models have been used for several decades to predict the severity of burn injury that would result from application of a given thermal stress to the surface of the skin. Solution of the governing mathematic equations has been achieved either by analytic methods, with required simplifying assumptions that may compromise the rigor with which the results are applied, or by numeric methods, which require programming of finite element or finite difference codes in computer languages. In recent years microcomputer hardware and the associated software have become both powerful and relatively simple to use, and the price per unit of computing capability has dropped dramatically. Thus it is now possible to perform on a desktop machine with relative case calculations that previously might have been prohibitively complex or expensive. Modeling of burn injuries fits into this category. This article presents a straightforward method for implementing a finite difference solution to the burn process through the combination of a Macintosh personal computer and a widely used spreadsheet software program; this hardware and software combination has been used widely for a broad spectrum of general computing activities. This article presents a model for a surface thermal burn, as implemented for solution on a spreadsheet, with example runs to illustrate and verify the method.
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Queimaduras , Simulação por Computador , Microcomputadores , Pele/lesões , Software , HumanosRESUMO
It is well understood that the solidification of a solution results in a redistribution of solute in the liquid zone. For the freezing of suspensions of cells it is anticipated that accumulation of solute in the region leading a growing ice phase will cause an osmotic response in cells before the ice phase reaches the cells. To measure this phenomenon in a specific algal species, the volume changes in Chlorococcum texanum during freezing were studied using directional solidification cryomicroscopy. The relative cell volume was tracked continuously as a function of temperature and position as cells encountered the moving phase front. The loss of cell volume was measured in the liquid region containing concentrated solute ahead of the growing solid phase.
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Tamanho Celular , Clorófitas/citologia , Clorófitas/fisiologia , Criopreservação/métodos , Congelamento , Microscopia/métodosRESUMO
Network thermodynamic modeling via bond graphs was used to describe the water and cryoprotectant additive (CPA) transport in a multicellular tissue. The model is presented as a tool to understand the osmotic behavior of the islets of Langerhans when exposed to ternary aqueous solutions containing an electrolyte and a CPA. It accounts for the effects of the location of cells within the tissue and an interstitial matrix, plus differential permeabilities to water and CPA. The interstitial matrix was assumed to be a porous medium able to store the chemical species being transported. Controlled osmotic stress experiments were conducted on isolated rat pancreas islets to measure the transient volumetric response to step-wise changes in dimethyl sulfoxide, Me2SO, concentration. The model provides a tool for predicting the transient volumetric response of peripheral and interior cells and of interstitial tissue, as well as the build up of solute concentration, during addition and removal of CPAs and freezing and thawing protocols. Inverse solution methods were applied to determine values for standard cell membrane permeability parameters Lp, omega and sigma as well as for the interstitial flow conductivities Kw and Kp'.
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Crioprotetores/farmacocinética , Dimetil Sulfóxido/farmacocinética , Ilhotas Pancreáticas/fisiologia , Modelos Biológicos , Animais , Transporte Biológico , Biofísica/métodos , Tamanho Celular , Criopreservação/métodos , Eletrólitos , Técnicas In Vitro , Ilhotas Pancreáticas/citologia , Matemática , Ratos , Soluções , Condutividade Térmica , TermodinâmicaRESUMO
The introduction and removal of cryoprotective agents (CPA) to a kidney via vascular perfusion may induce changes in cell volume that are destructive to the tubular epithelial or capillary endothelial cells as well as causing significant increases in vascular resistance that compromise the perfusion process. A network thermodynamic model of the coupled osmotic, hydrodynamic and elastic properties of the kidney was applied to evaluate the sensitivity of these critical outputs to a set of physiological and perfusion variables. Simulation results suggest that in the design of perfusion protocols for CPAs such as glycerol, it may be advantageous to: (a) select a CPA with as high a cell membrane permeability as possible; (b) increase the concentration of mannitol in the perfusate to about 200 mos/kg, beyond which there is no discernible benefit; (c) when glycerol is the CPA, limit the rate of reduction in the perfusate during removal to 30 mM/min or less; (d) limit the perfusion pressure to 20-30 mm Hg, within the practical constraints of the perfusion system; (e) increase the concentration of impermeant in the perfusate to as high as 400 mos/kg, although it is recognized that this departure from plasma-like composition might impose other problems that are not considered in this model. Further, it was observed that the vascular membrane permeability plays a relatively minor role in controlling cellular osmotic injury and vascular perfusion resistance and is therefore not a critical parameter in the perfusion design process.
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Criopreservação/métodos , Rim , Circulação Hepática/fisiologia , Animais , Permeabilidade Capilar , Permeabilidade da Membrana Celular , Crioprotetores , Glicerol , Rim/citologia , Rim/fisiologia , Manitol , Microcirculação/fisiologia , Perfusão/métodosRESUMO
BACKGROUND: The ability of rat pancreatic islets to revascularize after transplantation was examined via in vitro and in vivo imaging of the microvasculature using laser scanning confocal microscopy (LSCM). METHODS: Cultured or cryoprocessed islets were transplanted at the renal subcapsular site in rats. At various time intervals after transplantation, three-dimensional imaging of the graft was performed by LSCM. In vitro studies were conducted via microvascular corrosion casting of the grafted kidney in situations where it was difficult to obtain in vivo confocal data due to surgical complications. The vascular morphology of the islet grafts was evaluated quantitatively via digital image analysis algorithms to determine the morphology of the neovascular ingrowth and the rate of revascularization. RESULTS: In cultured islet grafts, the initiation of angiogenesis was observed within 1 week, characterized by the presence of capillary sprouts, tortuous vessels, and blood vessels with blind ends. The revascularization of the graft was typically completed within 2 weeks and could be distinguished as a network of completely perfused blood vessels consisting of intertwining capillaries, with surrounding arterioles and venules. The angiogenesis process in cryopreserved islet grafts required a longer time period to initiate (approximately 2 weeks), and the revascularization was completed in 1 week after the initiation. CONCLUSIONS: These results successfully demonstrate the potential of the described in vivo and in vitro LSCM techniques to measure the angiogenesis process in pancreatic islet grafts.