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1.
Phys Rev Lett ; 130(6): 061001, 2023 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-36827568

RESUMO

Instantons, which are nonperturbative solutions to Yang-Mills equations, provide a signal for the occurrence of quantum tunneling between distinct classes of vacua. They can give rise to decays of particles otherwise forbidden. Using data collected at the Pierre Auger Observatory, we search for signatures of such instanton-induced processes that would be suggestive of super-heavy particles decaying in the Galactic halo. These particles could have been produced during the post-inflationary epoch and match the relic abundance of dark matter inferred today. The nonobservation of the signatures searched for allows us to derive a bound on the reduced coupling constant of gauge interactions in the dark sector: α_{X}≲0.09, for 10^{9}≲M_{X}/GeV<10^{19}. Conversely, we obtain that, for instance, a reduced coupling constant α_{X}=0.09 excludes masses M_{X}≳3×10^{13} GeV. In the context of dark matter production from gravitational interactions alone, we illustrate how these bounds are complementary to those obtained on the Hubble rate at the end of inflation from the nonobservation of tensor modes in the cosmological microwave background.

2.
Phys Rev Lett ; 126(15): 152002, 2021 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-33929235

RESUMO

We present the first measurement of the fluctuations in the number of muons in extensive air showers produced by ultrahigh energy cosmic rays. We find that the measured fluctuations are in good agreement with predictions from air shower simulations. This observation provides new insights into the origin of the previously reported deficit of muons in air shower simulations and constrains models of hadronic interactions at ultrahigh energies. Our measurement is compatible with the muon deficit originating from small deviations in the predictions from hadronic interaction models of particle production that accumulate as the showers develop.

3.
Phys Rev Lett ; 125(12): 121106, 2020 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-33016715

RESUMO

We report a measurement of the energy spectrum of cosmic rays above 2.5×10^{18} eV based on 215 030 events. New results are presented: at about 1.3×10^{19} eV, the spectral index changes from 2.51±0.03(stat)±0.05(syst) to 3.05±0.05(stat)±0.10(syst), evolving to 5.1±0.3(stat)±0.1(syst) beyond 5×10^{19} eV, while no significant dependence of spectral features on the declination is seen in the accessible range. These features of the spectrum can be reproduced in models with energy-dependent mass composition. The energy density in cosmic rays above 5×10^{18} eV is [5.66±0.03(stat)±1.40(syst)]×10^{53} erg Mpc^{-3}.

4.
Phys Med ; 32(12): 1651-1658, 2016 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-27989415

RESUMO

PURPOSE: Glioblastoma Multiforme (GBM) is the most common malignant brain tumor and frequently recurs in the same location after radiotherapy. Intensive treatment targeting localized lesion is required to improve GBM outcome, but dose escalation using conventional methods is limited by healthy tissue tolerance. Helical Tomotherapy (HT) Dose Painting (DP) treatments were simulated to safely deliver high doses in the recurrent regions. MATERIALS AND METHODS: Apparent Diffusion Coefficient (ADC) data from five recurrent GBM were retrospectively considered for planning. Hypo-fractionated (25-50Gy, 5 fractions) voxel-based prescriptions were opportunely converted to personalized structured-based dose maps to create DP plans with a commercial Treatment Planning System. Optimized plans were generated and analyzed in terms of plan conformity to dose prescription (Q0.90-1.10), tolerance of the healthy tissues (DMAX), and dosimetry accuracy of the deliverable plans (γ-index). RESULTS: Only three of the five cases could receive a safe retreatment without violating the maximum critical organs dose constraints. The conformity of the simulated plans was between 40.9% and 79.9% (Q0.90-1.10), their delivery time was in the range of 38.3-63.6min, while the dosimetry showed γ-index of 82.4-92.4%. CONCLUSIONS: This study proved the ability of our method to simulate personalized, deliverable and dosimetrically accurate DPBN plans. HT hypo-fractionated treatments guided by ADC maps can be realized and applied to deliver high doses in the GBM recurrent regions, although there are some critical issues related to low Q0.90-1.10 values, to exceeding of healthy-tissue dose constraints for some patients and long delivery times.


Assuntos
Glioblastoma/diagnóstico por imagem , Glioblastoma/radioterapia , Doses de Radiação , Planejamento da Radioterapia Assistida por Computador/métodos , Radioterapia Guiada por Imagem , Radioterapia de Intensidade Modulada , Difusão , Estudos de Viabilidade , Humanos , Dosagem Radioterapêutica , Recidiva
5.
Phys Rev Lett ; 117(19): 192001, 2016 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-27858429

RESUMO

Ultrahigh energy cosmic ray air showers probe particle physics at energies beyond the reach of accelerators. Here we introduce a new method to test hadronic interaction models without relying on the absolute energy calibration, and apply it to events with primary energy 6-16 EeV (E_{CM}=110-170 TeV), whose longitudinal development and lateral distribution were simultaneously measured by the Pierre Auger Observatory. The average hadronic shower is 1.33±0.16 (1.61±0.21) times larger than predicted using the leading LHC-tuned models EPOS-LHC (QGSJetII-04), with a corresponding excess of muons.

6.
Phys Med ; 32(3): 506-11, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-27053449

RESUMO

The purpose of this study was to quantify the impact of inter-fraction modifications of bladder during RT of prostate cancer on bladder dose surface maps (DSM). Eighteen patients treated with daily image-guided Tomotherapy and moderate hypofractionation (70-72.8Gy at 2.5-2.6Gy/fr in 28 fractions and full bladder) were considered. Bladder contours were delineated on co-registered daily Megavoltage CT (MVCT) by a single observer and copied on the planning CT to generate dose-volume/surface histograms (DVH/DSH) and bladder DSMs. Discrepancies between planned and daily absorbed doses were analyzed through the average of individual systematic errors, the population systematic errors and the population random errors for the DVH/DSHs and DSMs. In total, 477 DVH/DSH and 472 DSM were available. DSH and DVH showed small population systematic errors of absolute surfaces (<3.4cm(2)) and volumes (<8.4cm(3)) at the highest doses. The dose to the posterior bladder base assessed on DSMs showed a mean systematic error below 1Gy, with population systematic and random errors within 4 and 3Gy, respectively. The region surrounding this area shows higher mean systematic errors (1-3Gy), population systematic (8-11Gy) and random (5-7Gy) errors. In conclusion, DVH/DSH and DSMs are quite stable with respect to inter-fraction variations in the high-dose region, within about 2cm from bladder base. Larger systematic variations occur in the anterior portion and cranially 2.5-3.5cm from the base. Results suggest that dose predictors related to the high dose area (including the trigone dose) are likely to be sufficiently reliable with respect to the expected variations due to variable bladder filling.


Assuntos
Neoplasias da Próstata/radioterapia , Lesões por Radiação/etiologia , Planejamento da Radioterapia Assistida por Computador/métodos , Bexiga Urinária/diagnóstico por imagem , Bexiga Urinária/efeitos da radiação , Transtornos Urinários/etiologia , Estudos de Coortes , Fracionamento da Dose de Radiação , Humanos , Masculino , Neoplasias da Próstata/diagnóstico por imagem , Lesões por Radiação/prevenção & controle , Radioterapia de Intensidade Modulada/métodos , Glândulas Seminais/anatomia & histologia , Glândulas Seminais/diagnóstico por imagem , Glândulas Seminais/efeitos da radiação , Bexiga Urinária/anatomia & histologia , Transtornos Urinários/prevenção & controle
7.
Radiol Med ; 116(7): 1039-49, 2011 Oct.
Artigo em Inglês, Italiano | MEDLINE | ID: mdl-21424564

RESUMO

PURPOSE: The aim of this study was to investigate the efficacy of a dedicated software tool for automated volume measurement of breast lesions in contrast-enhanced (CE) magnetic resonance mammography (MRM). MATERIAL AND METHODS: The size of 52 breast lesions with a known histopathological diagnosis (three benign, 49 malignant) was automatically evaluated using different techniques. The volume of all lesions was measured automatically (AVM) from CE 3D MRM examinations by means of a computer-aided detection (CAD) system and compared with the size estimates based on maximum diameter measurement (MDM) on MRM, ultrasonography (US), mammography and histopathology. RESULTS: Compared with histopathology as the reference method, AVM understimated lesion size by 4% on average. This result was similar to MDM (3% understimation, not significantly different) but significantly better than US and mammographic lesion measurements (24% and 33% size underestimation, respectively). CONCLUSIONS: AVM is as accurate as MDM but faster. Both methods are more accurate for size assessment of breast lesions compared with US and mammography.


Assuntos
Neoplasias da Mama/diagnóstico , Carcinoma Intraductal não Infiltrante/diagnóstico , Carcinoma Lobular/diagnóstico , Diagnóstico por Computador , Imageamento por Ressonância Magnética , Mamografia , Adulto , Idoso , Neoplasias da Mama/diagnóstico por imagem , Neoplasias da Mama/patologia , Carcinoma Ductal de Mama/diagnóstico , Carcinoma Intraductal não Infiltrante/diagnóstico por imagem , Carcinoma Intraductal não Infiltrante/patologia , Carcinoma Lobular/diagnóstico por imagem , Carcinoma Lobular/patologia , Meios de Contraste , Feminino , Humanos , Mamografia/métodos , Pessoa de Meia-Idade , Valor Preditivo dos Testes , Estudos Retrospectivos , Sensibilidade e Especificidade , Ultrassonografia
8.
Nutr Hosp ; 25(3): 428-36, 2010.
Artigo em Inglês | MEDLINE | ID: mdl-20593126

RESUMO

BACKGROUND: Since no growth standards for adolescents exist and a single reference applicable everywhere is still in debate, it is recognized that the best reference should be derived from the growth pattern of the healthy population that will use it. In 2007 a study developed references for body mass index for 12th to 18th y Bolivian school adolescent (BAP. OBJECTIVES: To compare nutritional status outcomes applying BMI references from the BAP, the Center for Disease Control and Prevention CDC 2000, the International Task Force (IOTF), and the 2007 WHO, to determine appropriateness of use in Bolivian adolescents. SUBJECTS/METHODS: References were applied in 3306 adolescents, 45.0% male, 55% female, 12th to 18th y selected from a nationally representative sample. RESULTS: Main findings reveal that the CDC and the 2007 WHO underestimate underweight (p<0.001) and the three international references overestimate overweight (p<0.001) with variation between ages and gender. CONCLUSIONS: Bolivian health providers are advised to replace CDC, OITF and 2007 WHO references for the use of BAP in Bolivia which reflects its healthy adolescent population growth pattern. International references may lead to incorrect conclusions when applied on Bolivian adolescents. They could deflect efforts from population which need prompt intervention and mislead treatments and budget to unnecessary ones. We recommend validation of international references where appropriate until a standard is released.


Assuntos
Índice de Massa Corporal , Estado Nutricional , Sobrepeso/diagnóstico , Magreza/diagnóstico , Adolescente , Fatores Etários , Bolívia , Criança , Feminino , Humanos , Internacionalidade , Masculino , Obesidade/diagnóstico , Valores de Referência
9.
Nutr. hosp ; 25(3): 428-436, mayo-jun. 2010. tab, graf
Artigo em Inglês | IBECS | ID: ibc-84722

RESUMO

Background: Since no growth standards for adolescents exist and a single reference applicable everywhere is still in debate, it is recognized that the best reference should be derived from the growth pattern of the healthy population that will use it. In 2007 a study developed references for body mass index for 12th to 18th y Bolivian school adolescent (BAP. Objectives: To compare nutritional status outcomes applying BMI references from the BAP, the Center for Disease Control and Prevention CDC 2000, the International Task Force (IOTF), and the 2007 WHO, to determine appropriateness of use in Bolivian adolescents. Subjects/methods: References were applied in 3306 adolescents, 45.0% male, 55% female, 12th to 18th y selected from a nationally representative sample. Results: Main findings reveal that the CDC and the 2007 WHO underestimate underweight (p < 0.001) and the three international references overestimate overweight (p < 0.001) with variation between ages and gender. Conclusions: Bolivian health providers are advised to replace CDC, OITF and 2007WHO references for the use of BAP in Bolivia which reflects its healthy adolescent population growth pattern. International references may lead to incorrect conclusions when applied on Bolivian adolescents. They could deflect efforts from population which need prompt intervention and mislead treatments and budget to unnecessary ones. We recommend validation of international references where appropriate until a standard is released (AU)


Introducción: Puesto que no existen estándares de crecimiento para adolescentes y la aplicación de una sola referencia a nivel mundial es aún debatible, se reconoce que la mejor referencia es aquella derivada del patrón de crecimiento de la población saludable en la que será posteriormente utilizada. Por ello en 2007 se efectuó un estudio para desarrollar la Referencia Boliviana de IMC poredad (BAP) para adolescentes entre 12 a 18 años). Objetivos: Comparar la clasificación de adolescentes por categorías nutricionales, aplicando las referencias de IMC boliviano (BAP), la referencia CDC 2000, los puntosde corte de IOTF y de la OMS, 2007. Métodos y población: Las referencias se aplicaron a los datos medidos de peso y talla de 3.306 adolescentes, 45% varones y 55% mujeres seleccionados de una muestrarepresentativa de la población boliviana. Resultados: Se observa que CDC y OMS 2007 subestiman la prevalencia de delgadez (P < 0,001) mientras que las tres referencias internacionales sobreestiman el sobrepeso(p < 0,001) con variaciones por edad y género. Conclusión: Se recomienda al personal de salud boliviano reemplazar las referencias CDC, IOTF y OMS 2007 por la Referencia BAP, la cual refleja el patrón de crecimiento de la población de adolescentes saludables. Las referencias internacionales pueden conducir a conclusiones erróneas cuando se aplican en la población boliviana. Su uso puede desperdiciar esfuerzos y recursos en poblaciones que no necesitan intervención, mientras desatienden aquellas que verdaderamente lo necesitan (AU)


Assuntos
Humanos , Masculino , Feminino , Criança , Adolescente , Índice de Massa Corporal , Estado Nutricional , Sobrepeso/diagnóstico , Magreza/diagnóstico , Fatores Etários , Bolívia , Internacionalidade , Obesidade/diagnóstico , Valores de Referência
10.
Rev Sci Instrum ; 81(3): 033905, 2010 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-20370190

RESUMO

NIMROD is the Near and InterMediate Range Order Diffractometer of the ISIS second target station. Its design is optimized for structural studies of disordered materials and liquids on a continuous length scale that extends from the atomic, upward of 30 nm, while maintaining subatomic distance resolution. This capability is achieved by matching a low and wider angle array of high efficiency neutron scintillation detectors to the broad band-pass radiation delivered by a hybrid liquid water and liquid hydrogen neutron moderator assembly. The capabilities of the instrument bridge the gap between conventional small angle neutron scattering and wide angle diffraction through the use of a common calibration procedure for the entire length scale. This allows the instrument to obtain information on nanoscale systems and processes that are quantitatively linked to the local atomic and molecular order of the materials under investigation.

11.
Nutr Hosp ; 24(3): 304-11, 2009.
Artigo em Inglês | MEDLINE | ID: mdl-19721903

RESUMO

Anthropometry is important as clinical tool for individual follow-up as well as for planning and health policy-making at population level. Recent references of Bolivian Adolescents are not available. The aim of this cross sectional study was to provide age and sex specific centile values and charts of Body Mass Index, height, weight, arm, wrist and abdominal circumference from Bolivian Adolescents. Data from the MEtabolic Syndrome in Adolescents (MESA) study was used. Thirty-two Bolivian clusters from urban and rural areas were selected randomly considering population proportions, 3445 school going adolescents, 12 to 18 y, 45% males; 55% females underwent anthropometric evaluation by trained personnel using standardized protocols for all interviews and examinations. Weight, height, wrist, arm and abdominal circumference data were collected. Body Mass Index was calculated. Smoothed age- and gender specific 3rd, 5th, 10th, 25th, 50th, 75th, 85th, 90th, 95th and 97th Bolivian adolescent percentiles(BAP) and Charts(BAC) where derived using LMS regression. Percentile-based reference data for the antropometrics of for Bolivian Adolescents are presented for the first time.


Assuntos
Braço/anatomia & histologia , Estatura , Índice de Massa Corporal , Peso Corporal , Circunferência da Cintura , Punho/anatomia & histologia , Adolescente , Bolívia , Criança , Estudos Transversais , Feminino , Humanos , Masculino , Valores de Referência
12.
J Phys Chem B ; 113(29): 10014-21, 2009 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-19569631

RESUMO

The results of a neutron diffraction experiment performed on aqueous solutions of KSCN are analyzed and discussed in comparison with similar data for KCl and KOH solutions. The effect of the different ions on the structure of water and the differences and similarities among the ion solvation shells are discussed in detail. In particular it is shown that the effect of KSCN on the structure of water is visible as a shift and a broadening of the second peak of the oxygen-oxygen radial distribution function, which corresponds to a lower number of interstitial water molecules, compared to pure water. The hydration shell of the cation is similar to that found in the case of KCl solutions, and more interestingly the hydration shell of SCN- is asymmetric, with water molecules H-bonded to the N site and weakly correlated to the S site. These results provide a reasonable microscopic description of the mechanism for the high efficiency of thiocyanate in crystallizing basic proteins.


Assuntos
Tiocianatos/química , Água/química , Difração de Nêutrons , Solubilidade
13.
Nutr. hosp ; 24(3): 304-311, mayo-jun. 2009. ilus, tab
Artigo em Inglês | IBECS | ID: ibc-134937

RESUMO

Anthropometry is important as clinical tool for individual follow-up as well as for planning and health policymaking at population level. Recent references of Bolivian Adolescents are not available. The aim of this cross sectional study was to provide age and sex specific centile values and charts of Body Mass Index, height, weight, arm, wrist and abdominal circumference from Bolivian Adolescents. Data from the Metabolic Syndrome in Adolescents (MESA) study was used. Thirty-two Bolivian clusters from urban and rural areas were selected randomly considering population proportions, 3445 school going adolescents, 12 to 18 y, 45% males; 55% females underwent anthropometric evaluation by trained personnel using standardized protocols for all interviews and examinations. Weight, height, wrist, arm and abdominal circumference data were collected. Body Mass Index was calculated. Smoothed age- and gender specific 3rd, 5th, 10th, 25th, 50th, 75th, 85th, 90th, 95th and 97th Bolivian adolescent percentiles(BAP) and Charts(BAC) where derived using LMS regression. Percentile-based reference data for the antropometrics of for Bolivian Adolescents are presented for the first time (AU)


La antropometría es una herramienta clínica importante para el seguimiento individual de los pacientes así como para la planificación de políticas públicas. En Bolivia no existen referencias antropométricas nacionales para adolescentes. El objetivo de este estudio transversal fue de desarrollar percentiles y diagramas de crecimiento para peso, talla, índice de masa corporal, presión arterial sistólica y diastólica, circunferencia de muñeca, brazo y abdominal de adolescentes bolivianos. Los datos antropométricos en el estudio MESA (Síndrome metabólico en adolescentes bolivianos) fueron obtenidos a partir de 32 unidades muestrales, considerando proporcionalidad muestral con reposición. Fueron evaluados 3445 adolescentes de 12 a 18, 45% hombres; 55% mujeres, de colegios de áreas urbanas y rurales. La evaluación fue efectuada por personal entrenado siguiendo procedimientos estandarizados. Se tomaron medidas del peso, talla circunferencias de muñeca, brazo y abdominal. El índice de masa corporal fue calculado. Se obtuvieron los valores de los percentiles 3º, 5º, 10º, 25º, 50º, 75º, 85º, 90º, 95º y 97º utilizando regresión por el método LMS. Las referencias antropométricas para los adolescentes bolivianos son presentadas por vez primera a la comunidad médica. ( En la versión electronica de Nutrición Hospitalaria se puede consultar el texto integro en castellano de este articulo) (AU)


Assuntos
Humanos , Masculino , Feminino , Adolescente , Antropometria/métodos , Pesos e Medidas Corporais/estatística & dados numéricos , Avaliação Nutricional , Estado Nutricional , Composição Corporal , Desenvolvimento do Adolescente/fisiologia , Peso-Estatura , Circunferência Abdominal , Índice de Massa Corporal , Nutrição do Adolescente , Bolívia
14.
Obes Rev ; 10(4): 373-7, 2009 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-19389056

RESUMO

Secondary analysis of Bolivian Demographic and Health Surveys 1994, 1998 and 2003 revealed a steady raising trend in levels of overweight and obesity among women in childbearing age (20-45 years), reaching 30% and 15% respectively in 2003. Adolescents' cross-sectional data suggest that overweight and obesity are mainly found in urban areas. Applying the Bolivian body mass index-for-age reference, obesity reached 5% in adolescents, while overweight affects 14% of adolescents. This overview highlights the importance of including the prevention of weight gain among the public health nutrition policies in Bolivia.


Assuntos
Índice de Massa Corporal , Sobrepeso/epidemiologia , Sobrepeso/prevenção & controle , Adolescente , Adulto , Bolívia/epidemiologia , Criança , Estudos Transversais , Feminino , Política de Saúde , Inquéritos Epidemiológicos , Humanos , Masculino , Pessoa de Meia-Idade , Obesidade/epidemiologia , Obesidade/prevenção & controle , Prevalência , Saúde Pública , Saúde da População Urbana , Aumento de Peso , Saúde da Mulher , Adulto Jovem
15.
Phys Rev E Stat Nonlin Soft Matter Phys ; 78(2 Pt 1): 021505, 2008 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-18850839

RESUMO

It is well established that at ambient and supercooled conditions water can be described as a percolating network of H bonds. This work is aimed at identifying, by neutron diffraction experiments combined with computer simulations, a percolation line in supercritical water, where the extension of the H-bond network is in question. It is found that in real supercritical water liquidlike states are observed at or above the percolation threshold, while below this threshold gaslike water forms small, sheetlike configurations. Inspection of the three-dimensional arrangement of water molecules suggests that crossing of this percolation line is accompanied by a change of symmetry in the first neighboring shell of molecules from trigonal below the line to tetrahedral above.

16.
Phys Rev Lett ; 100(12): 127802, 2008 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-18517911

RESUMO

We find, by means of a deep inelastic neutron scattering experiment, a significant excess of proton mean kinetic energy E_(k) in supercooled water, compared with that measured in stable liquid and solid phases. The measured values of E_(k) at moderate degrees of supercooling do not fit the predicted linear increase with temperature observed for the water stable phases. This anomalous behavior is confirmed by the shape of the measured momentum distribution, thus supporting a likely occurrence of ground-state quantum delocalization of a proton between the O atoms of two neighboring molecules. These results strongly suggest a transition from a single-well to a double-well potential felt by the delocalized proton, with a reduced first neighbor O-O distance, in the supercooled state, as compared to ambient condition.

17.
J Chem Phys ; 128(16): 164504, 2008 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-18447456

RESUMO

The microscopic structure of supercritical water-CO(2) mixture is investigated by neutron diffraction experiments exploiting the isotopic HD substitution. The investigated water reach mixtures are in the liquidlike region of the phase diagram, according to the behavior of the radial distribution functions, yet a reduction of the average number of hydrogen bonds, compared to equivalent states of pure water, is found. As a consequence, the average dimension of water clusters is reduced and the system stays below the percolation threshold. These results, along with the shift of the main peaks of the site-site radial distribution functions, suggest that the excess volume in these supercritical mixtures is likely associated with the CO(2) solvation shell.

18.
J Phys Chem B ; 111(48): 13570-7, 2007 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-17988114

RESUMO

Neutron diffraction data with hydrogen isotope substitution on aqueous solutions of NaCl and KCl at concentrations ranging from high dilution to near-saturation are analyzed using the Empirical Potential Structure Refinement technique. Information on both the ion hydration shells and the microscopic structure of the solvent is extracted. Apart from obvious effects due to the different radii of the three ions investigated, it is found that water molecules in the hydration shell of K+ are orientationally more disordered than those hydrating a Na+ ion and are inclined to orient their dipole moments tangentially to the hydration sphere. Cl- ions form instead hydrogen-bonded bridges with water molecules and are readily accommodated into the H-bond network of water. The results are used to show that concepts such as structure maker/breaker, largely based on thermodynamic data, are not helpful in understanding how these ions interact with water at the molecular level.

19.
Phys Chem Chem Phys ; 9(23): 2959-67, 2007 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-17551619

RESUMO

The ion induced modification to the tetrahedral structure of water is a topic of much current interest. We address this question by interpreting neutron diffraction data from monovalent ionic solutions of NaCl and KCl using a computer assisted structural modeling technique. We investigate the effect that these ions have on the water-water O-O, O-H and H-H radial distribution functions as a function of ionic concentration. It is found that the O-H and H-H functions are only marginally affected by ionic composition, signaling that hydrogen bonding between water molecules remains largely intact, even at the highest concentrations. On the other hand the O-O functions are strongly modified by the ions. In particular the position of the second peak in g(OO)(r), is found to move inwards with increasing salt concentration, in a manner closely analogous to what happens in pure water under pressure. Furthermore by recalculating g(OO)(r) after excluding all the water molecules in the first hydration shell of each ion, we show that this structural perturbation exists outside the first hydration shell of the ions.

20.
J Chem Phys ; 125(1): 014508, 2006 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-16863317

RESUMO

There is an ongoing debate on the nature of hydration of the hydrogen ion, H+ in solution, and the extent to which Eigen or Zundel complexes occur. Here, our previous neutron diffraction data on a solution of 1:9 HCl in water are reanalyzed using a new starting hypothesis for the Monte Carlo simulation of the data. Either bare H+ ions, all H3O+ ions, or all H5O2 + ions are allowed in the simulation box together with the water and chlorine ions. All three simulations give a satisfactory fit to the experimental data. From the simulation with simple H+ ions, it is found that all H+ ions form one strong and very short hydrogen bond with water molecules and that on average 75% of them also engage in a second, slightly longer hydrogen bond. This result can be interpreted alternatively either in terms of the formation of a high percentage of asymmetric Zundel complexes or in terms of the formation of distorted H3O+ ions, which in turn form two or three hydrogen bonds, respectively, with neighboring molecules opposite their unbonded hydrogen sites (thus forming Eigen complexes). Therefore the new analysis is not inconsistent with our previous conclusion that the solution consists primarily of Eigen complexes, but does highlight the difficulty of making a clear distinction between Eigen and Zundel complexes due to the continuous random network of hydrogen bonds formed between water and hydrated protons. The role of hydrogen ion to chloride counterion contacts is also discussed in these solutions.

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