Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 35
Filtrar
Más filtros










Base de datos
Intervalo de año de publicación
1.
J Stroke Cerebrovasc Dis ; 33(5): 107644, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38387761

RESUMEN

BACKGROUND: The rapid progress in imaging techniques has led to an upsurge in the incidence of optic nerve arteriovenous malformations (AVMs) diagnoses. Nevertheless, a comprehensive integration addressing their diagnostic and therapeutic attributes remains elusive. CASE DESCRIPTION AND THE LITERATURE REVIEW: In this report, we present a case of optic nerve AVM in a patient who initially presented with progressive visual deterioration in the right eye. An orbital magnetic resonance imaging (MRI) scan revealed an abnormal signal intensity within the optic nerve region of the affected eye, and Computed Tomography Angiography (CTA) demonstrated the presence of a vascular malformation involving the optic nerve in the right eye. The diagnosis of optic nerve AVMs relies on Digital Subtraction Angiography (DSA). Given the challenging nature of surgical intervention, the patient opted for conservative management. Upon subsequent evaluation, no significant changes were observed in the patient's right visual acuity and visual field. Furthermore, a comprehensive literature review was conducted. CONCLUSIONS: In summary, the principal clinical presentations associated with optic nerve AVMs include a deterioration in both visual acuity and visual field. Angiography serves as the preferred diagnostic modality to confirm optic nerve AVMs. Microsurgical intervention or interventional embolization techniques may offer effective management approaches to address this complex condition.


Asunto(s)
Embolización Terapéutica , Malformaciones Arteriovenosas Intracraneales , Humanos , Malformaciones Arteriovenosas Intracraneales/complicaciones , Malformaciones Arteriovenosas Intracraneales/diagnóstico por imagen , Malformaciones Arteriovenosas Intracraneales/terapia , Imagen por Resonancia Magnética , Nervio Óptico/diagnóstico por imagen , Agudeza Visual , Campos Visuales , Angiografía de Substracción Digital , Embolización Terapéutica/métodos
2.
Opt Lett ; 49(3): 558-561, 2024 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-38300058

RESUMEN

Auto-focusing technology in ultrafast laser processing, especially for non-planar structures, holds paramount importance. The existing methodologies predominantly rely on optical mechanisms, thereby being limited by the original system and material reflectivity. This work proposes an approach that utilizes laser-induced sound as a feedback signal for system control, thereby circumventing the need for optical system adjustments and facilitating almost real-time tracking. We established an ultrafast laser processing system augmented by acoustic emission technology, allowing for focus tracking on inclined planes. This system also exhibits the capability to generate diverse microscopic morphologies, including grooves and differently oriented laser-induced periodic surface structures (LIPSS), through the manipulation of the acoustic signal threshold. This method can be easily integrated into existing laser processing systems, offering new capabilities for curved surface processing, microstructure manufacturing, and transparent material processing.

3.
World Neurosurg ; 182: e414-e430, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38040330

RESUMEN

OBJECTIVE: The occurrence of dural arteriovenous fistulas (DAVFs) at the craniocervical junction (CCJ) is an uncommon vascular malformation. The diagnosis and treatment of CCJ DAVFs present a formidable challenge. This study aims to investigate the effect of endovascular embolization and microsurgery on improving patient prognosis. METHODS: This retrospective study included patients diagnosed with CCJ DAVFs who received treatment at the First Affiliated Hospital of Fujian Medical University between January 2000 and January 2023. The clinical records, imaging data, and treatment methods were obtained from the hospital's medical record system. The patients were classified into microsurgery and embolization groups based on the surgical technique employed for treatment. The primary outcome measures were surgical-associated neurological dysfunction (SAND) and long-term neurological outcomes. The Cox proportional hazard regression was utilized to determine hazard ratios and 95% confidence intervals (CI) to assess the relationship between treatment methods and prognosis. Kaplan-Meier survival analysis was employed to evaluate the incidence of SAND in both cohorts. RESULTS: This study recruited 46 patients with an average age of 53.72 ± 13.83 years. In the microsurgery group, there were 12 cases (26.1%) observed. While in the embolization group, there were 34 cases (73.9%). Of these patients, 16 (34.8%) experienced SAND after treatment. In the microsurgery group, there were 8 cases (75.0%), while in the embolization group, only 8 cases (23.5%) were reported. Specifically, the embolization group exhibited a significantly lower risk of SAND [adjusted hazard ratio = 0.259, 95% CI = 0.096-0.700; P = 0.008)] compared to the microsurgery group. Additionally, the combined Borden grade 2-3 was found to be significantly associated with SAND (adjusted hazard ratio = 3.150, 95% CI = 1.132-8.766; P = 0.028). The results of the Kaplan-Meier survival analysis indicated a statistically significant difference in the occurrence of favorable functional outcomes between the 2 groups (log-rank P = 0.0081). CONCLUSIONS: CCJ DAVFs are uncommon disorders characterized by a diverse range of clinical manifestations. The functional prognosis of endovascular treatment may be superior to microsurgery.


Asunto(s)
Malformaciones Vasculares del Sistema Nervioso Central , Embolización Terapéutica , Humanos , Adulto , Persona de Mediana Edad , Anciano , Estudios Retrospectivos , Microcirugia/métodos , Malformaciones Vasculares del Sistema Nervioso Central/diagnóstico por imagen , Malformaciones Vasculares del Sistema Nervioso Central/cirugía , Embolización Terapéutica/métodos , Pronóstico , Resultado del Tratamiento
4.
Front Biosci (Landmark Ed) ; 28(11): 289, 2023 11 16.
Artículo en Inglés | MEDLINE | ID: mdl-38062817

RESUMEN

BACKGROUND: Abnormalities in regulated cell death (RCD) are involved in multiple diseases. However, the role of RCD in intracranial aneurysms (IA) remains unknown. The aim of this study was to explore different RCD processes in the pathogenesis of IA. METHODS: Four microarray datasets (GSE75436, GSE54083, GSE13353, GSE15629) and one RNA sequencing (RNA-seq) dataset (GSE122897) were extracted from the Gene Expression Omnibus (GEO) database. The microarray datasets were merged to form the training set, while the RNA-seq dataset was used as the validation set. Differentially expressed genes (DEGs), gene set enrichment analysis (GSEA), and gene set variation analysis (GSVA) were used to investigate the role of different types of RCD, including apoptosis, necroptosis, autophagy, ferroptosis and pyroptosis in the formation of IA. A novel cell death classification system for IA was established using an unsupervised consensus clustering algorithm based on cell death signature genes. Differences in functional enrichment, cell death-related regulators, and immune infiltration between two cell death clusters were evaluated. Finally, predictive genes were identified using the least absolute shrinkage and selection operator (LASSO) regression, random forest and logistic regression, allowing a prediction model to be constructed for IA rupture. RESULTS: Multiple RCD processes were significantly activated in IAs compared to controls. A total of 33 signature genes related to cell death were identified. The IA samples were divided into two clusters based on the cell death signature. The cell death-high subtype had a relatively higher rate of rupture, and higher enrichment levels for multiple cell death processes and several signal transduction and immune-related pathways. Immune infiltration analysis showed that cell death scores were correlated with multiple immune cell types, including macrophages, mast cells, T cells and B cells. A six-gene prediction model was constructed to predict rupture. The area under curves (AUCs) for predicting rupture in the training and validation cohorts were 0.924 and 0.855, respectively. CONCLUSIONS: Comprehensively analysis of RCD in IA and found that multiple RCD types are likely to be involved in IA formation and rupture. These cell death processes were correlated with inflammation and immunity. We present novel insights into the mechanism of IA pathogenesis that should help to guide further research.


Asunto(s)
Aneurisma Intracraneal , Muerte Celular Regulada , Humanos , Aneurisma Intracraneal/genética , Muerte Celular/genética , Apoptosis/genética , Algoritmos
5.
World Neurosurg ; 180: e774-e785, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37839573

RESUMEN

BACKGROUND: Cardiac complications are related to poor prognosis after spontaneous intracerebral hemorrhage (ICH). This study aims to predict the cardiac complications arising from small intracranial hematoma at ultraearly stage. METHODS: The data of this work were derived from the Risk Stratification and Minimally Invasive Surgery in Acute ICH Patients study (ClinicalTrials.gov Identifier: NCT03862729). This work included patients with ICH but without brain herniation, as confirmed by a brain computed tomography scan within 48 hours of symptom onset. Every Patient's information recorded at the emergent department, including clinical, laboratory, electrocardiogram, and medical records, was derived from the electronic data capture. Cardiac complications were defined as the occurrence of myocardial damage, arrhythmias, and ischemic electrocardiogram changes during hospitalization. Variables associated with cardiac complications were filtrated by univariate and multivariate regression analyses. Independent risk factors were used to form the early predictive model. The restricted cubic splines were employed to investigate the nonlinear associations in a more sophisticated and scholarly manner. RESULTS: A total of 587 ICH patients were enrolled in this work, including 72 patients who suffered from cardiac complications after ICH. Out of the 78 variables, 24 were found to be statistically significant in the univariate logistic regression analysis. These significant variables were then subjected to multivariate logistic regression analysis and utilized for constructing risk models. Multivariate logistic regression analysis showed high plasma fibrinogen (FIB) level [odds ratio (OR) per standard deviation (SD) 1.327, 95% confidence intervals (CI) 1.037-1.697; P = 0. 024)] and older age (OR per SD 1.777, 95% CI 1.344-2.349; P <0.001) were associated with a higher incidence of cardiac complications after ICH. High admission pulse rate (OR 0.620, 95% CI 0.451-0.853; P = 0. 003) was considered a protective factor for cardiac complications after ICH. In the restricted cubic spline regression model, FIB and cardiac complications following ICH were positively correlated and almost linearly (P for nonlinearity = 0.073). The reference point for FIB in predicting cardiac complications after ICH was 2.64 g/L. CONCLUSIONS: Emergent factors, including plasma FIB level, age, and pulse rate, might be independently associated with cardiac complications after ICH, which warrants attention in the context of treatment.


Asunto(s)
Hemorragia Cerebral , Cardiopatías , Humanos , Hemorragia Cerebral/complicaciones , Factores de Riesgo , Hematoma/etiología , Hematoma/complicaciones , Incidencia , Cardiopatías/etiología , Cardiopatías/complicaciones , Fibrinógeno
6.
Adv Sci (Weinh) ; 10(5): e2205173, 2023 02.
Artículo en Inglés | MEDLINE | ID: mdl-36529950

RESUMEN

The RIIß subunit of  cAMP-dependent protein kinase A (PKA) is expressed in the brain and adipose tissue. RIIß-knockout mice show leanness and increased UCP1 in brown adipose tissue. The authors have previously reported that RIIß reexpression in hypothalamic GABAergic neurons rescues the leanness. However, whether white adipose tissue (WAT) browning contributes to the leanness and whether RIIß-PKA in these neurons governs WAT browning are unknown. Here, this work reports that RIIß-KO mice exhibit a robust WAT browning. RIIß reexpression in dorsal median hypothalamic GABAergic neurons (DMH GABAergic neurons) abrogates WAT browning. Single-cell sequencing, transcriptome sequencing, and electrophysiological studies show increased GABAergic activity in DMH GABAergic neurons of RIIß-KO mice. Activation of DMH GABAergic neurons or inhibition of PKA in these neurons elicits WAT browning and thus lowers body weight. These findings reveal that RIIß-PKA in DMH GABAergic neurons regulates WAT browning. Targeting RIIß-PKA in DMH GABAergic neurons may offer a clinically useful way to promote WAT browning for treating obesity and other metabolic disorders.


Asunto(s)
Tejido Adiposo Pardo , Subunidad RIIbeta de la Proteína Quinasa Dependiente de AMP Cíclico , Hipotálamo , Animales , Ratones , Tejido Adiposo Pardo/metabolismo , Subunidad RIIbeta de la Proteína Quinasa Dependiente de AMP Cíclico/metabolismo , Proteínas Quinasas Dependientes de AMP Cíclico/metabolismo , Neuronas GABAérgicas/metabolismo , Hipotálamo/metabolismo , Obesidad/metabolismo , Delgadez/metabolismo
7.
Nat Commun ; 13(1): 7900, 2022 Dec 22.
Artículo en Inglés | MEDLINE | ID: mdl-36550116

RESUMEN

Plasmonic MXenes are of particular interest, because of their unique electron and phonon structures and multiple surface plasmon effects, which are different from traditional plasmonic materials. However, to date, how electronic energy damp to lattice vibrations (phonons) in MXenes has not been unraveled. Here, we employed ultrafast broadband impulsive vibrational spectroscopy to identify the energy damping channels in MXenes (Ti3C2Tx and Mo2CTx). Distinctive from the well-known damping pathways, our results demonstrate a different energy damping channel, in which the Ti3C2Tx plasmonic electron energy transfers to coherent phonons by nonthermal electron mediation after Landau damping, without involving electron-electron scattering. Moreover, electrons are observed to strongly couple with A1g mode (~60 fs, 85-100%) and weakly couple with Eg mode (1-2 ps, 0-15%). Our results provide new insight into the electron-phonon interaction in MXenes, which allows the design of materials enabling efficient manipulation of electron transport and energy conversion.

8.
Appl Opt ; 61(29): 8678-8687, 2022 Oct 10.
Artículo en Inglés | MEDLINE | ID: mdl-36256004

RESUMEN

Evaluating the stress field based on photoelasticity is of vital significance in engineering fields. To achieve the goal of efficiently demodulating stress distribution and to overcome the limitations of conventional methods, it is essential to develop a deep learning method to simplify and accelerate the process of image acquisition and processing. A framework is proposed to enhance prediction accuracy. By adopting Resnet as the backbone, applying U-Net architecture, and adding a physical constraint module, our model recovers the stress field with higher structural similarity. Under different conditions, our model performs robustly despite complicated geometry and a large stress range. The results prove the universality and effectiveness of our model and offer an opportunity for instant stress detection.

9.
J Chem Phys ; 155(22): 224104, 2021 Dec 14.
Artículo en Inglés | MEDLINE | ID: mdl-34911307

RESUMEN

Modeling nonadiabatic dynamics in complex molecular or condensed-phase systems has been challenging, especially for the long-time dynamics. In this work, we propose a time series machine learning scheme based on the hybrid convolutional neural network/long short-term memory (CNN-LSTM) framework for predicting the long-time quantum behavior, given only the short-time dynamics. This scheme takes advantage of both the powerful local feature extraction ability of CNN and the long-term global sequential pattern recognition ability of LSTM. With feature fusion of individually trained CNN-LSTM models for the quantum population and coherence dynamics, the proposed scheme is shown to have high accuracy and robustness in predicting the linearized semiclassical and symmetrical quasiclassical mapping dynamics as well as the mixed quantum-classical Liouville dynamics of various spin-boson models with learning time up to 0.3 ps. Furthermore, if the hybrid network has learned the dynamics of a system, this knowledge is transferable that could significantly enhance the accuracy in predicting the dynamics of a similar system. The hybrid CNN-LSTM network is thus believed to have high predictive power in forecasting the nonadiabatic dynamics in realistic charge and energy transfer processes in photoinduced energy conversion.

10.
Phys Chem Chem Phys ; 23(31): 16998-17008, 2021 Aug 12.
Artículo en Inglés | MEDLINE | ID: mdl-34338705

RESUMEN

To achieve the goal of efficiently analyzing transient absorption spectra without arbitrary assumption and to overcome the limitations of conventional methods in fitting ability and highly noised backgrounds, it is essential to develop new tools to achieve more accurate and robust prediction based on the intrinsic properties of a spectrum even under strong noise. In this work, Lasso regression and neural network were combined to achieve an effective fitting. Compared to the conventional global fitting method, our network could automatically determine the exponential form on each wave unit, in which the accuracy was as high as 97%. Thereafter, the lifetime with the corresponding amplitude ratio could be easily predicted by the neural network on each wave unit. This kind of prediction is difficult to achieve by global fitting due to the limitation of computational resources. Furthermore, more accurate fitting even under weak signals could be achieved for the mean square error (MSE) decreasing by more than 100 times on average compared to conventional global fitting methods. Attributed to its improved accuracy and robustness, our developed algorithm could be readily applied to analyze time-resolved transient spectra.

11.
Small ; 17(11): e2006054, 2021 03.
Artículo en Inglés | MEDLINE | ID: mdl-33590637

RESUMEN

Recently, 2D materials are in great demand for various applications such as optical devices, supercapacitors, sensors, and biomedicine. MXenes as a kind of novel 2D material have attracted considerable research interest due to their outstanding mechanical, thermal, electrical, and optical properties. Especially, the excellent nonlinear optical response enables them to be potential candidates for the applications in ultrafast photonics. Here, a review of MXenes synthesis, optical properties, and applications in ultrafast lasers is presented. First, aqueous acid etching and chemical vapor deposition methods for preparing MXenes are introduced, in which the storage stability and challenges of the existing synthesis techniques are also discussed. Then, the optical properties of MXenes are discussed specifically, including plasmonic properties, optical detection, photothermal effects, and ultrafast dynamics. Furthermore, the typical ultrafast pulsed lasers enabled by MXene-based saturable absorbers operated at different wavelength regions are summarized. Finally, a summary and outlook on the development of MXenes is presented in the perspectives section.


Asunto(s)
Rayos Láser , Óptica y Fotónica
12.
Phys Chem Chem Phys ; 23(5): 3341-3350, 2021 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-33502424

RESUMEN

As a novel two-dimensional material, the most popular MXene (Ti3C2Tx) has presented promising therapeutic effects in cancer and bacterial infections under near infrared light illumination. However, there is still a lack of molecular level insight on the destruction of the cell membrane by MXene. In this work, a series of molecular dynamics simulations were conducted to capture the nanosheet destruction processes. The results showed that the penetration of the MXene nanosheet into the cell membrane is a non-spontaneous process, which required an enormous external force compared to other nanomaterials. Besides, the plasma membrane was disrupted during the penetration process. After the demonstration of disturbing the lipid membrane by higher temperature, we also found that there exists a significantly high effective thermal conduction pathway at the Ti3C2-POPC lipid interface mediated by van der Waals interactions and hydrogen bonds. The findings provide an understanding of the MXene-related cancer therapy and antibacterial activity, and offer guidance for the broader applications of MXene in the field of biomedicine.


Asunto(s)
Membrana Celular/efectos de los fármacos , Titanio/química , Membrana Celular/química , Calefacción , Simulación de Dinámica Molecular , Nanoestructuras/química , Fosfatidilcolinas/química , Temperatura
13.
J Phys Chem Lett ; 11(22): 9521-9527, 2020 Nov 19.
Artículo en Inglés | MEDLINE | ID: mdl-33112154

RESUMEN

The thermal management of MXene (Ti3C2Tx) plays a crucial role in its performance during various emerging applications. However, it is unclear how the inevitable oxidation structure of Ti3C2Tx influences the thermal dissipation, which might hinder its long-term performance and even create thermal damage. Here we show the thermal migration of a Ti3C2Tx flake with surface oxidation in film and water by combining ultrafast pump-probe technique with molecular dynamics (MD) simulations. The results demonstrate that the oxidation at the surface could facilitate interfacial thermal migration with shorter interfacial distances but would block the lateral thermal transfer. Besides, our results also identified that the slight oxidation could not obviously change the thermal decay of Ti3C2Tx nanosheets in water due to similar hydrogen bonds between water and interface. The research not only provides fundamental understanding of the thermal dissipation of MXene but also benefits for designing the thermal dissipation system to the MXene device.

14.
Inorg Chem ; 58(11): 7285-7294, 2019 Jun 03.
Artículo en Inglés | MEDLINE | ID: mdl-31090408

RESUMEN

Two-dimensional (2D) material-controllable degradation under light radiation is crucial for their photonics and medical-related applications, which are yet to be investigated. In this paper, we first report the laser illumination method to regulate the degradation rate of Ti3C2T x nanosheets in aqueous solution. Comprehensive characterization of intermediates and final products confirmed that plasmonic laser promoting the oxidation was strikingly different from heating the aqueous solution homogeneously. Laser illumination would nearly 10 times accelerate the degradation of Ti3C2T x nanosheets in initial stage and create many smaller-sized oxidized products in a short time. Laser-induced fast degradation was principally ascribed to surface plasmonic resonance effect of Ti3C2T x nanosheets. The degradation ability of such illumination could be controlled either by tuning the excitation wavelength or changing the excitation power. Furthermore, the laser- or thermal-induced degradation could be retarded by surface protection of Ti3C2T x nanosheets. Our results suggest that plasmonic electron excitation of Ti3C2T x nanosheets could build a new reaction channel and lead to the fast oxidation of nanosheets in aqueous solution, potentially enabling a series of water-based applications.

15.
Phys Chem Chem Phys ; 21(8): 4240-4245, 2019 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-30747170

RESUMEN

Three model systems are designed to investigate energy transport between molecules on metal nanoparticle surfaces. Energy is rapidly transferred from one carbon monoxide (CO) molecule to another CO molecule or an organic molecule on adjacent surface sites of 2 nm Pt particles within a few picoseconds. On the contrary, energy flow from a surface organic molecule to an adjacent CO molecule is significantly slower and, in fact, within experimental sensitivity and uncertainty the transfer is not observed. The energy transport on particle surfaces (about 2 km s-1) is almost ten times faster than inside a molecule (200 m s-1). The seemingly perplexing observations can be well explained by the combination of electron/vibration and vibration/vibration coupling mechanisms, which mediate molecular energy dynamics on metal nanoparticle surfaces: the strong electron/vibration coupling rapidly converts CO vibrational energy into heat that can be immediately sensed by nearby molecules; but the vibration/vibration coupling dissipates the vibrational excitation in the organic molecule as low-frequency intramolecular vibrations that may or may not couple to surface electronic motions.

16.
Nat Commun ; 7: 10749, 2016 Feb 17.
Artículo en Inglés | MEDLINE | ID: mdl-26883665

RESUMEN

Energy migrations at metal nanomaterial surfaces are fundamentally important to heterogeneous reactions. Here we report two distinctive energy migration pathways of monolayer adsorbate molecules on differently sized metal nanoparticle surfaces investigated with ultrafast vibrational spectroscopy. On a 5 nm platinum particle, within a few picoseconds the vibrational energy of a carbon monoxide adsorbate rapidly dissipates into the particle through electron/hole pair excitations, generating heat that quickly migrates on surface. In contrast, the lack of vibration-electron coupling on approximately 1 nm particles results in vibrational energy migration among adsorbates that occurs on a twenty times slower timescale. Further investigations reveal that the rapid carbon monoxide energy relaxation is also affected by the adsorption sites and the nature of the metal but to a lesser extent. These findings reflect the dependence of electron/vibration coupling on the metallic nature, size and surface site of nanoparticles and its significance in mediating energy relaxations and migrations on nanoparticle surfaces.

17.
J Phys Chem B ; 119(30): 9893-904, 2015 Jul 30.
Artículo en Inglés | MEDLINE | ID: mdl-26135548

RESUMEN

In this work, MD simulations with two different force fields, vibrational energy relaxation and resonant energy transfer experiments, and neutron scattering data are used to investigate ion pairing and clustering in a series of GdmSCN aqueous solutions. The MD simulations reproduce the major features of neutron scattering experimental data very well. Although no information about ion pairing or clustering can be obtained from the neutron scattering data, MD calculations clearly demonstrate that substantial amounts of ion pairs and small ion clusters (subnanometers to a few nanometers) do exist in the solutions of concentrations 0.5 M*, 3 M*, and 5 M* (M* denotes mole of GdmSCN per 55.55 mole of water). Vibrational relaxation experiments suggest that significant amounts of ion pairs form in the solutions. Experiments measuring the resonant energy transfers among the thiocyanate anions in the solutions suggest that the ions form clusters and in the clusters the average anion distance is 5.6 Å (5.4 Å) in the 3 M* (5 M*) Gdm-DSCN/D2O solution.

18.
J Phys Chem B ; 119(12): 4333-49, 2015 Mar 26.
Artículo en Inglés | MEDLINE | ID: mdl-25679402

RESUMEN

The methodology and principle using vibrational energy transfer to measure molecular distances in liquids are introduced. The application of the method to the studies of ion pairing and clustering in strong electrolyte aqueous solutions is demonstrated with MSCN aqueous solutions where M = Li, Na, K, Cs, and NH4. Experiments suggest that ions in the concentrated aqueous solutions can form substantial quantities of ion clusters in which both cations and anions are involved. More and larger clusters form in solutions that are relatively more concentrated and which include a larger cation. In KSCN solutions, the shortest anionic distance in the ion clusters is the same as that in the KSCN crystal. The rotational time of the anion and the nonresonant vibrational energy transfer time with a gap of 75 cm(-1) in the KSCN saturated solution are very similar to those in the KSCN crystal. However, the KSCN ion clusters are closer in structure to the melt. The clusters form an interconnected network with random ionic orientations. Because of ion clustering, the anion and water dynamics behave distinctly in the same solutions. At high concentrations, the anion rotation significantly slows down because of the increase in the size of the ion clusters, but the slowdown amplitude of water rotation is very modest because many of the water molecules still remain in the "bulk" state due to ion clustering. The rotational dynamics of both water and anions are slower in a solution with a smaller cation, primarily because a smaller cation has a stronger cation/anion interaction and a cation/water interaction that leads to more water molecules confined in the ion clusters. Adding ions or molecules into the KSCN solutions can perturb the ion clusters. Weakly hydrated anions can participate in clustering and form mixed ion clusters with KSCN, and strongly hydrated anions can reduce the effective water molecules solvating KSCN and facilitate the formation of more and larger KSCN ion clusters. Similarly, molecules which can strongly bind to SCN(-) prefer to participate in the KSCN ion clusters. Molecules which are strongly hydrated prefer to remain hydrated and facilitate the ion clustering of KSCN.

19.
J Phys Chem A ; 119(4): 669-80, 2015 Jan 29.
Artículo en Inglés | MEDLINE | ID: mdl-25549247

RESUMEN

Energy-gap-dependent vibrational-energy transfers among the nitrile stretches of KSCN/KS(13)CN/KS(13)C(15)N in D2O, DMF, and formamide liquid solutions at room temperature were measured by the vibrational-energy-exchange method. The energy transfers are slower with a larger energy donor/acceptor gap, independent of the calculated instantaneous normal mode ("phonons" in liquids) densities or the terahertz absorption spectra. The energy-gap dependences of the nonresonant energy transfers cannot be described by phonon compensation mechanisms with the assumption that phonons are the instantaneous normal modes of the liquids. Instead, the experimental energy-gap dependences can be quantitatively reproduced by the dephasing mechanism. A simple theoretical derivation shows that the fast molecular motions in liquids randomize the modulations on the energy donor and acceptor by phonons and diminish the phonon compensation efficiency on energy transfer. Estimations based on the theoretical derivations suggest that, for most nonresonant intermolecular vibrational-energy transfers in liquids with energy gaps smaller than the thermal energy, the dephasing mechanism dominates the energy-transfer process.

20.
J Phys Chem B ; 118(13): 3689-95, 2014 Apr 03.
Artículo en Inglés | MEDLINE | ID: mdl-24628604

RESUMEN

The coordination number of Li(+) in acetonitrile solutions was determined by directly measuring the rotational times of solvent molecules bound and unbound to it. The CN stretch of the Li(+) bound and unbound acetonitrile molecules in the same solution has distinct vibrational frequencies (2276 cm(-1) vs 2254 cm(-1)). The frequency difference allows the rotation of each type of acetonitrile molecule to be determined by monitoring the anisotropy decay of each CN stretch vibrational excitation signal. Regardless of the nature of anions and concentrations, the Li(+) coordination number was found to be 4-6 in the LiBF4 (0.2-2 M) and LiPF6 (1-2 M) acetonitrile solutions. However, the dissociation constants of the salt are dependent on the nature of anions. In 1 M LiBF4 solution, 53% of the salt was found to dissociate into Li(+), which is bound by 4-6 solvent molecules. In 1 M LiPF6 solution, 72% of the salt dissociates. 2D IR experiments show that the binding between Li(+) and acetonitrile is very strong. The lifetime of the complex is much longer than 19 ps.

SELECCIÓN DE REFERENCIAS
DETALLE DE LA BÚSQUEDA
...