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1.
J Oral Implantol ; 48(5): 436-454, 2022 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-34937086

RESUMEN

Partial extraction therapy (PET) is a collective concept encompassing a group of surgical techniques including socket shield, root membrane, proximal shield, pontic shield, and root submergence. PET uses the patient's own root structure to maintain blood supply derived from the periodontal ligament complex to preserve the periodontium and peri-implant tissues during restorative and implant therapy. This review aims to summarize the current knowledge regarding PET techniques and present a comprehensive evaluation of human clinical studies in the literature. Two independent reviewers conducted electronic and manual searches until January 1, 2021, in the following electronic bibliographic databases: PubMed, EMBASE, and Dentistry & Oral Sciences Source. Gray literature was searched to identify additional candidates for potential inclusion. Articles were screened by a group of 4 reviewers using the Covidence software and synthesized. A systematic search of the literature yielded 5714 results. Sixty-four articles were selected for full-text assessment, of which 42 eligible studies were included in the review. Twelve studies were added to the synthesis after a manual search of the reference lists. A total of 54 studies were examined in this review. In sum, PET techniques offer several clinical advantages: (1) preservation of buccal bone postextraction and limitation of alveolar ridge resorption, (2) mitigation of the need for invasive ridge augmentation procedures, and (3) soft-tissue dimensional stability and high esthetic outcomes. Further randomized clinical studies with larger sample sizes are needed to improve the understanding of the long-term clinical outcomes of PET.


Asunto(s)
Pérdida de Hueso Alveolar , Aumento de la Cresta Alveolar , Carga Inmediata del Implante Dental , Humanos , Alveolo Dental/cirugía , Extracción Dental/métodos , Estética Dental , Aumento de la Cresta Alveolar/métodos , Carga Inmediata del Implante Dental/métodos , Pérdida de Hueso Alveolar/cirugía
2.
J Contemp Dent Pract ; 23(2): 232-236, 2022 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-35748455

RESUMEN

AIM: The clinical case series presents a minimally invasive modified tunnel procedure with autogenous connective tissue graft (CTG) using a V-reverse sutures to treat multiple gingival recessions. BACKGROUND: In periodontal and peri-implant plastic procedures, proper graft and flap stabilization are crucial in the outcomes. The coronally advanced flap allows for better access with the possibility of suturing the graft to the de-epithelialized papillae of the periosteum; there is little evidence with using the V-reverse sutures technique in stabilizing the graft and the flap when performing tunnel techniques (TUN). The following case series presents a minimally invasive modified tunnel procedure with autogenous CTG using V-reverse sutures to treat gingival recessions. CASE DESCRIPTION: Three patients with Miller Class I maxillary buccal gingival recessions defects were selected for this study. All subjects were treated with the minimally invasive modified tunnel technique with autogenous subepithelial CTG. V-reverse sutures technique was performed to further improve the stability of the graft at the recipient site. Clinical parameters, including mean recession depth and root coverage esthetic score (RES), were recorded at baseline, 1 week, 2 weeks, 1 month, 3 months, 6 months, and 1-year postoperative follow-up visits. CONCLUSION: At the 1-year follow-up, complete root coverage was achieved in multiple gingival recessions defect sites. In conclusion, this technique represents an alternative treatment for Miller Class I gingival recessions defects with clinical and esthetically satisfactory outcomes. CLINICAL SIGNIFICANCE: Combining the advantages of V-reverse sutures and CTG in the treatment of gingival recessions is feasible and noninvasive.


Asunto(s)
Recesión Gingival , Tejido Conectivo , Estética Dental , Encía/cirugía , Recesión Gingival/cirugía , Humanos , Suturas , Raíz del Diente/cirugía , Resultado del Tratamiento
3.
Oral Dis ; 27 Suppl 3: 684-687, 2021 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-32472974

RESUMEN

The COVID-19 pandemic is a major public health crisis for countries around the world. In response to this global outbreak, the World Health Organization declared a public health emergency of international concern. Dental professionals are especially at high risk of contracting the COVID-19 virus due to the unique nature of dentistry, more specifically, exposure to aerosols and droplets. When it comes to dental emergencies, it was crucial to maintain urgent dental care services operational to help reduce the burden on our healthcare system and hospitals already under pressure. The COVID-19 pandemic has significantly impacted how dentistry is practiced in North America in both the private practice and academic settings. This article shares the perspectives of dentists practicing in private practice and clinician-researchers in academic dental institutions. More specifically, we discuss about measures implemented to minimize risks of disease transmission, challenges in emergency dental care, impact on patients, as well as impact on the professional and personal lives of the dental team during the COVID-19 crisis.


Asunto(s)
COVID-19 , Pandemias , Odontología , Humanos , América del Norte/epidemiología , Práctica Privada , SARS-CoV-2
4.
Molecules ; 26(22)2021 Nov 22.
Artículo en Inglés | MEDLINE | ID: mdl-34834134

RESUMEN

Dental, oral, and craniofacial (DOC) regenerative medicine aims to repair or regenerate DOC tissues including teeth, dental pulp, periodontal tissues, salivary gland, temporomandibular joint (TMJ), hard (bone, cartilage), and soft (muscle, nerve, skin) tissues of the craniofacial complex. Polymeric materials have a broad range of applications in biomedical engineering and regenerative medicine functioning as tissue engineering scaffolds, carriers for cell-based therapies, and biomedical devices for delivery of drugs and biologics. The focus of this review is to discuss the properties and clinical indications of polymeric scaffold materials and extracellular matrix technologies for DOC regenerative medicine. More specifically, this review outlines the key properties, advantages and drawbacks of natural polymers including alginate, cellulose, chitosan, silk, collagen, gelatin, fibrin, laminin, decellularized extracellular matrix, and hyaluronic acid, as well as synthetic polymers including polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), poly (ethylene glycol) (PEG), and Zwitterionic polymers. This review highlights key clinical applications of polymeric scaffolding materials to repair and/or regenerate various DOC tissues. Particularly, polymeric materials used in clinical procedures are discussed including alveolar ridge preservation, vertical and horizontal ridge augmentation, maxillary sinus augmentation, TMJ reconstruction, periodontal regeneration, periodontal/peri-implant plastic surgery, regenerative endodontics. In addition, polymeric scaffolds application in whole tooth and salivary gland regeneration are discussed.


Asunto(s)
Materiales Biocompatibles/uso terapéutico , Medicina Regenerativa , Andamios del Tejido , Humanos
5.
Langmuir ; 36(1): 84-95, 2020 Jan 14.
Artículo en Inglés | MEDLINE | ID: mdl-31820993

RESUMEN

Methane bubble dispersions in a water column can be observed in both vertical subsea piping as well as subsea gas seepages. Hydrate growth has been shown to occur at the gas-water interface under flowing conditions, yet the majority of the current literature is limited to quiescent systems. Gas hydrate risks in subsea piping have been shown to increase in late life production wells with increased water content and with gas-in-water bubble dispersions. The dissolution of subsea methane seepages into seawater, or methane release into the atmosphere, can be affected by hydrate film growth on rising bubbles. A high-pressure water tunnel (HPWT), was used to generate a turbulent, continuous water flow system representative of a vertical jumper line to study the relationship between bulk methane hydrate growth and bubble size during a production-well restart. The HPWT comprises a flow loop of 19.1 mm inner diameter and 4.9 m length, with a vertical section containing an optical window to enable visualization of the bubble and hydrate flow dynamics via a high-speed, high-resolution video camera. Additional online monitoring includes the differential pressure drop, viscosity, temperature, flow rates, and gas consumption. Experimental conditions were maintained at 275 K and 6.2 MPa during hydrate formation and 298 K and 1.4 MPa during hydrate dissociation. Hydrate growth using freshwater and saltwater (3.5 wt % NaCl) was measured at four flow velocities (0.8, 1.2, 1.6, and 1.9 m s-1). The addition of salt is shown in this work to alter the surface properties of bubbles, which introduces changes to bubble dynamics of dispersion and coalescence. Hydrate volume fractions and growth rates in the presence of salt were on average ∼32% lower compared to that in freshwater. This was observed and validated to be due to bubble size and dynamic factors and not due to the 1.5 K thermodynamic inhibition effect of salt. Throughout hydrate growth, methane bubbles in pure freshwater maintained larger diameters (2.4-4.2 mm), whereas the presence of salt promoted fine gas bubble dispersions (0.1-0.7 mm), increasing gas-water interfacial area. While gas bubble coalescence was observed in all freshwater experiments, the addition of salt limited coalescence between gas bubbles and reduced bubble size. Consequently, earlier formation of solid hydrate shells in saltwater produced early mass-transfer barriers reducing hydrate growth rates. While primarily directed toward flow assurance, the observed relationship between hydrates, bubble size, and saltwater also applies to broader research fields in subsea gas seepages and naturally occurring hydrates.

6.
Eur J Dent Educ ; 24(4): 825-827, 2020 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-32654328

RESUMEN

During the COVID-19 pandemic, the dental education community faced unprecedented challenges. In this commentary, we share the perspectives of faculty clinicians, residents and students in academic dental institutions in the United States and Canada. We discuss COVID-19's impact on various aspects of academic dentistry including patient care, education, research and raise key concerns regarding the future of dental education post-pandemic.


Asunto(s)
COVID-19 , Pandemias , Canadá , Educación en Odontología , Humanos , América del Norte , SARS-CoV-2 , Estados Unidos
7.
J Chem Phys ; 150(13): 134503, 2019 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-30954046

RESUMEN

In this paper, equilibrium properties of structure II hydrates of hydrogen were determined from Monte Carlo simulations in the isothermal-isobaric Gibbs ensemble. Water and hydrogen molecules are described by the TIP4P/Ice and Silvera-Goldman models, respectively. The use of the Gibbs ensemble has many key advantages for the simulation of hydrates. By the separation of hydrogen vapor and hydrate phases into their own domains, coupled with transfer moves of hydrogen molecules between domains, cage occupancies were determined. Furthermore, the choice of this ensemble also allows equilibrium lattice constants and guest molecule chemical potentials to be straightforwardly estimated. Results for hydrogen mass fractions indicate reasonable agreement with prior simulation data and theoretical models, while detailed analysis of cage occupancy distributions and neighboring cage pair occupancy combinations gives valuable insight into the behavior of this hydrate at the inter-cage scale. These results will aid in the construction of theoretical models, for which knowledge of the occupancy of neighboring cages is of great importance. In support of previous experimental and theoretical works, we also find evidence of double occupancy of a few small cages inside of the hydrate stability zone, albeit at very high pressures; approximately 0.1% of small cages are doubly occupied at 300 MPa, for temperatures of 225 K and 250 K.

8.
Eur J Dent Educ ; 23(2): 143-150, 2019 May.
Artículo en Inglés | MEDLINE | ID: mdl-30582648

RESUMEN

BACKGROUND: With current global trends in postgraduate education, graduate programmes must make evidence-based improvements to offer the best programme that aligns with student needs and prepare them for their future career prospects. The aim of this cross-sectional study was to investigate the postgraduation career pathways of MSc and PhD students who graduated within the past 15 years from the McGill University Postgraduate Dental Research Program. MATERIALS AND METHODS: An online questionnaire, composed of 10 closed-ended format items, was used that covered domains such as student profile, career profile, postgraduate skill development, job search experience and satisfaction. Descriptive statistics and interpretative qualitative analysis were used to evaluate student feedback. RESULTS: Sixty-six students responded to the online survey, out of which sixty-two students completed the survey (61% participation rate). The majority of the graduate students, 67% (n = 44), obtained MSc degree in Dental Sciences. Overall, our results showed that most graduates started careers in academia in their original field of study and were satisfied with their income. Most graduates reported "critical and creative thinking" to be the strongest acquired skills during their postgraduate training and identified fierce competition for their position of interest as the main challenge after graduation. DISCUSSION AND CONCLUSION: Our results showed that graduates in dental research appeared to be overall satisfied with their careers after postgraduate research training, both in terms of scope of practice and income. However, strong competition in obtaining the position of their interest seemed to be the main obstacle after graduation.


Asunto(s)
Movilidad Laboral , Competencia Clínica , Curriculum , Educación de Posgrado en Odontología , Estudiantes de Odontología/psicología , Estudios Transversales , Femenino , Humanos , Renta , Masculino , Satisfacción Personal , Encuestas y Cuestionarios , Factores de Tiempo
9.
J Chem Phys ; 148(18): 184501, 2018 May 14.
Artículo en Inglés | MEDLINE | ID: mdl-29764125

RESUMEN

To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

10.
Proc Natl Acad Sci U S A ; 112(20): 6307-12, 2015 May 19.
Artículo en Inglés | MEDLINE | ID: mdl-25941383

RESUMEN

Chiral molecules with opposite handedness exhibit distinct physical, chemical, or biological properties. They pose challenges as well as opportunities in understanding the phase behavior of soft matter, designing enantioselective catalysts, and manufacturing single-handed pharmaceuticals. Microscopic particles, arranged in a chiral configuration, could also exhibit unusual optical, electric, or magnetic responses. Here we report a simple method to assemble achiral building blocks, i.e., the asymmetric colloidal dimers, into a family of chiral clusters. Under alternating current electric fields, two to four lying dimers associate closely with a central standing dimer and form both right- and left-handed clusters on a conducting substrate. The cluster configuration is primarily determined by the induced dipolar interactions between constituent dimers. Our theoretical model reveals that in-plane dipolar repulsion between petals in the cluster favors the achiral configuration, whereas out-of-plane attraction between the central dimer and surrounding petals favors a chiral arrangement. It is the competition between these two interactions that dictates the final configuration. The theoretical chirality phase diagram is found to be in excellent agreement with experimental observations. We further demonstrate that the broken symmetry in chiral clusters induces an unbalanced electrohydrodynamic flow surrounding them. As a result, they rotate in opposite directions according to their handedness. Both the assembly and propulsion mechanisms revealed here can be potentially applied to other types of asymmetric particles. Such kinds of chiral colloids will be useful for fabricating metamaterials, making model systems for both chiral molecules and active matter, or building propellers for microscale transport.


Asunto(s)
Coloides/química , Campos Electromagnéticos , Sustancias Macromoleculares/química , Modelos Químicos , Poliestirenos/química , Dimerización , Fluorescencia , Microscopía por Video , Poliestirenos/síntesis química
11.
Phys Rev Lett ; 118(16): 167801, 2017 Apr 21.
Artículo en Inglés | MEDLINE | ID: mdl-28474912

RESUMEN

If you mix lines and circles, what happens at the edge of the mixture? The problem is simply stated, but the answer is not obvious. Twenty years ago it was proposed that a universal topological driving force would drive cyclic chains to enrich the surface of blends of linear and cyclic chains. Here such behavior is demonstrated experimentally for sufficiently long chains and the limit in molecular weight where packing effects dominate over the topological driving force is identified.

12.
Langmuir ; 33(42): 11436-11445, 2017 10 24.
Artículo en Inglés | MEDLINE | ID: mdl-28926254

RESUMEN

In situ rheological measurements for clathrate hydrate slurries were performed using a high pressure rheometer to determine the effect of hydrate particles on the viscosity and transportability of these slurries. These measurements were conducted using a well-characterized model water-in-oil emulsion ( Delgado-Linares et al. Model Water in-Oil Emulsions for Gas Hydrate Studies in Oil Continuous Systems . Energy Fuels 2013 , 27 , 4564 - 4573 ). The emulsion consists of a model liquid hydrocarbon, water, and a surfactant mixture of sorbitane monooleate 80 (Span 80) and sodium di-2-ethylhexylsulfosuccinate (Aerosol OT, AOT). This emulsion was used as an analog to water-in-crude oil (w/o) emulsions and provides reproducible results. The flow properties of the model w/o emulsion prior to hydrate formation were investigated in terms of several parameters including water percentage, temperature and pressure. A general equation that describes the viscosity of the emulsion as a function of the aforementioned parameters was developed. This general equation was able to predict the viscosity of a saturated emulsion at various temperatures and water percentages to within ±13% error. The general equation was then used to analyze the effect of hydrate formation on the transportability of gas hydrate slurries. As for hydrate slurries investigation, measurements were performed using methane gas as the hydrate former and a straight vane impeller as a stirring system. Tests were conducted at constant temperature and pressure (1 °C and 1500 psig of methane) and water percentages ranging from 5 to 30 vol %. Results of this work were analyzed and presented in terms of relative values, i.e., viscosities of the slurries relative to the viscosities of the continuous phase at similar temperature and pressure. In this work, a correlation to predict the relative viscosity of a hydrate slurry at various hydrate volume fractions was developed. Analysis of the developed correlation showed that the model was able to predict the relative viscosity of a hydrate slurry to within ±17% error.

13.
Phys Chem Chem Phys ; 19(18): 11326-11339, 2017 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-28418442

RESUMEN

Extraction of polar molecules by amphiphilic species results in a complex variety of clusters whose topologies and energetics control phase behavior and efficiency of liquid-liquid separations. A computational approach including quantum mechanical vibrational frequency calculations and molecular dynamics simulation with intermolecular network theory is used to provide a robust assessment of extractant and polar solute association through hydrogen bonding in the tributyl phosphate (TBP)/HNO3/H2O/dodecane system for the first time. The distribution of local topologies of the TBP/HNO3/H2O hydrogen bonded clusters is shown to be consistent with an equilibrium binding model. Mixed TBP/HNO3/H2O clusters are predicted that have not been previously observable in experiment due to limitations in scattering and spectroscopic resolution. Vibrational frequency calculations are compared with experimental data to validate the experimentally observed TBP-HNO3-HNO3 Chain structure. At high nitric acid and water loading, large hydrogen-bonded clusters of 20 to 80 polar solutes formed. The cluster sizes were found to be exponentially distributed, consistent with a constant average solute association free energy in that size range. Due to the deficit of hydrogen bond donors in the predominantly TBP/HNO3 organic phase, increased water concentrations lower the association free energy and enable growth of larger cluster sizes. For sufficiently high water concentrations, changes in the cluster size distribution are found to be consistent with the formation of a percolating cluster rather than reverse micelles, as has been commonly assumed for the occurrence of an extractant-rich third phase in metal-free solvent extraction systems. Moreover, the compositions of the large clusters leading to percolation agrees with the 1 : 3 TBP : HNO3 ratio reported in the experimental literature for TBP/HNO3/H2O third phases. More generally, the network analysis of cluster formation from atomic level interactions could allow for control of phase behavior in multi-component solutions of species with a variety of hydrogen bond types.

14.
Langmuir ; 32(22): 5623-8, 2016 06 07.
Artículo en Inglés | MEDLINE | ID: mdl-27172089

RESUMEN

The scaling of the thickness, hs, of a densely grafted polymer brush of chain length N and grafting density σ swollen in vapor agrees quantitatively with the scaling reported by Kuhl et al. for densely grafted brushes swollen in liquid. Deep in the brush, next to the substrate, the shape of the segment concentration profile is the same whether the brush is swollen by liquid or by vapor. Differences in the segment concentration profile are manifested primarily in the swollen brush interface with the surrounding fluid. The interface of the polymer brush swollen in vapor is much more abrupt than that of the same brush swollen in liquid. This has implications for the compressibility of the swollen brush surface and for fluctuations at that surface.

15.
J Chem Phys ; 144(17): 174709, 2016 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-27155649

RESUMEN

The effects of path-dependent wetting and drying manifest themselves in many types of physical systems, including nanomaterials, biological systems, and porous media such as soil. It is desirable to better understand how these hysteretic macroscopic properties result from a complex interplay between gasses, liquids, and solids at the pore scale. Coarse-Grained Monte Carlo (CGMC) is an appealing approach to model these phenomena in complex pore spaces, including ones determined experimentally. We present two-dimensional CGMC simulations of wetting and drying in two systems with pore spaces determined by sections from micro X-ray computed tomography: a system of randomly distributed spheres and a system of Ottawa sand. Results for the phase distribution, water uptake, and matric suction when corrected for extending to three dimensions show excellent agreement with experimental measurements on the same systems. This supports the hypothesis that CGMC can generate metastable configurations representative of experimental hysteresis and can also be used to predict hysteretic constitutive properties of particular experimental systems, given pore space images.


Asunto(s)
Modelos Biológicos , Método de Montecarlo , Nanoestructuras/química , Adsorción , Porosidad , Reproducibilidad de los Resultados , Tomografía Computarizada por Rayos X , Agua/química
16.
J Am Chem Soc ; 137(38): 12312-20, 2015 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-26348667

RESUMEN

Polymers are found near surfaces and interfaces in a wide range of chemical and biological systems, and the structure and dynamics of adsorbed polymer chains have been the subject of intense interest for decades. While polymer structure is often inferred from dynamic measurements in bulk solution, this approach has proven difficult to implement at interfaces, and the understanding of interfacial polymer conformation remains elusive. Here we used single-molecule tracking to study the interfacial diffusion of isolated poly(ethylene glycol) molecules at oil-water interfaces. Compared to diffusion in dilute aqueous solution, which exhibited the expected dependence of the diffusion coefficient (D) upon molecular weight (M) of D ∼ M(-1/2) for a Gaussian chain, the behavior at the interface was approximately D ∼ M(-2/3), suggesting a significantly more expanded polymer conformation, despite the fact that the oil was a poor solvent for the polymer. Interestingly, this scaling remained virtually unchanged over a wide range of oil viscosity, despite the fact that at low viscosities the magnitude of the diffusion coefficient was consistent with expectations based on viscous drag (i.e., Stokes-Einstein diffusion), and for high viscosity oil, the interfacial mobility was much faster than expected and consistent with the type of intermittent hopping transport observed at the solid-liquid interface. The dependence on molecular weight, in both regimes, was consistent with results from both self-consistent field theory and previous Monte Carlo simulations, suggesting that an adsorbed polymer chain adopted a partially swollen (loop-train-tail) interfacial conformation.


Asunto(s)
Simulación de Dinámica Molecular , Aceites/química , Polietilenglicoles/química , Agua/química , Difusión , Peso Molecular , Método de Montecarlo , Viscosidad
17.
Faraday Discuss ; 179: 463-74, 2015.
Artículo en Inglés | MEDLINE | ID: mdl-25876773

RESUMEN

Clathrate hydrates are solid crystalline structures most commonly formed from solutions that have nucleated to form a mixed solid composed of water and gas. Understanding the mechanism of clathrate hydrate nucleation is essential to grasp the fundamental chemistry of these complex structures and their applications. Molecular dynamics (MD) simulation is an ideal method to study nucleation at the molecular level because the size of the critical nucleus and formation rate occur on the nano scale. Various analysis methods for nucleation have been developed through MD to analyze nucleation. In particular, the mean first-passage time (MFPT) and survival probability (SP) methods have proven to be effective in procuring the nucleation rate and critical nucleus size for monatomic systems. This study assesses the MFPT and SP methods, previously used for monatomic systems, when applied to analyzing clathrate hydrate nucleation. Because clathrate hydrate nucleation is relatively difficult to observe in MD simulations (due to its high free energy barrier), these methods have yet to be applied to clathrate hydrate systems. In this study, we have analyzed the nucleation rate and critical nucleus size of methane hydrate using MFPT and SP methods from data generated by MD simulations at 255 K and 50 MPa. MFPT was modified for clathrate hydrate from the original version by adding the maximum likelihood estimate and growth effect term. The nucleation rates calculated by MFPT and SP methods are within 5%, and the critical nucleus size estimated by the MFPT method was 50% higher, than values obtained through other more rigorous but computationally expensive estimates. These methods can also be extended to the analysis of other clathrate hydrates.

18.
Phys Rev Lett ; 113(22): 225702, 2014 Nov 28.
Artículo en Inglés | MEDLINE | ID: mdl-25494077

RESUMEN

The contributions of chain ends and branch points to surface segregation of long-branched chains in blends with linear chains have been studied using neutron reflectometry and surface-enhanced Raman spectroscopy for a series of novel, well-defined polystyrenes. A linear response theory accounting for the number and type of branch points and chain ends is consistent with surface excesses and composition profile decay lengths, and allows the first determination of branch point potentials. Surface excess is determined primarily by chain ends with branch points playing a secondary role.

19.
Soft Matter ; 10(41): 8349-57, 2014 Nov 07.
Artículo en Inglés | MEDLINE | ID: mdl-25207502

RESUMEN

We apply an AC electric field to induce anisotropic interactions among asymmetric colloidal dimers. These anisotropic interactions, being shape-specific and orientation-dependent, can create complex and unique structures that are not possible for spherical particles or symmetric dimers. More specifically, we show a series of novel structures that closely resemble one- and two-dimensional antiferromagnetic lattices, including small clusters, linear chains, square lattices, and frustrated triangular arrays. All of them are uniquely formed by alternating association between dimers with opposite orientations. Our theoretical model attributes those patterns to an exquisite balance between electrostatic (primarily dipolar) and electrohydrodynamic interactions. Although similarly oriented dimers are strongly repulsive, the oppositely oriented dimers possess a concave shoulder in the pair interaction, which favors clustering to minimize the number of overlaps between neighboring particles. By combining the anisotropy in both particle geometry and field-induced interaction, our work suggests a new way to tailor colloidal interactions on anisotropic particles, which is important for both scientific understanding and practical applications.

20.
J Chem Phys ; 141(2): 024504, 2014 Jul 14.
Artículo en Inglés | MEDLINE | ID: mdl-25028024

RESUMEN

The quantum path integral/classical liquid-state theory of Chandler and co-workers, created to describe an excess electron in solvent, is re-examined for the hydrated electron. The portion that models electron-water density correlations is replaced by two equations: the range optimized random phase approximation (RO-RPA), and the Donley, Rajasekaran, and Liu (DRL) approximation to the "two-chain" equation, both shown previously to describe accurately the static structure and thermodynamics of strongly charged polyelectrolyte solutions. The static equilibrium properties of the hydrated electron are analyzed using five different electron-water pseudopotentials. The theory is then compared with data from mixed quantum/classical Monte Carlo and molecular dynamics simulations using these same pseudopotentials. It is found that the predictions of the RO-RPA and DRL-based polaron theories are similar and improve upon previous theory, with values for almost all properties analyzed in reasonable quantitative agreement with the available simulation data. Also, it is found using the Larsen, Glover, and Schwartz pseudopotential that the theories give values for the solvation free energy that are at least three times larger than that from experiment.

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