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Background and Objectives: There are weak data comparing the safety and efficacy of absorbable and permanent tacks in laparoscopic ventral hernia repair with tack-only mesh fixation. In this study, we compared recurrence and complications rates following hernia repair using either only absorbable or only permanent tacks. Methods: Data from the Americas Hernia Society Quality Collaborative database were retrospectively reviewed as accessed on June 30, 2017. The query included patients 18 years of age or older, who had undergone laparoscopic ventral hernia repair with mesh using tack-only fixation. Study groups were divided into patients who had only absorbable tacks used and those with only permanent tacks. Propensity score matching was applied to strengthen the groups. Results: There were no significant differences in demographics, comorbidities, or hernia characteristics between the groups. There were no significant differences in length of stay, hernia recurrence rate, or surgical site infection. The permanent tack group had a significantly higher rate of surgical site occurrences (SSOs), as evidenced by a higher rate of seroma formation. Conclusion: When comparing the rates of complications and recurrences between absorbable and permanent tacks in the setting of laparoscopic ventral hernia repair with tack-only mesh fixation, the only significant difference found was that the permanent group had a higher rate of SSO due to seroma formation. Because this complication did not lead to an increased intervention rate, the clinical significance of this finding remains in question.
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Hernia Ventral/cirugía , Herniorrafia/métodos , Laparoscopía/métodos , Complicaciones Posoperatorias/etiología , Suturas/efectos adversos , Adolescente , Adulto , Humanos , Masculino , Persona de Mediana Edad , Complicaciones Posoperatorias/epidemiología , Puntaje de Propensión , Recurrencia , Estudios Retrospectivos , Seroma/epidemiología , Seroma/etiología , Mallas Quirúrgicas , Técnicas de Sutura , Resultado del TratamientoRESUMEN
Studies of running mechanics often use a standardized lab shoe, ostensibly to reduce variance between subjects; however, this may induce unnatural running mechanics. The purpose of this study was to compare the step rate, vertical average loading rate, and ground contact time when running in standardized lab shoes versus participants' normal running shoes. Ground reaction forces were measured while the participants ran overground in both shoe conditions at a self-selected speed. The Student's t-test revealed that the vertical average loading rate magnitude was smaller in lab shoes versus normal shoes (42.09 [11.08] vs 47.35 [10.81] body weight/s, P = .013), while the step rate (170.92 [9.43] vs 168.98 [9.63] steps/min, P = .053) and ground contact time were similar (253 [25] vs 251 [20] ms, P = .5227) and the variance of all outcomes was similar in lab shoes versus normal shoes. Our results indicate that using standardized lab shoes during testing may underestimate the loads runners actually experience during their typical mileage.
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Structuring of aqueous suspensions of colloidal silica nanoparticles near an isolated planar silica-water interface is studied by specular neutron reflectivity. The reflectivity data clearly show that the suspensions develop a damped, oscillatory concentration profile in the normal direction to the interface. The wavelengths of these oscillations agree well with those independently determined by direct force measurements in the slit-geometry. The reflectivity data further demonstrate that the oscillatory structure persists over several layers and that the first particle layer is separated from the interface by a particle-free region.
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This review addresses experimental findings obtained with direct force measurements between two similar or dissimilar solid surfaces in aqueous electrolyte solutions. Interpretation of these measurements is mainly put forward in terms of the classical theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). This theory invokes a superposition of attractive van der Waals forces and repulsive double layer forces. DLVO theory is shown to be extremely reliable, even in the case of multivalent ions. However, such a description is only successful, when appropriate surface charge densities, charge regulation characteristics, and ion pairing or complexation equilibria in solution are considered. Deviations from DLVO theory only manifest themselves at distances of typically below few nm. More long-ranged non-DLVO forces can be observed in some situations, particularly, in concentrated electrolyte solutions, in the presence of strongly adsorbed layers, or for hydrophobic surfaces. The latter forces probably originate from patch-charge surface heterogeneities, which can be induced by ion-ion correlation effects, charge fluctuations, or other types of surface heterogeneities.
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Hydrocarbon films confined between smooth mica surfaces have long provided an experimental playground for model studies of structure and dynamics of confined liquids. However, fundamental questions regarding the phase behavior and shear properties in this simple system remain unsolved. With ultrasensitive resolution in film thickness and shear stress, and control over the crystallographic alignment of the confining surfaces, we here investigate the shear forces transmitted across nanoscale films of dodecane down to a single molecular layer. We resolve the conditions under which liquid-solid phase transitions occur and explain friction coefficients spanning several orders of magnitude. We find that commensurate surface alignment and presence of water at the interfaces each lead to moderate or high friction, whereas friction coefficients down to [Formula: see text] are observed for a single molecular layer of dodecane trapped between crystallographically misaligned dry surfaces. This ultralow friction is attributed to sliding at the incommensurate interface between one of the mica surfaces and the laterally ordered solid molecular film, reconciling previous interpretations.
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Double-layer forces acting between micron-sized silica particles are measured with the atomic force microscope in solutions of symmetric, multivalent electrolytes. In particular, the 2:2 electrolytes, CuSO4 and MgSO4, and the 3:3 electrolyte LaFe(CN)6 were investigated. For the multivalent electrolytes, the measured decay lengths are substantially larger than the ones expected on the basis of simple Debye-Hückel (DH) theory. These deviations can be explained quantitatively by the formation of neutral ion pairs. The measured surface charge density decreases in magnitude with increasing valence. Both effects are caused by ion-ion correlations, which are not included in the classical DH theory. However, this theory remains applicable, provided one considers the formation of ion pairs in solution and an effective surface charge density. This effective charge is substantially smaller in magnitude than the one of the bare surface. This reduction results from adsorption of counterions, which becomes stronger with increasing valence. These observations reveal that DH theory is applicable even in the presence of multivalent ions, provided the effective parameters are chosen appropriately.
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The structure of the ionic liquid 1-decyl-1-methylpyrrolidinium bis[(trifluoromethane)sulfonyl]imide, [C10C1Pyrr][NTf2], has been probed using Molecular Dynamics (MD) simulations. The simulations endeavour to model the behaviour of the ionic liquid in bulk isotropic conditions and also at interfaces and in confinement. The MD results have been confronted and validated with scattering and surface force experiments reported in the literature. The calculated structure factors, distribution functions, and density profiles were able to provide molecular and mechanistic insights into the properties of these long chain ionic liquids under different conditions, in particular those that lead to the formation of multi-layered ionic liquid films in confinement. Other properties inaccessible to experiment such as in-plane structures and relaxation rates within the films have also been analysed. Overall the work contributes structural and dynamic information relevant to many applications of ionic liquids with long alkyl chains, ranging from nanoparticle synthesis to lubrication.
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Direct force measurements involving amidine latex (AL) and sulfate latex (SL) particles in aqueous solutions containing multivalent ferrocyanide anions are presented. These measurements feature three different pairs of particles, namely SL-SL, AL-SL, and AL-AL. The force profiles are quantitatively interpreted in terms of the theory by Derjaguin, Landau, Verwey, and Overbeek (DLVO) that is combined with a short-ranged exponential attraction. In monovalent salt solutions, the AL particles are positively charged, while the SL particles are negatively charged. In solutions containing ferrocyanide, the charge of the AL particles is reversed as the concentration is increased. The longer-ranged component of all force profiles is fully compatible with DLVO theory, provided effects of charge regulation are included. At shorter distances, an additional exponential attraction must be introduced, whereby the respective decay length is about 2 nm for the AL-AL pair, and below 1 nm for the SL-SL pair. This non-DLVO force is intermediate for the asymmetric AL-SL pair. These additional forces are probably related to charge fluctuations, patch-charged interactions, or hydrophobic forces.
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The complex interplay of the tumour microenvironment (TME) and its role in disease progression and response to therapy is poorly understood. The majority of studies to date focus on individual components or molecules within the TME and so lack the power correlative analysis. Here we have performed a multi-parameter analysis of the TME in 62 resectable non-small cell lung cancer (NSCLC) specimens detailing number and location of immune infiltrate, assessing markers of cancer-associated fibroblasts, caveolin-1 and tenascin-C, and correlating with clinicopathological details, as well as markers of disease progression such as epithelial-to-mesenchymal transition (EMT). The influence of individual parameters on overall survival was determined in univariate and multivariate analysis and the combination of risk factors and interplay between components analysed. Low numbers of CD8 T cells, low stromal levels of caveolin-1 or high levels of tenascin-C were significant prognostic markers of decreased overall survival in both univariate and multivariate analysis. Patients with two or more risk factors had dramatically reduced overall survival and those with all three a median survival of just 7.5 months. In addition, low levels of tumour E-cadherin correlated with reduced immune infiltrate into the tumour nests, possibly linking EMT to the avoidance of CD8 T cell control. The multicomponent approach has allowed identification of the dominant influences on overall survival, and exploration of the interplay between different components of the TME in NSCLC.
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Many applications of ionic liquids involve their mixtures with neutral molecular solvents. The chemical physics of these high-concentration electrolytes, in particular at interfaces, still holds many challenges. In this contribution we begin to unravel the relationship between measurements of structural ('solvation') forces in mixtures of ionic liquid with polar solvent and the corresponding structure determined by molecular dynamics simulations of the same mixtures. In order to make the quantitative link between experiments with mica surfaces and simulations with fixed-charge surfaces, we present an experimental procedure for determining the effective surface charge on mica in ionic liquid. We find that a structural cross-over recently inferred from force measurements appears to be supported by the simulations: at the cross-over, the charge-oscillatory structure switches to charge-monotonic, and solvent layering becomes dominant. Finally, we map out a phase diagram in composition-surface charge space delineating regions of charge-oscillatory interfacial structure and regions of charge-monotonic decay. We note that these features of structure and oscillatory forces are distinct from (acting simultaneously with) the recently reported longer range monotonic forces arising from anomalously long bulk screening lengths in high-concentration electrolytes.
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Direct force measurements between negatively charged colloidal particles were carried out using an atomic force microscope (AFM) in aqueous solutions containing monovalent organic cations, namely tetraphenylarsonium (Ph4As+), 1-hexyl-3-methylimidazolium (HMIM+), and 1-octyl-3-methylimidazolium (OMIM+). These ions adsorb to the particle surface, and induce a charge reversal. The forces become attractive at the charge neutralization point, but they are stronger than van der Waals forces. This additional and unexpected attraction decays exponentially with a decay length of a few nanometers, and is strikingly similar to the one previously observed in the presence of multivalent ions. This attractive force probably originates from coupled spontaneous charge fluctuations on the respective surfaces as initially suggested by Kirkwood and Shumaker.
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The interaction between charged objects in an electrolyte solution is a fundamental question in soft matter physics. It is well known that the electrostatic contribution to the interaction energy decays exponentially with object separation. Recent measurements reveal that, contrary to the conventional wisdom given by the classic Poisson-Boltzmann theory, the decay length increases with the ion concentration for concentrated electrolytes and can be an order of magnitude larger than the ion diameter in ionic liquids. We derive a simple scaling theory that explains this anomalous dependence of the decay length on the ion concentration. Our theory successfully collapses the decay lengths of a wide class of salts onto a single curve. A novel prediction of our theory is that the decay length increases linearly with the Bjerrum length, which we experimentally verify by surface force measurements. Moreover, we quantitatively relate the measured decay length to classic measurements of the activity coefficient in concentrated electrolytes, thus showing that the measured decay length is indeed a bulk property of the concentrated electrolyte as well as contributing a mechanistic insight into empirical activity coefficients.
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Screening of a surface charge by an electrolyte and the resulting interaction energy between charged objects is of fundamental importance in scenarios from bio-molecular interactions to energy storage. The conventional wisdom is that the interaction energy decays exponentially with object separation and the decay length is a decreasing function of ion concentration; the interaction is thus negligible in a concentrated electrolyte. Contrary to this conventional wisdom, we have shown by surface force measurements that the decay length is an increasing function of ion concentration and Bjerrum length for concentrated electrolytes. In this paper we report surface force measurements to test directly the scaling of the screening length with Bjerrum length. Furthermore, we identify a relationship between the concentration dependence of this screening length and empirical measurements of activity coefficient and differential capacitance. The dependence of the screening length on the ion concentration and the Bjerrum length can be explained by a simple scaling conjecture based on the physical intuition that solvent molecules, rather than ions, are charge carriers in a concentrated electrolyte.
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The structure and interactions in electrolytes at high concentration have implications from energy storage to biomolecular interactions. However, many experimental observations are yet to be explained in these mixtures, which are far beyond the regime of validity of mean-field models. Here, we study the structural forces in a mixture of ionic liquid and solvent that is miscible in all proportions at room temperature. Using the surface force balance to measure the force between macroscopic smooth surfaces across the liquid mixtures, we uncover an abrupt increase in the wavelength above a threshold ion concentration. Below the threshold concentration, the wavelength is determined by the size of the solvent molecule, whereas above the threshold, it is the diameter of a cation-anion pair that determines the wavelength.
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Ionic liquids are pure salts that are liquid under ambient conditions. As liquids composed solely of ions, the scientific consensus has been that ionic liquids have exceedingly high ionic strengths and thus very short Debye screening lengths. However, several recent experiments from laboratories around the world have reported data for the approach of two surfaces separated by ionic liquids which revealed remarkable long range forces that appear to be electrostatic in origin. Evidence has accumulated demonstrating long range surface forces for several different combinations of ionic liquids and electrically charged surfaces, as well as for concentrated mixtures of inorganic salts in solvent. The original interpretation of these forces, that ionic liquids could be envisioned as "dilute electrolytes," was controversial, and the origin of long range forces in ionic liquids remains the subject of discussion. Here we seek to collate and examine the evidence for long range surface forces in ionic liquids, identify key outstanding questions, and explore possible mechanisms underlying the origin of these long range forces. Long range surface forces in ionic liquids and other highly concentrated electrolytes hold diverse implications from designing ionic liquids for energy storage applications to rationalizing electrostatic correlations in biological self-assembly.
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The layering of ionic liquids close to flat, charged interfaces has been identified previously through theoretical and some experimental measurements. Here we present evidence for oscillations in ion density ('layering') in a long chain ionic liquid (1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide) near the interface with mica using two complementary approaches. Neutron reflection at the ionic liquid-mica interface is used to detect structure at a single interface, and surface force balance (SFB) measurements carried out with the same ionic liquid reveal oscillatory density in the liquid confined between two mica sheets. Our findings imply the interfacial structure is not induced by confinement alone. Structural forces between two mica surfaces extend to approximately twice the distance of the density oscillations measured at a single interface and have similar period in both cases.
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A flow system to perform Chan-Lam coupling reactions of various amines and arylboronic acids has been realised employing molecular oxygen as an oxidant for the re-oxidation of the copper catalyst enabling a catalytic process. A tube-in-tube gas reactor has been used to simplify the delivery of the oxygen accelerating the optimisation phase and allowing easy access to elevated pressures. A small exemplification library of heteroaromatic products has been prepared and the process has been shown to be robust over extended reaction times.
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BACKGROUND: Perinatal regionalization is a system of maternal and neonatal risk-appropriate health care delivery in which resources are ideally allocated for mothers and newborns during pregnancy, labor and delivery, and postpartum, in order to deliver appropriate care. Typically, perinatal risk-appropriate care is provided in-person, but with the advancement of technologies, the opportunity to provide care remotely has emerged. Telemedicine provides distance-based care to patients by consultation, diagnosis, and treatment in rural or remote US jurisdictions (states and territories). OBJECTIVE: We sought to summarize the telemedicine policies of states and territories and assess if maternal and neonatal risk-appropriate care is specified. STUDY DESIGN: We conducted a 2014 systematic World Wide Web-based review of publicly available rules, statutes, regulations, laws, planning documents, and program descriptions among US jurisdictions (N = 59) on telemedicine care. Policies including language on the topics of consultation, diagnosis, or treatment, and those specific to maternal and neonatal risk-appropriate care were categorized for analysis. RESULTS: Overall, 36 jurisdictions (32 states; 3 territories; and District of Columbia) (61%) had telemedicine policies with language referencing consultation, diagnosis, or treatment; 29 (49%) referenced consultation, 30 (51%) referenced diagnosis, and 35 (59%) referenced treatment. In all, 26 jurisdictions (22 states; 3 territories; and District of Columbia) (44%), referenced all topics. Only 3 jurisdictions (3 states; 0 territories) (5%), had policy language specifically addressing perinatal care. CONCLUSION: The majority of states have published telemedicine policies, but few specify policy language for perinatal risk-appropriate care. By ensuring that language specific to the perinatal population is included in telemedicine policies, access to maternal and neonatal care can be increased in rural, remote, and resource-challenged jurisdictions.
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Política de Salud , Cuidado Intensivo Neonatal/legislación & jurisprudencia , Obstetricia/legislación & jurisprudencia , Atención Perinatal/legislación & jurisprudencia , Telemedicina/legislación & jurisprudencia , Samoa Americana , Servicios Centralizados de Hospital , Manejo de la Enfermedad , Femenino , Humanos , Recién Nacido , Micronesia , Embarazo , Puerto Rico , Derivación y Consulta , Medición de Riesgo , Estados Unidos , Islas Virgenes de los Estados UnidosRESUMEN
According to classical electrolyte theories interactions in dilute (low ion density) electrolytes decay exponentially with distance, with the Debye screening length the characteristic length scale. This decay length decreases monotonically with increasing ion concentration due to effective screening of charges over short distances. Thus, within the Debye model no long-range forces are expected in concentrated electrolytes. Here we reveal, using experimental detection of the interaction between two planar charged surfaces across a wide range of electrolytes, that beyond the dilute (Debye-Hückel) regime the screening length increases with increasing concentration. The screening lengths for all electrolytes studied-including aqueous NaCl solutions, ionic liquids diluted with propylene carbonate, and pure ionic liquids-collapse onto a single curve when scaled by the dielectric constant. This nonmonotonic variation of the screening length with concentration, and its generality across ionic liquids and aqueous salt solutions, demonstrates an important characteristic of concentrated electrolytes of substantial relevance from biology to energy storage.