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We investigate both analytically and by numerical simulation the relaxation of an overdamped Brownian particle in a 1D multiwell potential.We show that the mean relaxation time from an injection point inside the well down to its bottom is dominated by statistically rare trajectories that sample the potential profile outside the well. As a consequence, also the hopping time between two degenerate wells can depend on the detailed multiwell structure of the entire potential. The nonlocal nature of the transitions between two states of a disordered landscape is important for the correct interpretation of the relaxation rates in complex chemical-physical systems, measured either through numerical simulations or experimental techniques. [ABSTRACT FROM AUTHOR]

Polyurethane (PU) is a polymer widely used in the biomedical field with excellent mechanical properties and good biocompatibility. However, it usually exhibits poor antibacterial properties for practical applications. Efforts are needed to improve the antibacterial activities of PU films for broader application prospect and added application values. In the present work, two PU films, TDI-P(E-co-T) and TDI-N-100-P(E-co-T), were prepared. Silver nanoparticles (AgNPs) were composited into the TDI-N-100-P(E-co-T) film for better mechanical properties and antibacterial activities, and resultant PU/AgNPs composite film was systematically characterized and studied. The as-prepared PU/AgNPs composite film exhibits much better antibacterial properties than the traditional PU membrane, exhibiting broader application prospect. [ABSTRACT FROM AUTHOR]

A self-propelled artificial microswimmer is often modeled as a ballistic Brownian particle moving with constant speed aligned along one of its axis, but changing direction due to random collisions with the environment. Similarly to thermal noise, its angular randomization is described as a memoryless stochastic process. Here, we speculate that finite-time correlations in the orientational dynamics can affect the swimmer's diffusivity. To this purpose, we propose and solve two alternative models. In the first one, we simply assume that the environmental fluctuations governing the swimmer's propulsion are exponentially correlated in time, whereas in the second one, we account for possible damped fluctuations of the propulsion velocity around the swimmer's axis. The corresponding swimmer's diffusion constants are predicted to get, respectively, enhanced or suppressed upon increasing the model memory time. Possible consequences of this effect on the interpretation of the experimental data are discussed. [ABSTRACT FROM AUTHOR]

It is critically important to quantify the impact of land use land cover (LULC) changes on hydrology, and to understand the mechanism by which LULC changes affect the hydrological process in a river basin. To accurately simulate the hydrological process for a watershed like the Wei River Basin, where the surface characteristics are highly modified by human activities, we present an alternative approach of time-varying parameters in a hydrological model to reflect the changes in underlying land surfaces. The spatiotemporal impacts of LULC changes on watershed streamflow are quantified, and the mechanism that connects the changes in runoff generation and streamflow with LULC is explored. Results indicate the following: (1) time-varying parameters' calibration is effective to ensure model validity when dealing with significant changes in underlying land surfaces; (2) LULC changes have significant impacts on the watershed streamflow, especially on the streamflow during the dry season; (3) the expansion of cropland is the major contributor to the reduction of surface water, causing decline in annual and dry seasonal streamflow. However, the shrinkage of woodland is the main driving force that decreases the soil water, thus contributing to a small increase in streamflow during the dry season. [ABSTRACT FROM AUTHOR]

Rh(III)-catalyzed C–H activation of arenes and mild oxidative [4 + 2] annulative coupling with ketenes have been realized. The uniquely high reactivity of the C(3) of 2-phenylindoles was successfully utilized to facilitate the reductive elimination process, leading to efficient synthesis of cyclic products with a quaternary carbon stereocenter. [ABSTRACT FROM AUTHOR]

The synthsis of fluorinated isoxazolidines in bicyclic settings has been realized via Ru(II)-catalyzed C-H activation of aryl nitrones with perfluoroalkyl-substituted olefins as the coupling partner. The reaction proceeded via initial chelation-assisted C(aryl)-H allylation followed by regio- and diastereoselective intramolecular dipolar addition between the nitrone directing group and the olefin unit. [ABSTRACT FROM AUTHOR]

Rh-catalyzed C-H activation of phenacyl phosphoniums in coupling with α-diazocarbonyl compounds has been realized with the assistance of a mutifunctional phosphonium ylidic directing group, providing expedient accesses to 1-naphthols and isocoumarins. Switchable synthesis of 1-naphthols and isocoumarins was realized by substrate control, where these transformations were enabled by initial C-H activation and subsequent intramolecular Wittig reaction or nucleophilic C-O formation. [ABSTRACT FROM AUTHOR]

Rhodium(III)-catalyzed C-H activation of heteroarenes and functionalization with bifunctional substrates such as anthranils allows facile construction of quinoline-fused heterocycles under redox-neutral conditions. The couplings feature broad substrate scope and provide step-economical access to two classes of quinoline-fused condensed heterocycles. [ABSTRACT FROM AUTHOR]

Oxidized low-density lipoprotein (Ox-LDL)-induced macrophage pyroptosis is critical in atherosclerosis inflammation and plaque instability. It has been reported that mitochondrial (mt)DNA-depleted (rho0) cells demonstrate resistance to apoptosis. However, little is known about the susceptibility of rho0 cells to Ox-LDL-induced macrophage pyroptosis. Pyroptosis, a caspase-1-dependent programmed cell death, which compromises membrane integrity, cleaves pro-interleukin (IL)-1ß and pro-IL-18 into IL-1ß and IL-18, respectively and releases damage-associated molecular pattern molecules, is triggered by a variety of stimuli, including Ox-LDL. In the present study, the expression levels of cleaved caspase-1 and IL-1ß in Ox-LDL-treated J774A.1 rho0 cells were observed to be significantly decreased when compared with Ox-LDL-treated J774A.1 normal cells. Furthermore, J774A.1 rho0 cells exhibited a significant reduction in the ratios of dead cells and lactate dehydrogenase release following Ox-LDL stimulation compared with the J774A.1 normal cells. In addition, the loss of mtDNA did not influence Ox-LDL-induced cholesterol accumulation in J774A.1 rho0 cells, which was observed by Oil Red O staining and CHOD-PAP assay. Finally, J774A.1 rho0 cells exhibited reduced reactive oxygen species (ROS) production and were capable of maintaining the mitochondrial membrane potential following Ox-LDL treatment. Thus, the results indicate that the loss of mtDNA potentially rendered murine macrophage J774A.1 resistant to Ox-LDL-induced pyroptosis by mitigating NACHT, LRR and PYD domains-containing protein 3 inflammasome activation through reducing ROS production. In addition, mtDNA depletion did not interrupt Ox-LDL-induced intracellular lipid accumulation and continued to maintain the mitochondrial membrane potential. [ABSTRACT FROM AUTHOR]

We numerically investigate the motion of active artificial microswimmers diffusing in a fuel concentration gradient. We observe that, in the steady state, their probability density accumulates in the low-concentration regions, whereas a tagged swimmer drifts with velocity depending in modulus and orientation on how the concentration gradient affects the self-propulsion mechanism. Under most experimentally accessible conditions, the particle drifts toward the high-concentration regions (pseudochemotactic drift). A correct interpretation of experimental data must account for such an "anti-Fickian" behavior. [ABSTRACT FROM AUTHOR]

Rectification of electron wave-packets propagating along a quasi-one dimensional chain is commonly achieved via the simultaneous action of nonlinearity and longitudinal asymmetry, both confined to a limited portion of the chain termed wave diode. However, it is conceivable that, in the presence of an external magnetic field, spatial asymmetry perpendicular to the direction of propagation suffices to ensure rectification. This is the case of a nonlinear ring-shaped lattice with different upper and lower halves (diode), which is attached to two elastic chains (leads). The resulting device is mirror symmetric with respect to the ring vertical axis, but mirror asymmetric with respect to the chain direction. Wave propagation along the two diode paths can be modeled for simplicity by a discrete Schrβdinger equation with cubic nonlinearities. Numerical simulations demonstrate that, thanks to the Aharonov-Bohm effect, such a diode can be operated by tuning the magnetic flux across the ring. [ABSTRACT FROM AUTHOR]

An active swimmer can tow a passive cargo by binding it to form a self-propelling dimer. The orientation of the cargo relative to the axis of the active dimer's head is determined by the hydrodynamic interactions associated with the propulsion mechanism of the latter. We show how the tower-cargo angular configuration greatly influences the dimer's diffusivity and, therefore, the efficiency of the active swimmer as a micro-towing motor. [ABSTRACT FROM AUTHOR]

The dynamics of a pair of identical artificial microswimmers bound inside two harmonic traps, in a thin sheared fluid film, is numerically investigated. In a two-dimensional Oseen approximation, the hydrodynamic pair coupling is long-ranged and proportional to the particle radius to film thickness ratio. On increasing such ratio above a certain threshold, a transition occurs between a free regime, where each swimmer orbits in its own trap with random phase, and a strong synchronization regime, where the two swimmers strongly repel each other to an average distance larger than both the trap distance and their free orbit diameter. Moreover, the swimmers tend to synchronize their positions opposite the center of the system. [ABSTRACT FROM AUTHOR]

We model the two-dimensional dynamics of a pointlike artificial microswimmer diffusing in a harmonic trap subject to the shear flow of a highly viscous medium. The particle is driven simultaneously by the linear restoring force of the trap, the drag force exerted by the flow, and the torque due to the shear gradient. For a Couette flow, elliptical orbits in the noiseless regime, and the correlation functions between the particle's displacements parallel and orthogonal to the flow are computed analytically. The effects of thermal fluctuations (translational) and self-propulsion fluctuations (angular) are treated separately. Finally, we discuss how to extend our approach to the diffusion of a microswimmer in a Poiseuille flow. These results provide an accurate reference solution to investigate, both numerically and experimentally, hydrodynamics corrections to the diffusion of active matter in confined geometries. [ABSTRACT FROM AUTHOR]

Transport and the spread of heat in Hamiltonian one dimensional momentum conserving nonlinear systems is commonly thought to proceed anomalously. Notable exceptions, however, do exist of which the coupled rotator model is a prominent case. Therefore, the quest arises to identify the origin of manifest anomalous energy and momentum transport in those low dimensional systems. We develop the theory for both, the statistical densities for momentum- and energy-spread and particularly its momentum-/heat-diffusion behavior, as well as its corresponding momentum/heat transport features. We demonstrate that the second temporal derivative of the mean squared deviation of the momentum spread is proportional to the equilibrium correlation of the total momentum flux. Subtracting the part which corresponds to a ballistic momentum spread relates (via this integrated, subleading momentum flux correlation) to an effective viscosity, or equivalently, to the underlying momentum diffusivity. We next put forward the intriguing hypothesis: normal spread of this so adjusted excess momentum density causes normal energy spread and alike normal heat transport (Fourier Law). Its corollary being that an anomalous, superdiffusive broadening of this adjusted excess momentum density in turn implies an anomalous energy spread and correspondingly anomalous, superdiffusive heat transport. This hypothesis is successfully corroborated within extensive molecular dynamics simulations over large extended time scales. Our numerical validation of the hypothesis involves four distinct archetype classes of nonlinear pair-interaction potentials: (i) a globally bounded pair interaction (the noted coupled rotator model), (ii) unbounded interactions acting at large distances (the coupled rotator model amended with harmonic pair interactions), (iii) the case of a hard point gas with unbounded square-well interactions and (iv) a pair interaction potential being unbounded at short distances while displaying an asymptotic free part (Lennard–Jones model). We compare our findings with recent predictions obtained from nonlinear fluctuating hydrodynamics theory. [ABSTRACT FROM AUTHOR]

We numerically simulate the diffusion of overdampd pointlike Janus particles along narrow two-dimensional periodically corrugated channels with reflecting walls. The self-propulsion velocity of the particle is assumed to rotate subject to an intrinsic bias modeled by a torque. Breaking the mirror symmetry of the channel with respect to its axis suffices to generate a directed particle flow with orientation and magnitude which depend on the channel geometry and the particle swimming properties. This means that chiral microswimmers drift autonomously along a narrow channel under more general asymmetry conditions than previously reported, a property of potential impact on their fabrication and technological applications. [ABSTRACT FROM AUTHOR]

A Rh(III)-catalyzed site-selective C-H activation of C(3)-functionalized indoles in a coupling with diazo esters has been realized with carbonyl as a weakly coordinating group. The coupling selectivity is dictated by the temperature and additives, affording either C4-alkylated indoles or C2-annulated lactones in moderate to excellent efficiency. [ABSTRACT FROM AUTHOR]

In the absence of advection, confined diffusion characterizes transport in many natural and artificial devices, such as ionic channels, zeolites, and nanopores. While extensive theoretical and numerical studies on this subject have produced many important predictions, experimental verifications of the predictions are rare. Here, we experimentally measure colloidal diffusion times in microchannels with periodically varying width and contrast results with predictions from the Fick-Jacobs theory and Brownian dynamics simulation. While the theory and simulation correctly predict the entropic effect of the varying channel width, they fail to account for hydrodynamic effects, which include both an overall decrease and a spatial variation of diffusivity in channels. Neglecting such hydrodynamic effects, the theory and simulation underestimate the mean and standard deviation of first passage times by 40% in channels with a neck width twice the particle diameter. We further show that the validity of the Fick-Jacobs theory can be restored by reformulating it in terms of the experimentally measured diffusivity. Our work thus shows that hydrodynamic effects play a key role in diffusive transport through narrow channels and should be included in theoretical and numerical models. [ABSTRACT FROM AUTHOR]

Ir(III)-catalyzed synthesis of benzimidazoles has been realized under redox-neutral conditions by annulation of aniline derivatives with dioxazolones. The reaction proceeded via a C-H activation-amidation-cyclization pathway with a decent substrate scope. [ABSTRACT FROM AUTHOR]

Phytoplankton is the major source of labile organic matter in the sunlit ocean, and they are therefore key players in most biogeochemical cycles. However, studies examining the heterotrophic bacterial cycling of specific phytoplankton-derived nitrogen (N)- and sulfur (S)-containing organic compounds are currently lacking at the molecular level. Therefore, the present study investigated how the addition of N-containing (glycine betaine [GBT]) and S-containing (dimethylsulfoniopropionate [DMSP]) organic compounds, as well as glucose, influenced the microbial production of new organic molecules and the microbial community composition. The chemical composition of microbial-produced dissolved organic matter (DOM) was analyzed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) demonstrating that CHO-, CHON-, and CHOS-containing molecules were enriched in the glucose, GBT, and DMSP experiments, respectively. High-throughput sequencing showed that Alteromonadales was the dominant group in the glucose, while Rhodobacterales was the most abundant group in both the GBT and DMSP experiments. Cooccurrence network analysis furthermore indicated more complex linkages between the microbial community and organic molecules in the GBT compared with the other two experiments. Our results shed light on how different microbial communities respond to distinct organic compounds and mediate the cycling of ecologically relevant compounds. [ABSTRACT FROM AUTHOR]

Metal halide perovskite nanostructures have recently been the focus of intense research due to their exceptional optoelectronic properties and potential applications in integrated photonics devices. Charge transport in perovskite nanostructure is a crucial process that defines efficiency of optoelectronic devices but still requires a deep understanding. Herein, we report the study of the charge transport, particularly the drift of minority carrier in both all-inorganic CsPbBr3 and organic–inorganic hybrid CH3NH3PbBr3 perovskite nanoplates by electric field modulated photoluminescence (PL) imaging. Bias voltage dependent elongated PL emission patterns were observed due to the carrier drift at external electric fields. By fitting the drift length as a function of electric field, we obtained the carrier mobility of about 28 cm2 V–1 S–1 in the CsPbBr3 perovskite nanoplate. The result is consistent with the spatially resolved PL dynamics measurement, confirming the feasibility of the method. Furthermore, the electric field modulated PL imaging is successfully applied to the study of temperature-dependent carrier mobility in CsPbBr3 nanoplates. This work not only offers insights for the mobile carrier in metal halide perovskite nanostructures, which is essential for optimizing device design and performance prediction, but also provides a novel and simple method to investigate charge transport in many other optoelectronic materials. [ABSTRACT FROM AUTHOR]

Ewing sarcoma (EWS) is a kind of aggressive tumor of bone and soft tissues, which most occurring in children and adolescents. MicroRNAs (miRNAs) perform essential function in the progression and development of EWS, while the putative role of miR-638 in EWS remains uncertain. Accordingly, we detected the expression of miR-638 and explored its putative biological effects on the malignant phenotype of EWS cells. As expected, miR-638 was significantly down-regulated in EWS cells. Moreover, overexpression of miR-638 suppressed cell growth, induced cell apoptosis, and inhibited tubule formation of EWS cells in vitro. Among the putative target genes of miR-638 predicted by the miRNA target prediction tools, vascular endothelial cell growth factor A (VEGFA) attracted out attention most. The luciferase reporter assays reaffirmed that VEGFA was a targeted gene of miR-638 in EWS cells. Furthermore, miR-638 suppressed the mRNA and protein level of VEGFA, and restored the expression of VEGFA reversed the suppressed effects of miR-638 in EWS cells. Taken together, the results suggested that miR-638 might perform tumor suppressive effects in EWS, which might be mediated, at least partially, through suppressing the activity of VEGFA. [ABSTRACT FROM AUTHOR]

Rh(III)-catalyzed [3 + 2] annulation of cyclic N-sulfonyl or N-acyl ketimines with activated alkenes has been realized, leading to the synthesis of spirocycles with three continuous stereogenic centers. This atom-economic reaction proceeded efficiently under mild and redox-neutral conditions via a C--H activation pathway, and the coupling is diastereodivergent, with the diastereoselectivity being controlled by silver additives. [ABSTRACT FROM AUTHOR]

The main goal of this study is to introduce the Archimedean copulas, which overcome the low accuracy and subjective nature of the traditional double mass curve method, to investigate the precipitation-runoff relationship (PRR) and detect change points in the Weihe River Basin (WRB). With the construction of a joint distribution between precipitation and runoff by the Archimedean copulas, a statistical variable considering the distribution parameter was estimated to judge the change point of the PRR. The results show that: (1) annual precipitation and runoff present decreasing trends that are significant and insignificant, respectively, at the 95% significance level, while annual potential evapotranspiration (PET) increases slightly; (2) change points of the PRR occurred in 1971 and 1994; (3) the annual runoff changed more dramatically than precipitation during the periods from 1972 to 1994 and 1995 to 2010 compared with 1960-1971, which indicates that in addition to precipitation, there are some other non-precipitation factors that are responsible for the change in the PRR; and (4) the contributions to runoff from human activities declined from 1972 to 1994 (84.15%) and 1995 to 2010 (57.16%). These results suggest that human activities (e.g., irrigation, reservoirs, water-and-soil conservation) were the primary driving forces leading to changes in the PRR in the WRB. [ABSTRACT FROM AUTHOR]

Imidate esters and diazo compounds have been established as bifunctional substrates for the construction of biologically active fused heterocycles via rhodium-catalyzed C-H activation and C-C/C-N coupling. This reaction occurs under mild conditions with high efficiency, step economy, and low catalyst loading. [ABSTRACT FROM AUTHOR]

The aim of this study was to assess the long-term effects of community-based health management on elderly diabetic patients using a Markov model. A Markov decision model was used to simulate the natural history of diabetes. Data were obtained from our randomized trials of elderly with type 2 diabetes and from the published literature. One hundred elderly patients with type 2 diabetes were randomly allocated to either the management or the control group in a one-to-one ratio. The management group participated in a health management program for 18 months in addition to receiving usual care. The control group only received usual care. Measurements were performed on both groups at baseline and after 18 months. The Markov model predicted that for every 1000 diabetic patients receiving health management, approximately 123 diabetic patients would avoid complications, and approximately 37 would avoid death over the next 13 years. The results suggest that the health management program had a positive long-term effect on the health of elderly diabetic patients. The Markov model appears to be useful in health care planning and decision-making aimed at reducing the financial and social burden of diabetes. [ABSTRACT FROM AUTHOR]

In many natural and artificial devices diffusive transport takes place in confined geometries with corrugated boundaries. Such boundaries cause both entropic and hydrodynamic effects, which have been studied only for the case of spherical particles. Here we experimentally investigate the diffusion of particles of elongated shape confined in a corrugated quasi-two-dimensional channel. The elongated shape causes complex excluded-volume interactions between particles and channel walls which reduce the accessible configuration space and lead to novel entropic free-energy effects. The extra rotational degree of freedom also gives rise to a complex diffusivity matrix that depends on both the particle location and its orientation. We further show how to extend the standard Fick-Jacobs theory to incorporate combined hydrodynamic and entropic effects, so as, for instance, to accurately predict experimentally measured mean first passage times along the channel. Our approach can be used as a generic method to describe translational diffusion of anisotropic particles in corrugated channels. [ABSTRACT FROM AUTHOR]