Smart or stimuli-responsive materials are an emerging class of materials used for tissue engineering and drug delivery. A variety of stimuli (including temperature, pH, redox-state, light, and magnet ...fields) are being investigated for their potential to change a material's properties, interactions, structure, and/or dimensions. The specificity of stimuli response, and ability to respond to endogenous cues inherently present in living systems provide possibilities to develop novel tissue engineering and drug delivery strategies (for example materials composed of stimuli responsive polymers that self-assemble or undergo phase transitions or morphology transformations). Herein, smart materials as controlled drug release vehicles for tissue engineering are described, highlighting their potential for the delivery of precise quantities of drugs at specific locations and times promoting the controlled repair or remodeling of tissues.
While sensitivity analysis and calibration are common practice in integrated hydrologic modeling, little work has been done to understand how the design of the sensitivity analysis and calibration ...affects the simulation outcome in these often highly nonlinear models. This is especially true for irrigated agricultural basins with a strong connection between land use, groundwater, and surface water. Using a range rather than a single set of initial parameter values, multiple sensitivity analyses, calibrations, and linearity tests were performed using UCODE_2014 on the Scott Valley Integrated Hydrologic Model. Calibration results show that parameters related to crop demand and applied irrigation water are most sensitive. Influence statistics show that low streamflow observations provide the most information during model calibration, indicating preference should be given to these observations during model development, sensitivity analysis, and calibration. Importantly, due to the nonlinearity of the integrated model, significant differences are found in results when initial parameter values are sampled from within their respective expected ranges. Estimates for some parameters varied up to an order of magnitude between calibrations, while all produced similar final objective function values, groundwater elevations, and stream flow. Confidence intervals for individual sensitivity analyses and calibration runs only spanned a fraction of the ensemble estimated parameter range across multiple runs. Our work suggests that a calibration design with multiple sensitivity analyses and calibrations of integrated hydrologic models, each using one of several widely varying sets of initial values, provides a frugal approach to identify parameters across the global parameter space.
Key Points
Multiple sensitivity analyses varying initial parameters provide a frugal method to account for nonlinearity of integrated hydrologic models
Calibration results from integrated hydrologic models of irrigated landscapes may be sensitive to parameters of the crop water demand system
Weakly coupled integrated models are a viable and efficient approach for reproducing observed groundwater‐surface water interactions
We evaluate the utility of three interrelated means of using data to calibrate the fully distributed rainfall-runoff model TOPKAPI as applied to the Maggia Valley drainage area in Switzerland. The ...use of error-based weighting of observation and prior information data, local sensitivity analysis, and single-objective function nonlinear regression provides quantitative evaluation of sensitivity of the 35 model parameters to the data, identification of data types most important to the calibration, and identification of correlations among parameters that contribute to nonuniqueness. Sensitivity analysis required only 71 model runs, and regression required about 50 model runs. The approach presented appears to be ideal for evaluation of models with long run times or as a preliminary step to more computationally demanding methods. The statistics used include composite scaled sensitivities, parameter correlation coefficients, leverage, Cook's D, and DFBETAS. Tests suggest predictive ability of the calibrated model typical of hydrologic models.
The extension of nonlinear optical techniques to the extreme-ultraviolet (EUV), soft and hard x-ray regime represents one of the open challenges of modern science since it would combine chemical ...specificity with background-free detection and ultrafast time resolution. We report on the first observation of a four-wave-mixing (FWM) response from solid-state samples stimulated exclusively by EUV pulses. The all-EUV FWM signal was generated by the diffraction of high-order harmonics of the FERMI free-electron laser (FEL) from the standing wave resulting from the interference of two crossed FEL pulses at the fundamental wavelength. From the intensity of the FWM signal, we are able to extract the first-ever estimate of an effective value of ∼6×10^{-24} m^{2} V^{-2} for the third-order nonlinear susceptibility in the EUV regime. This proof of principle experiment represents a significant advance in the field of nonlinear optics and sets the starting point for a manifold of techniques, including frequency and phase-resolved FWM methods, that are unprecedented in this photon-energy regime.
Ultrafast optical-domain spectroscopies allow to monitor in real time the motion of nuclei in molecules. Achieving element-selectivity had to await the advent of time resolved X-ray spectroscopy, ...which is now commonly carried at X-ray free electron lasers. However, detecting light element that are commonly encountered in organic molecules, remained elusive due to the need to work under vacuum. Here, we present an impulsive stimulated Raman scattering (ISRS) pump/carbon K-edge absorption probe investigation, which allowed observation of the low-frequency vibrational modes involving specific selected carbon atoms in the Ibuprofen RS dimer. Remarkably, by controlling the probe light polarization we can preferentially access the enantiomer of the dimer to which the carbon atoms belong.
The recent construction of free electron lasers allows extending laboratory-based laser experiments to shorter wavelengths, accessing wavevectors typical of nanoscale dynamics and adding element and ...chemical state specificity by exploiting electronic transitions from core levels. The high pulse energies available ensure that this new wavelength range can be advantageously used for nonlinear optics, as in the pioneering case of transient grating spectroscopy: a time-resolved four-wave mixing technique in which two pump pulses are crossed at the sample to generate a spatially periodic excitation whose dynamics is monitored via diffraction of a probe pulse. We will show how extreme ultraviolet photon pulses have been successfully deployed in the last seven years to carry out transient grating experiments, mainly performed at the FERMI free electron laser, addressing a variety of scientific questions, ranging from the study of thermal transport in semiconductors approaching the ballistic regime to the modelling of ultrafast demagnetization at the nanoscale. We will also discuss possible future developments of the transient grating method specifying the impact this could have in various fields of scientific research ranging from molecular chirality to spintronics.
The electronic and structural properties of a material are strongly determined by its symmetry. Changing the symmetry via a photoinduced phase transition offers new ways to manipulate material ...properties on ultrafast timescales. However, to identify when and how fast these phase transitions occur, methods that can probe the symmetry change in the time domain are required. Here we show that a time-dependent change in the coherent phonon spectrum can probe a change in symmetry of the lattice potential, thus providing an all-optical probe of structural transitions. We examine the photoinduced structural phase transition in VO(2) and show that, above the phase transition threshold, photoexcitation completely changes the lattice potential on an ultrafast timescale. The loss of the equilibrium-phase phonon modes occurs promptly, indicating a non-thermal pathway for the photoinduced phase transition, where a strong perturbation to the lattice potential changes its symmetry before ionic rearrangement has occurred.
Key Points
Predictions from alternative models is advised
Criteria do not consistently identify more accurate models
Results expected to be generally applicable to environmental models
Model adequacy ...is evaluated with alternative models rated using model selection criteria (AICc, BIC, and KIC) and three other statistics. Model selection criteria are tested with cross‐validation experiments and insights for using alternative models to evaluate model structural adequacy are provided. The study is conducted using the computer codes UCODE_2005 and MMA (MultiModel Analysis). One recharge alternative is simulated using the TOPKAPI hydrological model. The predictions evaluated include eight heads and three flows located where ecological consequences and model precision are of concern. Cross‐validation is used to obtain measures of prediction accuracy. Sixty‐four models were designed deterministically and differ in representation of river, recharge, bedrock topography, and hydraulic conductivity. Results include: (1) What may seem like inconsequential choices in model construction may be important to predictions. Analysis of predictions from alternative models is advised. (2) None of the model selection criteria consistently identified models with more accurate predictions. This is a disturbing result that suggests to reconsider the utility of model selection criteria, and/or the cross‐validation measures used in this work to measure model accuracy. (3) KIC displayed poor performance for the present regression problems; theoretical considerations suggest that difficulties are associated with wide variations in the sensitivity term of KIC resulting from the models being nonlinear and the problems being ill‐posed due to parameter correlations and insensitivity. The other criteria performed somewhat better, and similarly to each other. (4) Quantities with high leverage are more difficult to predict. The results are expected to be generally applicable to models of environmental systems.
Following fertilization, the blastocyst has to complete two distinct steps to assure further development of pregnancy. After apposition it establishes a firm connection with the luminal epithelium of ...the endometrium (attachment) and subsequently enters the decidualizing stroma (invasion). If this step is not achieved successfully, fertility problems arise. Development of the placenta ensures an adequate supply of nutrients and gas between the mother and the fetus. Preeclampsia is a prevalent disorder arising from defects in the process of placentation. It is associated with an increase of maternal morbidity and mortality. Numerous attempts have been made in order to elucidate the etiology of the syndrome and identify women at risk. The lack of reliable animal models has turned the attention to the development of in vitro assays, which could provide a better insight into the individual processes that will later trigger preeclampsia symptoms. In particular, 3D in vitro models more closely resemble the complexity of the extracellular environment. The choice of the scaffolding material should be done carefully as cell-matrix interactions are very often as important as cell-cell interactions for the correct attachment, proliferation and differentiation of cells. The following review is aimed to provide a general overview of the scaffolds available for the in vitro modeling of these complicated systems as well as to discuss the importance surrounding the choice of the scaffolding material and its influence on the results obtained.
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