Investigation of mechanical properties and structural integrity of graphene aerogels via molecular dynamics simulations.

Graphene aerogel (GA), a 3D carbon-based nanostructure built on 2D graphene sheets, is well known for being the lightest solid material ever synthesized. It also possesses many other exceptional properties, such as high specific surface area and large liquid absorption capacity, thanks to its ultra-high porosity. Computationally, the mechanical properties of GA have been studied by molecular dynamics (MD) simulations, which uncover nanoscale mechanisms beyond experimental observations. However, studies on how GA structures and properties evolve in response to simulation parameter changes, which provide valuable insights to experimentalists, have been lacking. In addition, the differences between the calculated properties via simulations and experimental measurements have rarely been discussed. To address the shortcomings mentioned above, in this study, we systematically study various mechanical properties and the structural integrity of GA as a function of a wide range of simulation parameters. Results show that during the in silico GA preparation, smaller and less spherical inclusions (mimicking the effect of water clusters in experiments) are conducive to strength and stiffness but may lead to brittleness. Additionally, it is revealed that a structurally valid GA in the MD simulation requires the number of bonds per atom to be at least 1.40, otherwise the GA building blocks are not fully interconnected. Finally, our calculation results are compared with experiments to showcase both the power and the limitations of the simulation technique. This work may shed light on the improvement of computational approaches for GA as well as other novel nanomaterials.

Ion correlation-driven like-charge attraction in multivalent salt solutions.

The electrostatic double layer force is key to determining the stability and self-assembly of charged colloids and many other soft matter systems. Fully understanding the attractive force between two like-charged surfaces remains a great challenge. Here, we apply the modified Gaussian renormalized fluctuation theory to study ion correlation-driven like-charge attraction in multivalent salt solutions. The effects of spatially varying ion correlations on the structure of overlapping double layers and their free energy are self-consistently accounted for. In the presence of multivalent salts, increasing surface charge or counterion valency leads to a short-range attraction. We demonstrate that although both overcharging and like-charge attraction are outcomes of ion correlation, there is no causal relationship between them. Our theory also captures the non-monotonic dependence of like-charge attraction on multivalent salt concentration. The reduction of attraction at high salt concentrations could be a contributing factor toward the reentrant stability of charged colloidal suspensions. Our theoretical predictions are consistent with the observations reported in experiments and simulations.

Probiotics Function in Preventing Atopic Dermatitis in Children.

Atopic dermatitis (AD) is a chronic inflammatory skin disorder characterized by relapsing eczematous injuries and severe pruritus. In the last few years, the AD prevalence has been increasing, reaching 20% in children and 10% in adults in high-income countries. Recently, the potential role of probiotics in AD prevention has generated considerable interest. As many clinical studies show, the gut microbiota is able to modulate systemic inflammatory and immune responses influencing the development of sensitization and allergy. Probiotics are used increasingly against AD. However, the molecular mechanisms underlying the probiotics mediated anti-allergic effect remain unclear and there is controversy about their efficacy. In this narrative review, we examine the actual evidence on the effect of probiotic supplementation for AD prevention in the pediatric population, discussing also the potential biological mechanisms of action in this regard.

Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties.

Some nanoporous, crystalline materials possess dynamic constituents, for example, rotatable moieties. These moieties can undergo a conformation change in response to the adsorption of guest molecules, which qualitatively impacts adsorption behavior. We pose and solve a statistical mechanical model of gas adsorption in a porous crystal whose cages share a common ligand that can adopt two distinct rotational conformations. Guest molecules incentivize the ligands to adopt a different rotational configuration than maintained in the empty host. Our model captures inflections, steps, and hysteresis that can arise in the adsorption isotherm as a signature of the rotating ligands. The insights disclosed by our simple model contribute a more intimate understanding of the response and consequence of rotating ligands integrated into porous materials to harness them for gas storage and separations, chemical sensing, drug delivery, catalysis, and nanoscale devices. Particularly, our model reveals design strategies to exploit these moving constituents and engineer improved adsorbents with intrinsic thermal management for pressure-swing adsorption processes.

Transistor-Based Work-Function Measurement of Metal-Organic Frameworks for Ultra-Low-Power, Rationally Designed Chemical Sensors.

A classic challenge in chemical sensing is selectivity. Metal-organic frameworks (MOFs) are an exciting class of materials because they can be tuned for selective chemical adsorption. Adsorption events trigger work-function shifts, which can be detected with a chemical-sensitive field-effect transistor (power ≈microwatts). In this work, several case studies were used towards generalizing the sensing mechanism, ultimately towards our metal-centric hypothesis. HKUST-1 was used as a proof-of-principle humidity sensor. The response is thickness independent, meaning the response is surface localized. ZIF-8 is demonstrated to be an NO2 -sensing material, and the response is dominated by adsorption at metal sites. Finally, MFM-300(In) shows how standard hard-soft acid-base theory can be used to qualitatively predict sensor responses. This paper sets the groundwork for using the tunability of metal-organic frameworks for chemical sensing with distributed, scalable devices.

Prevention of recurrent lower urinary tract infections in postmenopausal women with genitourinary syndrome: outcome after 6 months of treatment with ospemifene.

Aim of this study was to evaluate the efficacy of ospemifene in the prevention of recurrent lower urinary tract infections in postmenopausal women with vulvovaginal atrophy. The study have a retrospective design. Thirty-nine patients were enrolled. Patients underwent clinical examination and urine culture. The urinary symptoms and the quality of life were evaluated with UTISA score, PUF and SF-36 questionnaires before and after treatment. All 39 patients received ospemifene 60 mg one tablet/daily for 6 months. Adverse effects and complications were assessed. Thirty-nine patients were enrolled in the study. Two patients experienced one new UTI episode and the mean number of positive urine culture decreased significantly after 6 months (3.65 ± 2.12 vs 0.25 ± 0.17, p < .0001). The mean number of urinary infection symptoms decreased significantly after treatment; dysuria reduced (4.76 ± 2.45 vs 0.89 ± 1.12). PUF score and SF-36 showed a statistically significant change (22.43 ± 5.89 vs 12.14 ± 3.21) and (52.86 ± 9.21 vs 83.43 ± 10.76). No adverse effects were reported and the total success rate was the 92.3% after 6 months at PGI-I. Ospemifene is a valid alternative with excellent tolerability for the UTIS prevention in postmenopausal patients.

Strong interlayer coupling in van der Waals heterostructures built from single-layer chalcogenides.

Semiconductor heterostructures are the fundamental platform for many important device applications such as lasers, light-emitting diodes, solar cells, and high-electron-mobility transistors. Analogous to traditional heterostructures, layered transition metal dichalcogenide heterostructures can be designed and built by assembling individual single layers into functional multilayer structures, but in principle with atomically sharp interfaces, no interdiffusion of atoms, digitally controlled layered components, and no lattice parameter constraints. Nonetheless, the optoelectronic behavior of this new type of van der Waals (vdW) semiconductor heterostructure is unknown at the single-layer limit. Specifically, it is experimentally unknown whether the optical transitions will be spatially direct or indirect in such hetero-bilayers. Here, we investigate artificial semiconductor heterostructures built from single-layer WSe2 and MoS2. We observe a large Stokes-like shift of ∼ 100 meV between the photoluminescence peak and the lowest absorption peak that is consistent with a type II band alignment having spatially direct absorption but spatially indirect emission. Notably, the photoluminescence intensity of this spatially indirect transition is strong, suggesting strong interlayer coupling of charge carriers. This coupling at the hetero-interface can be readily tuned by inserting dielectric layers into the vdW gap, consisting of hexagonal BN. Consequently, the generic nature of this interlayer coupling provides a new degree of freedom in band engineering and is expected to yield a new family of semiconductor heterostructures having tunable optoelectronic properties with customized composite layers.

Selective ultrathin carbon sheath on porous silicon nanowires: materials for extremely high energy density planar micro-supercapacitors.

Microsupercapacitors are attractive energy storage devices for integration with autonomous microsensor networks due to their high-power capabilities and robust cycle lifetimes. Here, we demonstrate porous silicon nanowires synthesized via a lithography compatible low-temperature wet etch and encapsulated in an ultrathin graphitic carbon sheath, as electrochemical double layer capacitor electrodes. Specific capacitance values reaching 325 mF cm(-2) are achieved, representing the highest specific ECDL capacitance for planar microsupercapacitor electrode materials to date.

Hole selective MoOx contact for silicon solar cells.

Using an ultrathin (∼ 15 nm in thickness) molybdenum oxide (MoOx, x < 3) layer as a transparent hole selective contact to n-type silicon, we demonstrate a room-temperature processed oxide/silicon solar cell with a power conversion efficiency of 14.3%. While MoOx is commonly considered to be a semiconductor with a band gap of 3.3 eV, from X-ray photoelectron spectroscopy we show that MoOx may be considered to behave as a high workfunction metal with a low density of states at the Fermi level originating from the tail of an oxygen vacancy derived defect band located inside the band gap. Specifically, in the absence of carbon contamination, we measure a work function potential of ∼ 6.6 eV, which is significantly higher than that of all elemental metals. Our results on the archetypical semiconductor silicon demonstrate the use of nm-thick transition metal oxides as a simple and versatile pathway for dopant-free contacts to inorganic semiconductors. This work has important implications toward enabling a novel class of junctionless devices with applications for solar cells, light-emitting diodes, photodetectors, and transistors.

Two-fluid wetting behavior of a hydrophobic silicon nanowire array.

The two-fluid wetting behavior of surfaces textured by an array of silicon nanowires is investigated systematically. The Si nanowire array is produced by a combination of colloidal patterning and metal-catalyzed etching, with control over its roughness depending upon the wire length. The nanowires are made hydrophobic and oleophobic by treatment with hydrocarbon and fluorinated self-assembled monolayers, respectively. Static, advancing, and receding contact angles are measured with water, hexadecane, and perfluorotripentylamine in both single-fluid (droplet on solid in an air environment) and two-fluid (droplet on solid in a liquid environment) configurations. The single-fluid measurements show wetting behavior similar to that expected by the Wenzel and Cassie-Baxter models, where the wetting or non-wetting behaviors are amplified with increasing roughness. The two-fluid systems on the rough surface exhibit more complex configurations because either the droplet or the environment fluid can penetrate the asperities depending upon the wettability of each fluid. It is observed that, when the Young contact angles are significantly increased or reduced from single-liquid to two-liquid systems, the effect of roughness is relatively minimal. However, when the Young contact angles are similar, roughness has almost identical influence on apparent contact angles in single- and two-liquid systems. The Wenzel and Cassie-Baxter models are modified to describe various two-fluid wetting states. In cases where metastable behavior is observed for the droplet, advancing and receding measurements are performed to suggest the equilibrium state of the droplet.

Highly flexible, all solid-state micro-supercapacitors from vertically aligned carbon nanotubes.

We report a highly flexible planar micro-supercapacitor with interdigitated finger electrodes of vertically aligned carbon nanotubes (VACNTs). The planar electrode structures are patterned on a thin polycarbonate substrate with a facile, maskless laser-assisted dry transfer method. Sputtered Ni is used to reduce the in-plane resistance of the VACNT electrodes. An ionogel, an ionic liquid in a semi-solid matrix, is used as an electrolyte to form a fully solid-state device. We measure a specific capacitance of 430 µF cm(-2) for a scan rate of 0.1 V s(-1) and achieve rectangular cyclic voltammograms at high scan rates of up to 100 V s(-1). Minimal change in capacitance is observed under bending. Mechanical fatigue tests with more than 1000 cycles confirm the high flexibility and durability of the novel material combination chosen for this device. Our results indicate that this scalable and facile fabrication technique shows promise for application in integrated energy storage for all solid-state flexible microdevices.

Gold-coated silver dendrites as SERS substrates with an improved lifetime.

Nanostructured silver is known to yield the highest signal-enhancement factors in surface-enhanced Raman spectroscopy, but its low chemical stability toward oxidation presents a challenge in the realization of Ag-based SERS substrates with long operating lifetimes. Here, a study of the long-term stability of silver dendrites as SERS substrates is reported. SERS spectra of 1,2-benzenedithiol monolayers on Ag dendrites, acquired over a period of time in excess of 1 year, shows appreciable degradation with time. However, no degradation is observed in the spectra of monolayers deposited on Ag dendrites that were coated with a monolayer-thin Au film deposited by an immersion plating process. X-ray photoelectron spectra confirm the oxidation of the uncoated Ag dendrites whereas no chemical changes are detected in the Au-coated ones. These results suggest that the galvanic displacement of Au on preformed Ag nanostructures provides a suitable route to producing SERS-active substrates with long operating and/or shelf lifetimes.

Single crystal silicon nanopillars, nanoneedles and nanoblades with precise positioning for massively parallel nanoscale device integration.

Arrays of precisely positioned single crystal silicon nanopillars, nanoneedles, and nanoblades with minimum feature sizes as small as 30 nm are fabricated using entirely scalable top-down fabrication techniques. Using the same scalable technologies, devices consisting of electrically connected silicon nanopillars with multiple addressable electrodes for each nanostructure are realized. The arrays of nanopillars, nanoneedles, and nanoblades are shown to exhibit Raman signal enhancement on 1,2-benzenedithiol monolayers, opening a path to nanodevices that manipulate, position, detect and analyze molecules.

Cobalt Oxide-Decorated Silicon Carbide Nano-Tree Array Electrode for Micro-Supercapacitor Application.

A cobalt oxide (Co3O4)-decorated silicon carbide (SiC) nano-tree array (denoted as Co3O4/SiC NTA) electrode is synthesized, and it is investigated for use in micro-supercapacitor applications. Firstly, the well-standing SiC nanowires (NWs) are prepared by nickel (Ni)-catalyzed chemical vapor deposition (CVD) method, and then the thin layer of Co3O4 and the hierarchical Co3O4 nano-flower-clusters are, respectively, fabricated on the side-walls and the top side of the SiC NWs via electrodeposition. The deposition of Co3O4 on the SiC NWs benefits the charge transfer at the electrode/aqueous electrolyte interface due to its extremely hydrophilic surface characteristic after Co3O4 decoration. Furthermore, the Co3O4/SiC NTA electrode provides a directional charge transport route along the length of SiC nanowires owing to their well-standing architecture. By using the Co3O4/SiC NTA electrode for micro-supercapacitor application, the areal capacitance obtained from cyclic voltammetry measurement reaches 845 mF cm-2 at a 10 mV s-1 scan rate. Finally, the capacitance durability is also evaluated by the cycling test of cyclic voltammetry at a high scan rate of 150 mV s-1 for 2000 cycles, exhibiting excellent stability.

Silver dendrites from galvanic displacement on commercial aluminum foil as an effective SERS substrate.

A silver galvanic displacement process on commercial aluminum foil has been carried out to produce cost-effective SERS substrates. The process is based on an extremely simple redox process where aluminum is oxidized while silver ions are reduced, yielding a final silver dendritic structure that offers a large surface area-to-volume ratio. XPS measurements confirmed the metallic nature of the formed dendrites. SERS substrates were fabricated by spreading of the dendrites on double side Scotch tape attached to a paper slide. Three different thiols were incubated to achieve SAM formation on the Ag dendrites and measured by Raman spectroscopy. The obtained spectra presented well resolved bands and provided valuable information regarding the orientation of the thiols. The high Raman intensity also demonstrates the high enhancement capacities of the produced silver structures. The overall method is cost-effective and allows the use of silver dendrite paste for the mass production of SERS-active substrates, including on flexible substrates and/or via screen printing.

Galvanic deposition of Pt clusters on silicon: effect of HF concentration and application as catalyst for silicon nanowire growth.

We report on the galvanic deposition of Pt on Si from solutions containing PtCl(2) and different concentrations of HF. The results show that for low [HF]/[Pt] ratios (

Transient swelling behavior of the bovine caudal disc.

The intervertebral disc is an avascular composite structure, comprised of the nucleus pulposus (NP) and the annulus fibrosus (AF). Previous tissue-level experiments either examined relative differences in swelling capacity of the two disc regions at a single time point or tested explant structures that did not replicate in situ boundary conditions. Previous joint-level studies that investigated time-dependent fluid flow into the disc provided limited information about swelling-induced intradiscal strains with respect to time and boundary constraints. Therefore, the objective of this study was to investigate time-dependent swelling behavior of the intervertebral disc ex situ. The first study investigated time-dependent free-swelling response of the whole disc and the disc's subcomponents separately (i.e., NP and AF). Findings from this study showed that the swelling rate and swelling capacity of NP explants under free-swelling conditions were greater than AF explants. The second study evaluated the effect of boundary conditions on in-plane strain distributions of intact discs and AF rings. Swelling-induced strain was highly heterogeneous in AF rings, where negative circumferential strains were observed in the inner AF and tensile circumferential strains were observed in the outer AF. Radial strains in AF rings were an order of magnitude greater than circumferential strains. Restricting fluid flow only to the outer AF periphery reduced the swelling of the inner AF. Swelling of intact discs affected both NP and AF swelling behaviors, where NP hydration decreased by 60%. Furthermore, the presence of the NP reduced peak radial strains in the AF and resulted in uniform strain distribution throughout the AF. In conclusion, these studies highlight that tissue hydration and swelling-induced strains largely depend on regional biochemical composition and geometric boundary constraints.

Polymer-oligopeptide composite coating for selective detection of explosives in water.

The selective detection of a specific target molecule in a complex environment containing potential contaminants presents a significant challenge in chemical sensor development. Utilizing phage display techniques against trinitrotoluene (TNT) and dinitrotoluene (DNT) targets, peptide receptors have previously been identified with selective binding capabilities for these molecules. For practical applications, these receptors must be immobilized onto the surface of sensor platforms at high density while maintaining their ability to bind target molecules. In this paper, a polymeric matrix composed of poly(ethylene-co-glycidyl methacrylate) (PEGM) has been prepared. A high density of receptors was covalently linked through reaction of amino groups present in the receptor with epoxy groups present in the co-polymer. Using X-ray photoelectron spectroscopy (XPS) and gas-chromatography/mass spectroscopy (GC/MS), this attachment strategy is demonstrated to lead to stably bound receptors, which maintain their selective binding ability for TNT. The TNT receptor/PEGM conjugates retained 10-fold higher TNT binding ability in liquid compared to the lone PEGM surface and 3-fold higher TNT binding compared to non-specific receptor conjugates. In contrast, non-target DNT exposure yielded undetectable levels of binding. These results indicate that this polymeric construct is an effective means of facilitating selective target interaction both in an aqueous environment. Finally, real-time detection experiments were performed using a quartz crystal microbalance (QCM) as the sensing platform. Selective detection of TNT vs DNT was demonstrated using QCM crystals coated with PEGM/TNT receptor, highlighting that this receptor coating can be incorporated as a sensing element in a standard detection device for practical applications.

Real-time observation of reactive spreading of gold on silicon.

The spreading of a bilayer gold film propagating outward from gold clusters, which are pinned to clean Si(111), is imaged in real time by low-energy electron microscopy. By monitoring the evolution of the boundary of the gold film at fixed temperature, a linear dependence of the spreading radius on time is found. The measured spreading velocities in the temperature range of 800 < T < 930 K varied from below 100 pm/s to 50 nm/s. We show that the spreading rate is limited by the reaction to form Au silicide, and the spreading velocity is likely regulated by the reconstruction of the gold silicide that occurs at the interface.

Multi- and instabilities in gas partitioning between nanoporous materials and rubber balloons.

In the two-balloon experiment, two rubber balloons are connected and allowed to exchange gas. Owing to the non-monotonic relationship between the radius of the balloon and the pressure of gas inside it, the two-balloon system presents multi- and in-stabilities. Herein, we consider a two-adsorbent system, where two different adsorbents are allowed to exchange gas. We show that, for rigid adsorbents, the thermodynamic equilibrium state is unique. Then, we consider an adsorbent-balloon system, where an adsorbent exchanges gas with a rubber balloon. This system can exhibit multiple states at thermodynamic equilibrium- two (meta)stable and one unstable. The size of the balloon, pressure of gas in the balloon, and partitioning of gas between the adsorbent and the balloon differ among the equilibrium states. Temperature changes and the addition/removal of gas into/from the adsorbent-balloon system can induce catastrophe bifurcations and show hysteresis. Furthermore, the adsorbent-balloon system exhibits a critical temperature where, when approached from below, the discrepancy of balloon size between the two (meta)stable states decreases and, beyond, bistability is impossible. Practically, our findings preclude multiple partitions of adsorbed gas in rigid, mixed-linker or stratified metal-organic frameworks and may inspire new soft actuator and sensor designs.