Remote Activation of H-H Bonds by Platinum in Dilute Alloy Catalysts.

With heterogeneous catalysts, chemical promotion takes place at their surfaces. Even in the case of single-atom alloys, where small quantities of a reactive metal are dispersed within the main host, it is assumed that both elements are exposed and available to bond with the reactants. Here, we show, on the basis of in situ X-ray absorption spectroscopy data, that in alloy catalysts made from Pt highly diluted in Cu the Pt atoms are located at the inner interface between the metal nanoparticles and the silica support instead. Kinetic experiments indicated that these catalysts still display better selectivity for the hydrogenation of unsaturated aldehydes to unsaturated alcohols than the pure metals. Density functional theory calculations corroborated the stability of Pt at the metal-support interface and explained the catalytic performance as being due to a remote lowering of the activation barrier for the dissociation of H2 at Cu sites by the internal Pt atoms.

Three-dimensional nanoscale metal, metal oxide, and semiconductor frameworks through DNA-programmable assembly and templating.

Controlling the three-dimensional (3D) nanoarchitecture of inorganic materials is imperative for enabling their novel mechanical, optical, and electronic properties. Here, by exploiting DNA-programmable assembly, we establish a general approach for realizing designed 3D ordered inorganic frameworks. Through inorganic templating of DNA frameworks by liquid- and vapor-phase infiltrations, we demonstrate successful nanofabrication of diverse classes of inorganic frameworks from metal, metal oxide and semiconductor materials, as well as their combinations, including zinc, aluminum, copper, molybdenum, tungsten, indium, tin, and platinum, and composites such as aluminum-doped zinc oxide, indium tin oxide, and platinum/aluminum-doped zinc oxide. The open 3D frameworks have features on the order of nanometers with architecture prescribed by the DNA frames and self-assembled lattice. Structural and spectroscopic studies reveal the composition and organization of diverse inorganic frameworks, as well as the optoelectronic properties of selected materials. The work paves the road toward establishing a 3D nanoscale lithography.

Highly active, ultra-low loading single-atom iron catalysts for catalytic transfer hydrogenation.

Highly effective and selective noble metal-free catalysts attract significant attention. Here, a single-atom iron catalyst is fabricated by saturated adsorption of trace iron onto zeolitic imidazolate framework-8 (ZIF-8) followed by pyrolysis. Its performance toward catalytic transfer hydrogenation of furfural is comparable to state-of-the-art catalysts and up to four orders higher than other Fe catalysts. Isotopic labeling experiments demonstrate an intermolecular hydride transfer mechanism. First principles simulations, spectroscopic calculations and experiments, and kinetic correlations reveal that the synthesis creates pyrrolic Fe(II)-plN3 as the active center whose flexibility manifested by being pulled out of the plane, enabled by defects, is crucial for collocating the reagents and allowing the chemistry to proceed. The catalyst catalyzes chemoselectively several substrates and possesses a unique trait whereby the chemistry is hindered for more acidic substrates than the hydrogen donors. This work paves the way toward noble-metal free single-atom catalysts for important chemical reactions.

Zn-Doped P-Type InAs Nanocrystal Quantum Dots.

Doped heavy metal-free III-V semiconductor nanocrystal quantum dots (QDs) are of great interest both from the fundamental aspects of doping in highly confined structures, and from the applicative side of utilizing such building blocks in the fabrication of p-n homojunction devices. InAs nanocrystals (NCs), that are of particular relevance for short-wave IR detection and emission applications, manifest heavy n-type character poising a challenge for their transition to p-type behavior. The p-type doping of InAs NCs is presented with Zn - enabling control over the charge carrier type in InAs QDs field effect transistors. The post-synthesis doping reaction mechanism is studied for Zn precursors with varying reactivity. Successful p-type doping is achieved by the more reactive precursor, diethylzinc. Substitutional doping by Zn2+ replacing In3+ is established by X-ray absorption spectroscopy analysis. Furthermore, enhanced near infrared photoluminescence is observed due to surface passivation by Zn as indicated from elemental mapping utilizing high-resolution electron microscopy corroborated by X-ray photoelectron spectroscopy study. The demonstrated ability to control the carrier type, along with the improved emission characteristics, paves the way towards fabrication of optoelectronic devices active in the short-wave infrared region utilizing heavy-metal free nanocrystal building blocks.

Will Natural Media Make Online Physicians More Trustworthy? The Effect of Media Naturalness on Patients' Intention to Use HIT.

Although previous studies have recognized the important role of patients' trust in promoting their intention to use health information technologies (HIT), most of those studies were under the "risk-benefit" theoretical framework. To deepen the understanding of patients' online consultation decisions, this paper develops a dual-path model investigating how patients develop trust beliefs toward online physicians from the perspective of communication. Drawing on media naturalness theory, we propose that HIT media naturalness will improve patients' perception of communication effort from online physicians and decrease communication ambiguity between patients and online physicians. This improved communication will further strengthen patients' trust in online physicians and promote their intention to use HIT. Based on a two-wave time-lagged survey from 361 participants, the empirical results demonstrated that the relationship between HIT media naturalness and patients' intention to use HIT is individually and serially mediated by two chains, including (1) perceived communication effort and patients' trust and (2) perceived communication ambiguity and patients' trust. We thus contribute to the related literature and provide practical implications.

Impact of Myocardial Energy Expenditure and Diastolic Dysfunction on One Year Outcome Patients With HFpEF.

Objective: To explore the correlation between characteristics of myocardial energy expenditure (MEE) and the degree of diastolic dysfunction in patients of heart failure with preserved ejection fraction (HFpEF) and its clinical significance. Methods: 125 consecutive patients diagnosed with HFpEF in the Department of Cardiology, Affiliated Zhongshan Hospital of Dalian University from January 2018 to October 2018 were enrolled. According to the degree of diastolic dysfunction, patients were divided into group A (8 ≤ E/e' ≤15) and group B (E/e'> 15), and MEE was calculated, patients finished 1-year clinical follow-up. Results: The level of MEE in group A was significantly lower than that in group B (p < 0.05). During 1-year follow up, MEE over 3145.69 kcal/systole was associated with increased risk of death as compared to patients with MEE less 3145.69 kcal/systole, and in patients with MEE over 101.68 kcal/min than in patients with MEE less than 101.68 kcal/min. Conclusion: There is a significant correlation between MEE and diastolic dysfunction and MEE over 3145.69 kcal/systole as well as MEE over 101.68 kcal/min are linked with increased risk of 1-year mortality in HFpEF.

Solving the structure of "single-atom" catalysts using machine learning - assisted XANES analysis.

"Single-atom" catalysts (SACs) have demonstrated excellent activity and selectivity in challenging chemical transformations such as photocatalytic CO2 reduction. For heterogeneous photocatalytic SAC systems, it is essential to obtain sufficient information of their structure at the atomic level in order to understand reaction mechanisms. In this work, a SAC was prepared by grafting a molecular cobalt catalyst on a light-absorbing carbon nitride surface. Due to the sensitivity of the X-ray absorption near edge structure (XANES) spectra to subtle variances in the Co SAC structure in reaction conditions, different machine learning (ML) methods, including principal component analysis, K-means clustering, and neural network (NN), were utilized for in situ Co XANES data analysis. As a result, we obtained quantitative structural information of the SAC nearest atomic environment, thereby extending the NN-XANES approach previously demonstrated for nanoparticles and size-selective clusters.

How Does Leader Empowering Behavior Promote Employee Knowledge Sharing? The Perspective of Self-Determination Theory.

Although scholars have recognized the important role of leader empowering behavior in promoting employee knowledge sharing, investigations on the potential underlying mechanism are still limited. To enrich studies revealing the possible underlying paths, drawing on self-determination theory, this paper proposes a moderated mediation model. We propose that employee self-determination plays a mediating role and employee proactivity moderates the mediating effect. We test our hypotheses based on data collected from 230 employees across a three-wave study. The empirical results demonstrate that leader empowering behavior promotes employee knowledge sharing by enhancing employee self-determination. Employees' proactive personality moderates the indirect effect such that the indirect effect is stronger when employees have high levels of proactive personality. This paper thus contributes to the related literature and reveals practical implications.

Engineered Silicon Carbide Three-Dimensional Frameworks through DNA-Prescribed Assembly.

The ability to create nanoengineered silicon carbide (SiC) architectures is important for the diversity of optical, electronic, and mechanical applications. Here, we report a fabrication of periodic three-dimensional (3D) SiC nanoscale architectures using a self-assembled and designed 3D DNA-based framework. The assembly is followed by the templating into silica and subsequent conversion into SiC using a lower temperature pathway (<700 °C) via magnesium reduction. The formed SiC framework lattice has a unit size of about 50 nm and domains over 5 µm, and it preserves the integrity of the original 3D DNA lattice. The spectroscopic and electron microscopy characterizations reveal SiC crystalline morphology of 3D nanoarchitectured lattices, whereas electrical probing shows 2 orders of magnitude enhancements of electrical conductivity over the precursor silica framework. The reported approach offers a versatile methodology toward creating highly structured and spatially prescribed SiC nanoarchitectures through the DNA-programmable assembly and the combination of templating processes.

The Effect of Leaders' Coaching Behaviors on Employee Learning Orientation: A Regulatory Focus Perspective.

Although scholars have recognized leaders' importance in facilitating employee learning, the potential role that leaders' specific behaviors play in followers' learning outcomes remains elusive. Based on the literature, we identified two styles of leaders' coaching behaviors that may promote followers' learning, namely encourage-to-explore behaviors and guide-to-learn behaviors. We expect that these two styles of coaching behaviors would have different relationships with employee learning orientation, moderated by employees' regulatory focus. To test our hypotheses, we conducted two studies: an experimental study using scenarios of leader behavior with data collected from 124 undergraduate students (study 1), and a field study with data from 334 pairs of employees and their direct supervisors (study 2). Results showed that encourage-to-explore behaviors had a positive relationship with employee learning orientation, whereas guide-to-learn behaviors had an inverted U-shaped relationship with employee learning orientation. When employees had low levels of promotion regulatory focus, encourage-to-explore behaviors showed a positive correlation with employee learning orientation. However, when they had low levels of prevention regulatory focus, employee learning orientation increased as the guide-to-learn behaviors increased; this increased up to an intermediate level and then decreased. As such, this study provides novel theoretical and empirical insights into leadership and learning literature.

Enhancement of the Fouling Resistance of Zwitterion Coated Ceramic Membranes.

Ceramic membranes suffer from rapid permeability loss during filtration of organic matter due to their fouling propensity. To address this problem, iron oxide ultrafiltration membranes were coated with poly(sulfobetaine methacrylate) (polySBMA), a superhydrophilic zwitterionic polymer. The ceramic-organic hybrid membrane was characterized by scanning electron microscopy (SEM) and optical profilometry (OP). Membranes with and without polySBMA coating were subjected to fouling with bovine serum albumin solution. Hydraulic cleaning was significantly more effective for the coated membrane than for the non-coated one, as 56%, 66%, and 100% of the fouling was removed for the first, second, and third filtration cycle, respectively. Therefore, we can highlight the improved cleaning due to an increased fouling reversibility. Although some loss of polymer during operation was detected, it did not affect the improved behavior of the tested membranes.

Engineering Organization of DNA Nano-Chambers through Dimensionally Controlled and Multi-Sequence Encoded Differentiated Bonds.

Engineering the assembly of nanoscale objects into complex and prescribed structures requires control over their binding properties. Such control might benefit from a well-defined bond directionality, the ability to designate their engagements through specific encodings, and the capability to coordinate local orientations. Although much progress has been achieved in our ability to design complex nano-objects, the challenges in creating such nano-objects with fully controlled binding modes and understanding their fundamental properties are still outstanding. Here, we report a facile strategy for creating a DNA nanochamber (DNC), a hollow cuboid nano-object, whose bonds can be fully prescribed and complexly encoded along its three orthogonal axes, giving rise to addressable and differentiated bonds. The DNC can host nanoscale cargoes, which allows for the integration with functional nano-objects and their organization in larger-scale systems. We explore the relationship between the design of differentiated bonds and a formation of one-(1D), two-(2D), and three-(3D) dimensional organized arrays. Through the realization of different binding modes, we demonstrate sequence encoded nanoscale heteropolymers, helical polymers, 2D lattices, and mesoscale 3D nanostructures with internal order, and show that this assembly strategy can be applied for the organization of nanoparticles. We combine experimental investigations with computational simulation to understand the mechanism of structural formation for different types of ordered arrays, and to correlate the bonds design with assembly processes.

Three-Dimensional Patterning of Nanoparticles by Molecular Stamping.

Directing the formation of nanoscale architectures from nanoparticles is one of the key challenges in designing nanomaterials with prescribed functions. Atomic systems, given their ability to form molecules and crystals via directional chemical bonds, provide an inspiration for establishing approaches where nanoparticles with designed anisotropic binding modalities can be assembled into nanoscale architectures. However, fabricating such nanoparticles has been challenging due to their small dimensions and limited ways for site-specific control of their surface. To this end, we present a molecular stamping (MOST) approach to pattern DNA-coated nanoparticles with molecules at the predefined positions on a nanoparticle surface. This patterning is realized by use of a rigid and coordinative DNA frame as a molecular stamping apparatus (MOST App). The MOST App transfers multiple types of molecular "inks", DNA sequences, onto a nanoparticle surface and fixes these molecular inks into place to form a designed pattern. After a nanoparticle is released the from MOST App, it possesses single-molecule patches that can provide anisotropic bonds with distinctive affinities. We further use these stamped nanoparticles to assemble prescribed clusters, whose structure is determined by the locations of patches. Using electron microscopy and tomographic methods, we investigate the efficiency of cluster formation and the resulting spatial arrangements of nanoparticles. The presented approach provides a single-molecule and spatially determined control over nanoparticle functionalization for creating nanoparticles with designed placement of different molecules and for realizing a rational fabrication of nanomaterial architectures.

A metabolomic study for chronic heart failure patients based on a dried blood spot mass spectrometry approach.

Objective: a dried blood spot (DBS) method integrated with direct infusion mass spectrometry (MS) focused on a metabolomic analysis was applied to detect and compare the difference of metabolites between the heart failure (HF) patients and non-HF patients in order to facilitate the early detection of heart failures, provide targeted intervention and offer prognostic insights. Methods: the method we used was an untargeted metabolic approach. The dry blood spot mass spectrometry (DBS) was used to analyze 23 types of amino acids and 26 types of carnitine in blood samples. In the current study, 49 metabolites were selected to establish the PLS-DA model to compare the differences between the 117 HF patients and 118 non-HF patients, which inclined to detect the difference between the two groups. Multiple algorithms were run for selecting different metabolites as potential biomarkers. Ten-fold cross validation method was used to verify and evaluate the selected potential biomarkers. Results: through significant analysis of the microarrays (SAM) and analysis of 9 parameters, 8 metabolites showed significant discrepancies between the HF and non-HF groups. Among these metabolites, the levels of 5 metabolites were increased, and the other 3 metabolites were decreased in the HF group compared with the non-HF group. However, 7 metabolites including Asn, C0, C14, C4DC, C5-OH, C6 and Glu were selected to distinguish the HF group from the non-HF group with specificity and sensitivity of 0.8475 and 0.8974, respectively. Conclusion: metabolomic study for chronic heart failure (CHF) patients based on the dried blood spot mass spectrometry approach would be beneficial to understand the metabolic pathway of HF, and probably work as biomarkers to predict the prognosis of HF and provide the basis for an individualized treatment.

Controllable Covalent-Bound Nanoarchitectures from DNA Frames.

Could one manipulate nanoscale building blocks using chemical reactions like molecular synthesis to yield new supra-nanoscale objects? The precise control over the final architecture might be challenging due to the size mismatch of molecularly scaled reactive functional groups and nanoscale building blocks, which limits a control over the valence and specific locations of reaction spots. Taking advantage of programmable octahedral DNA frame, we report a facile approach of engineering chemical reactions between nanoscale building blocks toward formation of controlled nanoarchitectures. Azide and alkyne moieties were specifically anchored onto desired vertices of DNA frames, providing chemically reactive nanoconstructs with directionally defined valence. Akin to the conventional molecular reactions, the formation of a variety of nanoscale architectures was readily achieved upon mixing of the frames with the different reactive valence and at different stoichiometric ratios. This strategy may open a door for a programmable synthesis of supra-nanoscale structures with complex architectures and diversified functions.

Photonic Molecularly Imprinted Polymer Film for the Detection of Testosterone in Aqueous Samples.

The detection of testosterone in aqueous solutions is a difficult task due to the low concentration levels that are relevant in environmental and physiological samples. Current analytical methods are expensive and/or complex. To address this issue, we fabricated a molecularly imprinted polymer (MIP) photonic film for the detection of testosterone in water. The films were obtained using colloidal crystals as templates for the pore morphology. Monodispersed silica particles with an average diameter 330 nm were used to obtain the colloidal crystal by vertical deposition. A solution of acrylic acid with testosterone as the imprinted template was infiltrated in the colloidal crystal and polymerized via bulk polymerization; the particles were then removed by acid etching and the testosterone eluted by a suitable solvent. The material was characterized by FTIR, swelling experiments and microscopy; MIPs were investigated by equilibrium rebinding, kinetics and reuse experiments. The results showed that the MIPs exhibited selectivity to the template, a 30-min equilibration time and stability after at least six cycles of use and regeneration. After incubation, the reflectance spectra of the films showed a shift of the Bragg diffraction peak that correlated with testosterone concentration in the 5⁻100 ppb range.