A concise approach to 2-pyrrolin-5-one scaffold construction from α-halohydroxamates and ß-keto compounds.

A concise approach to the construction of the 2-pyrrolin-5-one scaffold was developed via a one-pot reaction with formal [3 + 2] annulation/elimination between ß-keto nitrile/ß-keto ester and unsubstituted α-halohydroxamates. This reaction features mild conditions, easy handling, broad substrate scope and good yields. Remarkably, the products could be readily converted into potentially bioactive alkylidenepyrrolinones, pyrroles, pyran-fused pyrrole heterocycles and other useful compounds, exhibiting versatile synthetic potential.

Highly Fluorescent Collagen-Based Quantum Dots as an Efficient Interlinkage in the 2D Perovskite Bulk for Improved Solar Cells.

A design-inexpensive, effective, and easy-to-prepare additive in the large-scale preparation of perovskite solar cells (PSCs) is urgently desired to alleviate the future energy crisis. Carbon-based quantum dots have demonstrated novel nanomaterials with excellent chemical stability and high electrical conductivity, which exhibit great potential as additives for perovskite optoelectronics. Herein, we designed novel highly fluorescent collagen-based quantum dots (Col-QDs) and thoroughly studied the micromorphological characteristics, photoluminescence properties, and the states of surface-functionalized groups on the Col-QDs. It is found that the introduction of Col-QDs in the two-dimensional (2D) perovskite precursor can be further confirmed as an efficient interlinkage via Col-Pb bands in the pure 2D perovskite heterojunction, which significantly improves the crystallinity, orientation, and interlayer coupling of perovskite crystal plates, as observed by grazing incidence X-ray diffraction (GIWAXS) and X-ray photoelectron spectroscopy (XPS). Finally, the champion Col-QD additive can efficiently modulate the photovoltaic performance of pure 2D PSCs with a significant increase of photoelectric conversion efficiency (PCE) from 8.18% up to 10.45%, which ranks among the best efficiencies of highly pure 2D PSCs. These results provide a facile and feasible approach to modulate the interlayer interaction of pure 2D perovskites and further improve their output of PSCs, which would further facilitate the burgeoning applications of the Col-QDs in various perovskite-based optical-related fields.

Energy Saving and Energy Generation Smart Window with Active Control and Antifreezing Functions.

Windows are the least energy efficient part of the buildings, as building accounts for 40% of global energy consumption. Traditional smart windows can only regulate solar transmission, while all the solar energy on the window is wasted. Here, for the first time, the authors demonstrate an energy saving and energy generation integrated smart window (ESEG smart window) in a simple way by combining louver structure solar cell, thermotropic hydrogel, and indium tin oxides (ITO) glass. The ESEG smart window can achieve excellent optical properties with ≈90% luminous transmission and ≈54% solar modulation, which endows excellent energy saving performance. The outstanding photoelectric conversion efficiency (18.24%) of silicon solar cells with louver structure gives the smart window excellent energy generation ability, which is more than 100% higher than previously reported energy generation smart window. In addition, the solar cell can provide electricity to for ITO glass to turn the transmittance of hydrogel actively, as well as the effect of antifreezing. This work offers an insight into the design and preparation together with a disruptive strategy of easy fabrication, good uniformity, and scalability, which opens a new avenue to realize energy storage, energy saving, active control, and antifreezing integration in one device.

Determination of dynamic interactions of droplets in continuous fluids using droplet probe.

HYPOTHESIS: Interactions between droplets are of fundamental importance for understanding phenomena involving droplet collision and coalescence that determine multiphase flow behavior. The quantitative understanding of these interactions is essential for the manipulation and control of emulsions or complex fluids. The existing methods for interaction force determination are typically based on expensive mechanical probes and fine distance control. Therefore, further development of new techniques for interaction force determination is expected to be beneficial for research on surface force. EXPERIMENTS: In this study, droplet deformation during the interaction between two droplets was captured and analyzed to determine the interaction force. The approach speed of the two droplets was controlled by the injection rate of the fluid. The dynamic interaction force between two tetradecane droplets in various aqueous solutions was determined using the newly developed method, and the effects of two-phase physical properties and operating conditions on the measurement errors were investigated. FINDINGS: The droplet profile deformation was first applied as a probe to detect the interaction force. The measurement results were in good agreement with those obtained using the precise weighing sensor of a commercial interfacial tensiometer (K100, Kruss, Germany). The newly developed method was reliable, simple, and did not require the use of expensive devices. Furthermore, droplet deformability was found to be the key parameter in determining the total interaction force between the droplets.

Comparison of toxicity of Ti3 C2 and Nb2 C Mxene quantum dots (QDs) to human umbilical vein endothelial cells.

Recently, we developed highly fluorescent Ti3 C2 and Nb2 C Mxene quantum dots (QDs) for labeling of in vitro models. However, the mechanism of the toxicity of the prepared QDs was not explored before. In this study, we addressed the possible mechanism associated with cytotoxicity of the QDs to human umbilical vein endothelial cells (HUVECs). Exposure to up to 100 µg/ml Ti3 C2 but not Nb2 C QDs for 24 h significantly induced cytotoxicity. The exposure also increased intracellular Ti and Nb elements, indicating the internalization of both types of QDs. None of the QDs promoted interleukin 6 (IL-6) and IL-8 releases. Rather, Ti3 C2 QDs significantly reduced IL-6 and IL-8 release, indicating that the toxicity of Ti3 C2 QDs was not due to elevated inflammatory responses. Exposure to Ti3 C2 but not Nb2 C QDs resulted in increased LC3B-II/I ratio and beclin-1 proteins, biomarkers of autophagy, as well as the accumulation of autophagic substance p62. Ti3 C2 QDs also more effectively promoted pro-caspase 3 but not pro-caspase 8 compared with Nb2 C QDs. Furthermore, pre-treatment with autophagic modulators altered the cytotoxicity of Ti3 C2 QDs, which further confirmed the role of autophagic dysfunction in Ti3 C2 QD-induced toxicity to HUVECs. In conclusion, the results from this study suggested that high levels of Ti3 C2 QDs could induce cytotoxicity to HUVECs by inducing the dysfunction of autophagy. Nb2 C QDs appeared to be more biocompatible to HUVECs compared with Ti3 C2 QDs at the same mass concentrations, which suggested a role of composition of Mxene QDs to determine their toxicity to human endothelial cells.

Biomimicry Surface-Coated Proppant with Self-Suspending and Targeted Adsorption Ability.

Proppant is a key material, which can increase the production of unconventional petroleum and gas. Excellent proppants with a long migration distance are required in the fracture network. Resin-coated proppants have been confirmed as a good choice because of the long migration and the self-suspending ability in fracturing fluids. However, the distribution of the resin-coated proppants in fracture networks is random. The design of proppants with targeted adsorption is urgently needed. In this study, a novel proppant coated with a phenolic resin shell doped with Fe3O4 nanoparticles on ceramic (coated proppant) was designed and investigated. Based on the results, the coated proppant was adsorbed on the magnetic component's parts of the fracture network surface, which helps in enhancing the uniform distribution of the proppant in the fracture rock cracks. Meanwhile, the self-suspending ability of the coated proppant is five times higher than that of the uncoated proppant and can migrate a longer distance in the fracture network. Moreover, the liquid conductivity of the coated proppant is 30% higher than that of the uncoated ones at a closure pressure of 6.9 MPa. In summary, new insights into the design of functional proppants and further guidelines on the production of unconventional petroleum and gas have been provided in this study.

Novel Stable DNA Nanoscale Material and Its Application on Specific Enrichment of DNA.

DNA nanostructures are a new type of technology for constructing nanomaterials that has been developed in recent years. By relying on the complementary pairing of DNA molecules to form a double-stranded property, DNA molecules can construct a variety of nanoscale structures of 2D and 3D shapes. However, most of the previously reported DNA nanostructures rely solely on hydrogen bonds to maintain structural stability, resulting in DNA structures that can be maintained only at low temperature and in the presence of Mg2+, which greatly limits the application of DNA nanostructures. This study designed a DNA nanonetwork structure (nanonet) and changed its topological structure to DNA nanomesh by using DNA topoisomerase to make it thermally stable, while escaping the dependence on Mg2+, and the stability of the structure can be maintained in a nonsolution state. Moreover, the nanomesh also has a large amount of ssDNA (about 50%), providing active sites capable of exerting biological functions. Using the above characteristics, we prepared the nanomesh into a device capable of adsorbing specific DNA molecules, and used the device to enrich DNA. We also tried to mount antibodies using DNA probes. Preliminary results show that the DNA nanomesh also has the ability to enrich specific proteins.

Enantioselective one-pot synthesis of 4H-chromene derivatives catalyzed by a chiral Ni(ii) complex.

A Ni(ii)-bis(oxazoline) complex and p-TSOH are used to form enantioenriched 4H-chromenes from ortho-quinone methides (o-QMs) and dicarbonyls, providing the desired products in up to 95% ee. The method is compatible with various ß-ketoester substrates, and the products obtained could be converted into biologically active 4H-chromene derivatives.

Cross-lagging analysis of teachers praise classroom environment and eighth grade students’ mental health / 中国学校卫生

Objective@#To explore the relationship between teachers praise, classroom environment and eighth grade students’ mental health.@*Methods@#Based on the baseline data in 2013-2014 and panel data in 2014-2015 of China Education Panel Survey, 9 207 eight grade students followed up for 1 years were selected as subjects. Associations between teacher praise with classroom environment and mental health among students were analyzed by cross lagging analysis.@*Results@#Teachers’ praise at T1 could significantly predict the classroom environment at T2(β=0.09, P<0.01), and couldn’t significantly predict the mental health at T2(β=0.02, P>0.05); Classroom environment at T1 could significantly predict teachers’ praises (β=0.10, P<0.01) and mental health at T2 (β=0.08, P<0.01); Mental health at T1 significantly predicted the teachers’ praises at T2(β=0.09, P<0.01), and the class environment of T2(β=0.06, P<0.01).@*Conclusion@#There is a causal relationship between teacher’ praise, class environment and students’ mental health.

Prognostic value of time to generalization in 71 Chinese patients with sporadic amyotrophic lateral sclerosis.

BACKGROUND: It is important to determine prognostic factors for the outcome of amyotrophic lateral sclerosis (ALS) at an early stage. The time taken for symptoms to spread from spinal or bulbar regions to both (time to generalization; TTG) is considered a strong predictor of survival; however, this has rarely been studied in Asian populations. The aim of this retrospective study was to evaluate potential factors affecting prognosis in Chinese patients with sporadic ALS, with a focus on the association between TTG and overall survival. METHODS: Seventy-one patients with sporadic ALS who were hospitalized at Chinese PLA General Hospital from 2009 to 2016 were followed up until December 2017. Survival analysis was performed using univariate Kaplan-Meier log-rank and multivariate Cox proportional hazards models. The clinical data of the patients were recorded and analyzed. Variables studied were age at symptom onset, sex, site of symptom onset, diagnostic latency, TTG, diagnostic category, ALS Functional Rating Scale-revised score, percent predicted forced vital capacity (FVC%), and disease progression rate (DPR) at diagnosis. RESULTS: The mean age at onset was 54 (SD = 10.2) years, and the median survival time from symptom onset was 41 months (95% confidence interval: 34-47). By univariate analysis, factors independently affecting survival were age at symptom onset (Log rank = 15.652, P < 0.0001), TTG (Log rank = 14.728, P < 0.0001), diagnostic latency (Log rank = 11.997, P = 0.001), and DPR (Log rank = 6.50, P = 0.011). In the Cox multivariate model, TTG had the strongest impact on survival time (hazard ratio = 0.926, P = 0.01). CONCLUSIONS: TTG can be used as an effective indicator of prognosis in patients with sporadic ALS.

Elevated serum ferritin level as a predictor of reduced survival in patients with sporadic amyotrophic lateral sclerosis in China: a retrospective study.

Objective: The objective of this study was to compare iron metabolic variables in the serum and cerebrospinal fluid (CSF) of patients with sporadic amyotrophic lateral sclerosis (sALS) with those of patients with multiple system atrophy (MSA) and control subjects. We also assessed the correlations of these variables with sALS progression and severity and estimated their roles in predicting prognosis. Methods: We retrospectively collected iron metabolic parameters, including serum levels of iron, ferritin, transferrin levels and total iron binding capacity and the CSF level of ferritin, from 435 sALS patients, 176 MSA patients and 431 control subjects. Results: Serum ferritin levels were significantly higher in the sALS group compared with the MSA and control groups in both males (p = 0.001 and p < 0.0001, respectively) and females (p = 0.034 and p < 0.0001, respectively). However, serum transferrin levels were significantly lower in females of the sALS group compared with the MSA (p = 0.016) and control (p = 0.015) groups. The CSF ferritin level and the serum levels of total iron binding capacity and iron were similar among the sALS, MSA and control groups. Survival analysis demonstrated that higher serum ferritin levels were predictors of reduced survival of sALS patients. No correlations between iron metabolic variables and clinical parameters were found. Conclusion: An elevated serum ferritin level is associated with reduced survival of sALS patients. However, the levels of iron metabolic parameters were not associated with clinical deterioration or disease severity at diagnosis.

Tough Reversible Adhesion Properties of a Dry Self-Cleaning Biomimetic Surface.

Geckos have one of the world's most efficient reversible adhesion systems. Even walking in dusty conditions, geckos can dislodge up to 80% of contaminants and recover their adhesion capability after walking as few as four steps. Thus far, artificial dry self-cleaning materials inspired by the geckos' hierarchical fibrillar structure have been only able to remove 55% of collected large particle contaminants with 30 steps. Challenges, including low mechanical strength, low stiffness, and short fatigue time keep these materials from being used in practical applications. This study involves the novel fabrication of dry self-cleaning surfaces with a high mechanical performance and an outstanding dry self-cleaning property. Imposing a load-drag-pull process similar to a gecko's foot adhesion process, our biomimetic surfaces could dislodge up to 59% of microparticles (∼8 µm) with as few as five steps. Furthermore, the surface had an excellent screening ability at low temperatures regardless of the surface roughness similarity. The surfaces were also proven to be scratch resistant. The biomimetic surfaces exhibit enhanced dry self-cleaning and mechanical properties and could be promising in applications such as reusable adhesives, biochips, aerospace satellite waste collection, and screening equipment.

Voltage-Rectified Current and Fluid Flow in Conical Nanopores.

Ion current rectification (ICR) refers to the asymmetric potential-dependent rate of the passage of solution ions through a nanopore, giving rise to electrical current-voltage characteristics that mimic those of a solid-state electrical diode. Since the discovery of ICR in quartz nanopipettes two decades ago, synthetic nanopores and nanochannels of various geometries, fabricated in membranes and on wafers, have been extensively investigated to understand fundamental aspects of ion transport in highly confined geometries. It is now generally accepted that ICR requires an asymmetric electrical double layer within the nanopore, producing an accumulation or depletion of charge-carrying ions at opposite voltage polarities. Our research groups have recently explored how the voltage-dependent ion distributions and ICR within nanopores can induce novel nanoscale flow phenomena that have applications in understanding ionics in porous materials used in energy storage devices, chemical sensing, and low-cost electrical pumping of fluids. In this Account, we review our most recent investigations on this topic, based on experiments using conical nanopores (10-300 nm tip opening) fabricated in thin glass, mica, and polymer membranes. Measurable fluid flow in nanopores can be induced either using external pressure forces, electrically via electroosmotic forces, or by a combination of these two forces. We demonstrate that pressure-driven flow can greatly alter the electrical properties of nanopores and, vice versa, that the nonlinear electrical properties of conical nanopores can impart novel and useful flow phenomena. Electroosmotic flow (EOF), which depends on the magnitude of the ion fluxes within the double layer of the nanopore, is strongly coupled to the accumulation/depletion of ions. Thus, the same underlying cause of ICR also leads to EOF rectification, i.e., unequal flows occurring for the same voltage but opposite polarities. EOF rectification can be used to electrically pump fluids with very precise control across membranes containing conical pores via the application of a symmetric sinusoidal voltage. The combination of pressure and asymmetric EOF can also provide a means to generate new nanopore electrical behaviors, including negative differential resistance (NDR), in which the current through a conical pore decreases with increasing driving force (applied voltage), similar to solid-state tunnel diodes. NDR results from a positive feedback mechanism between the ion distributions and EOF, yielding a true bistability in both fluid flow and electrical current at a critical applied voltage. Nanopore-based NDR is extremely sensitive to the surface charge near the nanopore opening, suggesting possible applications in chemical sensing.

A Paper-Based "Pop-up" Electrochemical Device for Analysis of Beta-Hydroxybutyrate.

This paper describes the design and fabrication of a "pop-up" electrochemical paper-based analytical device (pop-up-EPAD) to measure beta-hydroxybutyrate (BHB)-a biomarker for diabetic ketoacidosis-using a commercial combination BHB/glucometer. Pop-up-EPADs are inspired by pop-up greeting cards and children's books. They are made from a single sheet of paper folded into a three-dimensional (3D) device that changes shape, and fluidic and electrical connectivity, by simply folding and unfolding the structure. The reconfigurable 3D structure makes it possible to change the fluidic path and to control timing; it also provides mechanical support for the folded and unfolded structures that enables good registration and repeatability on folding. A pop-up-EPAD designed to detect BHB shows performance comparable to commercially available plastic test strips over the clinically relevant range of BHB in blood when used with a commercial glucometer that integrates the ability to measure glucose and BHB (combination BHB/glucometer). With simple modifications of the electrode and the design of the fluidic path, the pop-up-EPAD also detects BHB in buffer using a simple glucometer-a device that is more available than the combination BHB/glucometer. Strategies that use a "3D pop-up"-that is, large-scale changes in 3D structure and fluidic paths-by folding/unfolding add functionality to EPADs (e.g., controlled timing, fluidic handling and path programming, control over complex sequences of steps, and alterations in electrical connectivity) and should enable the development of new classes of paper-based diagnostic devices.

Differential proteomics analysis of mononuclear cells in cerebrospinal fluid of Parkinson's disease.

Parkinson's disease (PD) is one common neurodegenerative disease featured with degeneration of dopaminergic neurons in substantia nigra. Multiple factors participate in the pathogenesis and progression of PD. In this study, we investigated the proteomics profiles of mononuclear cells in cerebrospinal fluids from both PD patients and normal people, in order to explore the correlation between disease factors and PD. Cerebrospinal fluid samples were collected from both PD and normal people and were separated for mononuclear cells in vitro. Proteins were then extracted and separated by 2-dimensional gel electrophoresis. Proteins with differential expressions were identified by comparison to standard proteome expression profile map, followed by software and database analysis. In PD patients, there were 8 proteins with consistent expression profile and 16 proteins with differential expressions. Those differential proteins identified include cytoskeleton proteins (actin, myosin), signal transduction proteins (adenosine cyclase binding protein 1, calcium binding protein, talin) and anti-oxidation factor (thioredoxin peroxide reductase). PD patients had differential protein expressional profiles in the mononuclear cells of cerebrospinal fluids compared to normal people, suggesting the potential involvement of cytoskeleton and signal transduction proteins in apoptosis of neuronal apoptosis and PD pathogenesis.

Paper-based potentiometric ion sensing.

This paper describes the design and fabrication of ion-sensing electrochemical paper-based analytical devices (EPADs) in which a miniaturized paper reference electrode is integrated with a small ion-selective paper electrode (ISPE) for potentiometric measurements. Ion-sensing EPADs use printed wax barriers to define electrochemical sample and reference zones. Single-layer EPADs for sensing of chloride ions include wax-defined sample and reference zones that each incorporate a Ag/AgCl electrode. In EPADs developed for other electrolytes (potassium, sodium, and calcium ions), a PVC-based ion-selective membrane is added to separate the sample zone from a paper indicator electrode. After the addition of a small volume (less than 10 µL) of sample and reference solutions to different zones, ion-sensing EPADs exhibit a linear response, over 3 orders of magnitude, in ranges of electrolyte concentrations that are relevant to a variety of applications, with a slope close to the theoretical value (59.2/z mV). Ion-selective EPADs provide a portable, inexpensive, and disposable way of measuring concentrations of electrolyte ions in aqueous solutions.

Resistive-pulse analysis of nanoparticles.

The development of nanopore fabrication methods during the past decade has led to the resurgence of resistive-pulse analysis of nanoparticles. The newly developed resistive-pulse methods enable researchers to simultaneously study properties of a single nanoparticle and statistics of a large ensemble of nanoparticles. This review covers the basic theory and recent advances in applying resistive-pulse analysis and extends to more complex transport motion (e.g., stochastic thermal motion of a single nanoparticle) and unusual electrical responses (e.g., resistive-pulse response sensitive to surface charge), followed by a brief summary of numerical simulations performed in this field. We emphasize the forces within a nanopore governing translocation of low-aspect-ratio, nondeformable particles but conclude by also considering soft materials such as liposomes and microgels.

Redox preparation of mixed-valence cobalt manganese oxide nanostructured materials: highly efficient noble metal-free electrocatalysts for sensing hydrogen peroxide.

High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material preparation. We demonstrated redox preparation strategies to successfully synthesize highly homogeneous, noble metal-free H2O2 sensors of spinel nanostructured cobalt manganese oxides with enhanced conductivity, multiple mixed-valence features, and efficient H2O2 sensing activities. The designed redox reactions accompanied with material nucleation/formation are the key factors for compositional homogeneity. High conductivity (1.5 × 10(-2) S cm(-1)) and H2O2 sensing activity (12 times higher than commercial Co3O4) were achieved due to the homogeneous multiple mixed-valence systems of Co(ii)/(iii) and Mn(iii)/(iv). A wide linear detection range (from 0.1 to 25 mM) with a detection limit of 15 µM was observed. Manganese species assist the formation of large surface area nanostructures, enhancing the H2O2 reduction activities, and inhibit the sensing interference. The material controls of hierarchical nanostructures, elemental compositions, porosity, and electrochemical performances are highly associated with the reaction temperatures. The temperature-dependent properties and nanostructure formation mechanisms based on a reaction rate competition are proposed.

Rectification of ion current in nanopipettes by external substrates.

We describe ion distribution and the current-voltage (i-V) response of nanopipettes at different probe-to-substrate distances (Dps) as simulated by finite-element methods. Results suggest electrostatic interactions between a charged substrate and the nanopipette dominate electrophoretic ion transport through the nanopipette when Dps is within 1 order of magnitude of the Debye length (∼10 nm for a 1 mM solution as employed in the simulation). Ion current rectification (ICR) and permselectivity associated with a neutral or charged nanopipette can be reversibly enhanced or reduced dependent on Dps, charge polarity, and charge density (σ) of the substrate. Regulation of nanopipette current is a consequence of the enrichment or depletion of ions within the nanopipette interior, which influences conductivity of the nanopipette. When the external substrate is less negatively charged than the nanopipette, the substrate first reduces, and then enhances the ICR as Dps decreases. Surprisingly, both experimental and simulated data show that a neutral substrate was also able to reduce and reverse the ICR of a slightly negatively charged nanopipette. Simulated results ascribe such effects to the elimination of ion depletion within the nanopipette at positive potentials.

Paper-based electroanalytical devices with an integrated, stable reference electrode.

This paper describes the development of a referenced Electrochemical Paper-based Analytical Device (rEPAD) comprising a sample zone, a reference zone, and a connecting microfluidic channel that includes a central contact zone. We demonstrated that the rEPADs provide a simple system for direct and accurate voltammetric measurements that are referenced by an electrode with a constant, well-defined potential. The performance of the rEPADs is comparable to commercial electrochemical cells, and the layout can be easily integrated into systems that permit multiplexed analysis and pipette-free sampling. The cost of this portable device is sufficiently low that it could be for single-use, disposable applications, and its method of fabrication is compatible with that used for other paper-based systems.