4.8 nm Concave {M_(72)}(M=Co,Ni,Fe) metal-organic polyhedra capped by 18 calixarenes

Three 4.8 nm isostructural{M₇₂}(M=Co^Ⅱ for CIAC-128,Ni^Ⅱ for CIAC-129,Fe^Ⅱ for CIAC-130) metal-organic polyhedra(MOPs) are constructed by eighteen M₄-p-tert-butylthiacalix[4]arene (M₄-TC4A) units bridged via sixteen four-connected 5,5′-(1H-1,2,4-triazole-3,5-diyl) diisophthalic acid (H₄TADIPA) linkers.These MOPs are featured with a rarely reported concave coordination cage,which can be simplified as a squeezed double-decker hexagonal prism pressed from the top and bottom hexagonal faces.Furthermore,CIAC-128,CIAC-129 and CIAC-130 are the highest nuclearity discrete clusters of Co,Ni and Fe reported so far.CIAC-128 has higher separation selectivity of C₃H₈ than CH₄ under ambient conditions,and also exhibits separation selectivity for C₂H₆/CH₄,C₂H₂/CH₄,and C₂H₄/CH₄.In addition,CIAC-128 can provide the cavity for the confined synthesis of noble metal nanoclusters such as Pd nanoclusters and the resulting Pd@CIAC-128 hybrids show higher electrocatalytic activity than commercial Pt/C towards hydrogen evolution reaction (HER).     

Magnetron sputtering deposition of silicon nitride on polyimide separator for high-temperature lithium-ion batteries

To date,lithium-ion batteries are becoming increasingly significant in the application of portable devices and electrical vehicles,and revolutionary progress in theoretical research and industrial application has been achieved.However,the commercial polyolefin separators with unsatisfying electrolytes affinity and poor thermal stability have extremely restricted the further application of lithium-ion batteries,especially in the high-temperature fields.In this work,magnetron sputtering deposition technique is employed to modify the commercial polyimide separator by coating silicon nitride on both sides.Magnetron sputtering deposition modified polyimide(MSD-PI)composite separator shows high thermal stability and ionic conductivity.More importantly,compared with the cells using Celgard separator,the cells with MSD-PI separator exhibit superior electrochemical performance,especially long-term cycle performance under high temperature environment,owing to the high thermal conductivity of surface Si3 N4 particles.Hence,lithium-ion batteries with MSD-PI separator are capable of improving thermal safety and capacity retention,which demonstrates that magnetron sputtering deposition technique could be regarded as a promising strategy to develop advanced organic/inorganic composite separators for high-temperature lithium-ion batteries.     

Application of QPLEXTM biomarkers in cognitively normal individuals across a broad age range and diverse regions with cerebral amyloid deposition

The deposition of beta-amyloid (Aβ) in the brain precedes the onset of symptoms such as cognitive impairment in Alzheimer’s disease (AD); therefore, the early detection of Aβ accumulation is crucial. We previously reported the applicability of the QPLEX^TM Alz plus assay kit for the prescreening of Aβ accumulation. Here, we tested the specific application of the kit in a large cohort of cognitively normal (CN) individuals of varying ages for the early detection of Aβ accumulation. We included a total of 221 CN participants with or without brain Aβ. The QPLEX^TM biomarkers were characterized based on age groups (1^st–3^rd tertile) and across various brain regions with cerebral amyloid deposition. The 3^rd tertile group (>65 years) was found to be the most suitable age group for the application of our assay kit. Receiver operating characteristic curve analysis showed that the area under the curve (AUC, discrimination power) was 0.878 with 69.7% sensitivity and 98.4% specificity in the 3^rd tertile group. Additionally, specific correlations between biomarkers and cerebral amyloid deposition in four different brain regions revealed an overall correlation with general amyloid deposition, consistent with previous findings. Furthermore, the combinational panel with plasma Aβ1–42 levels maximized the discrimination efficiency and achieved an AUC of 0.921 with 95.7% sensitivity and 67.3% specificity. Thus, we suggest that the QPLEX^TM Alz plus assay is useful for prescreening brain Aβ levels in CN individuals, especially those aged >65 years, to prevent disease progression via the early detection of disease initiation.Subject terms: Alzheimer''s disease, Neural ageing, ELISA     

Two-dimensional tellurium saturable absorber for ultrafast solid-state laser

Two-dimensional(2 D) Te nanosheets were successfully fabricated through the liquid-phase exfoliation(LPE) method. The nonlinear optical properties of 2 D Te nanosheets were studied by the open-aperture Z-scan technique. Furthermore, the continuous wave mode-locked Nd:YVO_4 laser was successfully realized by using 2 D Te as a saturable absorber(SA) for the first time, to the best of our knowledge. Ultrashort pulses as short as 5.8 ps were obtained at 1064.3 nm with an output power of 851 m W. This primary investigation indicates that the 2 D Te SA is a promising photonic device in the fields of ultrafast solid-state lasers.     

Highly effective and chemoselective hydrodeoxygenation of aromatic alcohols

Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (e.g., saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon–nitrogen hybrid material-supported Co catalysts. The C–OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C–N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.

Porous carbon–nitrogen hybrid material-supported Co catalysts can effectively promote the chemoselective hydrodeoxygenation reaction of a various of aromatic alcohols in ethanol and hydrogen atmosphere, under relatively mild conditions.     

反应条件对钌基氨合成催化剂性能的影响

用氨合成催化剂性能评价装置,研究了反应温度、压力、空速和氢氮比对以活性炭为载体的钌基氨合成催化剂活性的影响。研究表明,低于400℃时,随着反应温度降低,催化剂的活性急剧降低。随着压力升高,催化剂活性增大。但钌催化剂具有较高的低压活性,适宜低压合成氨。随着空速的降低,催化剂的活性明显提高。在空速和压力一定的条件下,最佳氢氮比随反应温度而异,并且当空速较高或反应温度较低时,氢氮比的变化对催化剂活性的影响更加明显。     

Stereocontrolled enantioselective addition of diethylzinc to aldehydes using new chiral aminoalcohols

The new chiral β-aminoalcohols of indolinylmethanols ( 1 ) and their reduced derivatives ( 2 ) were synthesized from (S)-indoline-2-carboxylic acid. Both (R) and (S) enantiomers of the optically active secondary alcohols have been successfully obtained in high enantiomeric excess from the stereoselective addition of diethylzinc to the aldehydes catalyzed by the chiral aminoalcohols ( 1 and 2 ). The sense of the asymmetric induction and the degrees of enantioselectivities turned out to be highly dependent on the structure of the catalysts: The presence of the catalyst 1 afforded the (S)-configuration of the corresponding alcohols; on the other hand, the presence of 2 afforded the (R)-configuration of the alcohols in high enantiomeric selectivity.     

Structural Entropy of the Stochastic Block Models

With the rapid expansion of graphs and networks and the growing magnitude of data from all areas of science, effective treatment and compression schemes of context-dependent data is extremely desirable. A particularly interesting direction is to compress the data while keeping the “structural information” only and ignoring the concrete labelings. Under this direction, Choi and Szpankowski introduced the structures (unlabeled graphs) which allowed them to compute the structural entropy of the Erdős–Rényi random graph model. Moreover, they also provided an asymptotically optimal compression algorithm that (asymptotically) achieves this entropy limit and runs in expectation in linear time. In this paper, we consider the stochastic block models with an arbitrary number of parts. Indeed, we define a partitioned structural entropy for stochastic block models, which generalizes the structural entropy for unlabeled graphs and encodes the partition information as well. We then compute the partitioned structural entropy of the stochastic block models, and provide a compression scheme that asymptotically achieves this entropy limit.     

Complexation of poly(vinyl alcohol)–congo red aqueous solutions. 3. Dynamic light scattering study

Mesoscopic structures of poly(vinyl alcohol)(SINGLEBOND)Congo red (PVA(SINGLEBOND) CR) complexes in aqueous solutions were investigated in terms of dynamic light scattering (DLS) technique. The intensity-intensity time correlation function, g⁽²⁾(t), was analyzed with an equation including a single and a stretched exponential function. Two diffusion coefficients, D_f (fast) and D_s (slow) were evaluated. D_f was converted to the apparent correlation length, ξ_app, via the mode-mode coupling hypothesis. The estimated ξ_app was insensitive to the sol(SINGLEBOND)to(SINGLEBOND)gel transition but decreased with CR concentration. This change may be related to the electrostatic screening effect. On the other hand, D_s oscillates with increasing CR concentration at a specific PVA concentration range. This explains well the reentrant sol(SINGLEBOND)gel(SINGLEBOND)sol(SINGLEBOND)gel transition behavior observed in the PVA(SINGLEBOND)CR systems. D_s seems to represent the mobility of the PVA(SINGLEBOND)CR complexes, which annihilates at the gel point. © 1996 John Wiley & Sons, Inc.     

Catalytic hydrogenation of aromatic nitro compounds by non-noble metal complexes of chitosan

Silica-supported mono-metal (such as Ni, Cu) complexes and mixed metal (such as Cu/Zn, Cu/Cr) complexes of chitosan have been prepared. It is found that these non-noble metal complexes could be used as efficient catalysts for the hydrogenation of aromatic nitro compounds. The effects of type of metal, reaction temperature and pressure, solvent, nitrogen/metal molar ratio in the complex catalysts on the yields from nitrobenzene to aniline have been examined. It was also found that catalysts are active for the catalytic hydrogenation of other aromatic nitro compounds such as 2-nitroanisole, 2-nitroaniline, 2-nitrotoluene and 1-chloro-4-nitrobenzene.