Bimetallic Covalent Organic Frameworks for Constructing Multifunctional Electrocatalyst

Covalent organic frameworks (COFs) are a new class of crystalline porous polymers comprised mainly of carbon atoms, and are versatile for the integration of heteroatoms such as B, O, and N into the skeletons. The designable structure and abundant composition render COFs useful as precursors for heteroatom-doped porous carbons for energy storage and conversion. Herein, we describe a multifunctional electrochemical catalyst obtained through pyrolysis of a bimetallic COF. The catalyst possesses hierarchical pores and abundant iron and cobalt nanoparticles embedded with standing carbon layers. By integrating these features, the catalyst exhibits excellent electrochemical catalytic activity in the oxygen reduction reaction (ORR), with a 50 mV positive half-wave potential, a higher limited diffusion current density, and a much smaller Tafel slope than a Pt-C catalyst. Moreover, the catalyst displays superior electrochemical performance toward the hydrogen evolution reaction (HER), with overpotentials of −0.26 V and −0.33 V in acidic and alkaline aqueous solution, respectively, at a current density of 10 mA cm⁻². The overpotential in the catalysis of the oxygen evolution reaction (OER) was 1.59 V at the same current density.     

Change of evaporation rate of single monocomponent droplet with temperature using time-resolved phase rainbow refractometry

Droplet evaporation characterization, although of great significance, is still challenging. The recently developed phase rainbow refractometry (PRR) is proposed as an approach to measuring the droplet temperature, size as well as evaporation rate simultaneously, and is applied to a single flowing n-heptane droplet produced by a droplet-on-demand generator. The changes of droplet temperature and evaporation rate after a transient spark heating are reflected in the time-resolved PRR image. Results show that droplet evaporation rate increases with temperature, from ?1.28$\times {10}^{?8}$ m²/s at atmospheric 293 K to a range of (?1.5, ?8)$\times {10}^{?8}$ m²/s when heated to (294, 315) K, agreeing well with the Maxwell and Stefan–Fuchs model predictions. Uncertainty analysis suggests that the main source is the indeterminate gradient inside droplet, resulting in an underestimation of droplet temperature and evaporation rate. With the demonstration on simultaneous measurements of droplet refractive index as well as droplet transient and local evaporation rate in this work, PRR is a promising tool to investigate single droplet evaporation in real engine conditions.     

Measured and Predicted Solubility Phase Diagrams of Quaternary Systems LiBr-NaBr-MgBr2-H2O and LiBr-KBr-MgBr2-H2O at 298.15 K

The stable phase equilibria of quaternary systems LiBr-NaBr-MgBr₂-H₂O and LiBr-KBr-MgBr₂-H₂O at 298.15 K were studied by both experimental measurement(isothermal solution saturation method) and theoretical prediction(Pitzer model). The solubilities of the saturated solution have been determined experimentally and two stable phase diagrams and relevant water diagrams of the two quaternary systems were obtained. Results show that quaternary system LiBr-NaBr-MgBr₂-H₂O is hydrate II type as NaBr and NaBr·2H₂O coexistence. Its phase diagram consists of only one invariant point, four univariant curves, and five crystallization fields. The quaternary system LiBr-KBr-MgBr₂-H₂O is a complex type as the double salt KBr·MgBr₂·6H₂O formed. In addition to this double salt, the three single salts LiBr·2H₂O, KBr and MgBr₂·6H₂O also crystallize. In this paper, the solubilities of phase equilibria in above quaternary systems were also calculated by the Pitzer's electrolyte solution model. All the needed parameters can be obtained from the literature or be fitted by experimental data. On the Basis of the experimental and calculated results, the phase diagram of the quaternary system was plotted for comparison. It shows that the calculation results are consistent with the experimental ones.     

Scattering of a Gaussian beam by an anisotropically coated circular cylinder

A solution to the problem of Gaussian beam scattering by an anisotropically coated circular cylinder is presented. The incident Gaussian beam source is expanded as an approximate expression in the simple form with a Tayor’s series. The transmitted field in the anisotropically coated region is expressed as a infinite summation of eigen plane waves with different polar angles. The unknown coefficients of the scattered fields are obtained with the aid of the boundary conditions. The infinite series can be truncated under the prerequisite of achieving the solution convergence. Only the case of transverse-electric polarization is discussed. The similar formulation of transverse-magnetic polarization can be obtained by adopting the similar method. Some numerical results are presented and discussed. The result is in agreement with that available as expected when the Gaussian beam degenerates to a plane wave incidence case.     

Comparative absorption kinetics of seven active ingredients of Eucommia ulmoides extracts by intestinal in situ circulatory perfusion in normal and spontaneous hypertensive rats

Eucommia ulmoides Oliv. (E. ulmoides) is a valuable and nourishing medicinal herb in China that has been used in the treatment of hypertension. Given the fact that most traditional Chinese medicine is mainly used to treat disease, investigating the pharmacokinetics of traditional Chinese medicines in the pathological state is more useful than that in the normal state. However, the differences in the absorption kinetics of active ingredients of E. ulmoides extract between pathological and physiological conditions have not been reported. Therefore, in this study, the rat intestinal in situ circulatory perfusion model was used to investigate the differences in absorption kinetics of seven active ingredients of E. ulmoides extract in normal and spontaneously hypertensive rats, namely, genipinic acid, protocatechuic acid, neochlorogenic acid, chlorogenic acid, cryptochlorogenic acid, (+)-pinoresinol di-O-β-D -glucopyranoside and (+)-pinoresinol 4′-O-β-D -glucopyranoside. Our results indicate that the pathological state of spontaneous hypertension may change the absorption of active components of E. ulmoides extracts, and these findings may provide a reference for improving the rational use of E. ulmoides in the clinic.     

Development of an LC‐MS/MS method for determining the pharmacokinetics of clonidine following oral administration of Zhenju antihypertensive compound

Zhenju antihypertensive compound (ZJAHC) is a combined Chinese–Western medicine formula including clonidine (CLO), hydrochlorothiazide (HCT), rutin, Chrysanthemum indicum extract and pearl powder. Compared with CLO preparations, ZJAHC shows improved activities and decreased adverse effects. It is believed that the side effects of CLO are caused by its high peak plasma concentration. Hence, study of the influence of ZJAHC on the pharmacokinetic behaviors of clonidine seems essential. In present study, the plasma concentrations of CLO were determined with a liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method. The MS/MS transitions monitored for clonidine and internal standard were 230.2 → 213.1 and 152.2 → 110.2, respectively. The analyte was quantified in a single run within 3 min. The pharmacokinetic study showed that the area under the plasma concentration–time curve of CLO in ZJAHC (60 µg/kg CLO) was similar to that of CLO‐HCT‐high (120 µg/kg CLO) but the peak concentration was much lower than that in CLO‐HCT‐high. ZJAHC could enhance the bioavailability without greatly increasing peak concentration of clonidine. This comprehensive effect of enhancing the bioavailability and avoiding the high peak plasma concentration for CLO might mainly result from the co‐contribution of Western medicine and traditional Chinese medicine (TCM), while the effect of TCM was stronger than that of Western medicine. Copyright © 2014 John Wiley & Sons, Ltd.     

The Berry–Esseen bounds of the weighted estimator in a nonparametric regression model

Consider the following nonparametric model: \(Y_{ni}=g(x_{ni})+ \varepsilon _{ni},1\le i\le n,\) where \(x_{ni}\in {\mathbb {A}}\) are the nonrandom design points and \({\mathbb {A}}\) is a compact set of \({\mathbb {R}}^{m}\) for some \(m\ge 1\), \(g(\cdot )\) is a real valued function defined on \({\mathbb {A}}\), and \(\varepsilon _{n1},\ldots ,\varepsilon _{nn}\) are \(\rho ^{-}\)-mixing random errors with zero mean and finite variance. We obtain the Berry–Esseen bounds of the weighted estimator of \(g(\cdot )\). The rate can achieve nearly \(O(n^{-1/4})\) when the moment condition is appropriate. Moreover, we carry out some simulations to verify the validity of our results.

     

Unlocking the Drug Potential of the Bryostatin Family: Recent Advances in Product Synthesis and Biomedical Applications

Bryostatins are a class of naturally occurring macrocyclic lactones with a unique fast developing portfolio of clinical applications, including treatment of AIDS, Alzheimer's disease, and cancer. This comprehensive account summarizes the recent progress (2014–present) in the development of bryostatins, including their total synthesis and biomedical applications. An emphasis is placed on the discussion of bryostatin 1 , the most-studied analogue to date. This review highlights the synthetic and biological challenges of bryostatins and provides an outlook on their future development.     

Water-induced formation of an alkali-ion dimer in cryptomelane nanorods

Tunneled metal oxides such as α-Mn₈O₁₆ (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K⁺ ions (which act as structure-stabilizing dopants) and H₂O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K⁺-doped α-Mn₈O₁₆ (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H₂O displaces K⁺ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K²⁺ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li⁺/Na⁺ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.

Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K²⁺) in the tunnels of hollandite.     

Existence of the uniformly minimum risk equivariant estimators of parameters in a class of normal linear models

In this paper, we study the existence of the uniformly minimum risk equivariant (UMRE) estimators of parameters in a class of normal linear models, which include the normal variance components model, the growth curve model, the extended growth curve model, and the seemingly unrelated regression equations model, and so on. The necessary and sufficient conditions are given for the existence of UMRE estimators of the estimable linear functions of regression coefficients, the covariance matrixV and (trV)^α, where α > 0 is known, in the models under an affine group of transformations for quadratic losses and matrix losses, respectively. Under the (extended) growth curve model and the seemingly unrelated regression equations model, the conclusions given in literature for estimating regression coefficients can be derived by applying the general results in this paper, and the sufficient conditions for non-existence of UMRE estimators ofV and tr(V) are expanded to be necessary and sufficient conditions. In addition, the necessary and sufficient conditions that there exist UMRE estimators of parameters in the variance components model are obtained for the first time.