A novel silane coupling agent with peroxy groups used as an initiator in the graft polymerization of AN or MMA on nano-TiO<Subscript>2</Subscript>

A novel peroxy group-containing silane coupling agent was synthesized and anchored on the surface of titanium dioxide nanoparticles (nano-TiO₂) to form an immobilized-initiator-modified nano-TiO₂ species. In this study, the kinetic parameters of the peroxy group-containing silane were tested and assessed using DSC. The pre-exponential factor (A_d) was 8.973?×?10⁸ and the activation energy (E_a) was 80.736 kJ mol^?1. Moreover, the empirical Arrhenius equation was determined to be ln K_d?=???80.736/RT?+?ln(8.973?×?10⁸). To obtain continuous polymers, acrylonitrile (AN) and methyl methacrylate (MMA) were polymerized using the novel peroxy group-containing silane and FeSO₄ as an initiator system. The number average molecular weights (M_n of PAN?=?3×10⁴ and M_n of PMMA?=?1.4?×?10⁵) and polydispersity indexes (PDI of PAN?=?2.76 and PDI of PMMA?=?1.65) were determined by GPC. It was suggested that the redox initiation system can generate highly reactive species on the surfaces of inorganic nanoparticles. The nano-TiO₂-grafted polymers were successfully obtained.     

Heterogeneous liquid phase oxidation of ethylbenzene to acetophenone with graphene carbon-based catalyst

The series of graphene materials and N-doped graphene materials were successfully synthesized and improved by high-temperature treatment with trace iron oxide. XRD, Raman, FT-IR, TEM and XPS were employed for these catalysts. The catalytic performance of these catalysts was investigated in the selective oxidation of ethylbenzene with tert-butyl hydroperoxide as oxidant. The impacts of temperature, mass of catalysts, reaction time and oxidants on the selective oxidation of ethylbenzene were also investigated. The N-doped graphene materials exhibit greatly remarkable catalytic performance than others. The conversion of ethylbenzene is more than 90% and the selectivity of acetophenone is more than 95% at 353 K. Graphene can be used as catalyst owing to its unique structures and chemical properties. The characterization tests show that the doping of N atoms can create more defects and more active sites in the N-doped graphene materials which could greatly improve the catalytic performance. Furthermore, such cost-effective graphene-based catalysts possess good stability and could be reused at least five times without remarkable loss of the catalytic activity.     

Prediction of the solvation and structural properties of ionic liquids in water by two-dimensional correlation spectroscopy

Two-dimensional vibrational spectroscopy is applied to investigate the dilution process of 1-ethyl-3-methyl-imidazolium tetrafluoroborate ([Emim][BF4]) in water. With increasing water content in ionic liquid (IL)/water mixtures, the C-H stretching vibration of the imidazolium cation showed systematic blue-shifts, which reflect the weakening of the cohesion between the cation and anion of ILs. The two-dimensional IR results reveal that the ILs sense quite different environments during the whole dilution process. First, the three-dimensional network structure of pure ILs was destroyed gradually into ionic clusters, then the clusters were further dissociated into ionic pairs surrounded by water molecules, and finally the latter became the dominant form in bulk water. Within the concentration range we investigated (0.02相似文献   

In vivo Degradation and histocompatibility of a novel class of fluorescent copolyanhydrides, poly{[di(p-carboxyphenyl) succinate]-co-(sebacic anhydride)}

In this work, the in vivo degradation and tissue compatibility of a novel class of inherently fluorescent copolyanhydrides, P(dCPS:SA), were investigated. It was found that the degradation of the copolyanhydrides increased with the increase of SA content in the copolymers. The in vivo degradation rate of the copolymers was slower than that studied in vitro. A surface erosion characteristic of the copolyanhydrides was revealed by SEM and fluorescent microscopy. Mild inflammatory reactions were observed on days 6 and 10 after implantation for all the studied copolymers. By the end of 30 d, there were almost no inflammation reactions taking place.     

The SC property of an expected residual function arising from stochastic complementarity problems

The stochastic nonlinear complementarity problem has been recently reformulated as an expected residual minimization problem which minimizes an expected residual function defined by an NCP function. In this work, we show that the expected residual function defined by the Fischer–Burmeister function is an function.     

Reversible Solid–Solid Conversion of Sulfurized Polyacrylonitrile Cathodes in Lithium–Sulfur Batteries by Weakly Solvating Ether Electrolytes

Despite carbonate electrolytes exhibiting good stability to sulfurized polyacrylonitrile (SPAN), their chemical incompatibility with lithium (Li) metal anode leads to poor electrochemical performance of Li||SPAN full cells. While the SPAN employs conventional ether electrolytes that suffer from the shuttle effect, leading to rapid capacity fading. Here, we tailor a dilute electrolyte based on a low solvating power ether solvent that is both compatible with SPAN and Li metal. Unlike conventional ether electrolytes, the weakly solvating ether electrolyte enables SPAN to undergo reversibly “solid–solid” conversion. It features an anion–rich solvation structure that allows for the formation of a robust cathode electrolyte interphase on the SPAN, effectively blocking the dissolution of polysulfides into the bulk electrolyte and avoiding the shuttle effect. What's more, the unique electrolyte chemistry endowed Li ions with fast electroplating kinetics and induced high reversibility Li deposition/stripping process from 25 °C to −40 °C. Based on tailored electrolyte, Li||SPAN full cells matched with high loading SPAN cathodes (≈3.6 mAh cm⁻²) and 50 μm Li foil can operate stably over a wide range of temperatures. Additionally, Li||SPAN pouch cell under lean electrolyte and 5 % excess Li conditions can continuously operate stably for over a month.     

High-performance liquid chromatography micro-fraction bioactive evaluation combined with countercurrent chromatographic separation of antioxidants from Citrus peel and their tyrosinase inhibition activities

In the present study, high-performance liquid chromatography micro-fraction bioactive evaluation and high speed countercurrent chromatography were performed on screening, identification and isolation of antioxidants from Citrus peel. Three compounds were screened as antioxidants and tyrosinase inhibitors using 2,2′-azino-bis (3-ethyl-benzothiazoline-6-sulfonic acid) radical cation scavenging assay and tyrosinase activity test, then they were identified as eriocitrin, narirutin and hesperidin. Moreover, the solvent system ethyl acetate-n-butanol-water (6:4:10, v/v/v) was used for separation of ethyl acetate extract of Citrus peel by high speed countercurrent chromatography. In total, 0.45 mg of eriocitrin with 87.10% purity, 2.04 mg of narirutin with 95.19% purity and 1.35 mg of hesperidin with 95.19% purity were obtained from 20 mg of ethyl acetate extract of Citrus peel in a single run and then each component was subjected to 2,2′-azino-bis (3-ethyl-benzothiazoline-6-sulfonic acid) radical cation scavenging assay and tyrosinase inhibition assay. Eriocitrin showed great antioxidant activity (the half-maximum concentration: 3.65 µM) and tyrosinase inhibition activity (the half-maximum concentration: 115.67 µM), while narirutin and hesperidin exhibited moderate activity. Tyrosinase inhibition activity for eriocitrin in vitro was reported for the first time. Furthermore, molecular docking between eriocitrin and mushroom tyrosinase was also studied.     

Matrix solid-phase dispersion combined with micro-fractionation bioactivity evaluation screening polymethoxylated flavones from Citrus peels

Polymethoxyflavones were a unique class of natural and safe flavonoids containing two or more methoxy groups, which were also the most abundant edible part in Citrus peel. The optimum condition in the process of selective extraction of polymethoxylated flavones from Citrus peel by matrix solid-phase dispersion (MSPD) was as follows: SBA-15 as adsorbent, ethyl acetate as eluent, the mass ratio of adsorbent to sample 1:1, and the mixture of sample and adsorbent was ground for 3 min. Twelve antioxidants were successfully screened by micro-fractionation bioactivity evaluation assay, in which four of them were flavonoid glycosides, seven of them were polymethoxylated flavones, and one was phenylpropanoid. 1-sinapoly-β-D-glucopyranoside (1) was reported for the first time in Citrus peel. And antioxidant capacity of 1-sinapoly-β-D-glucopyranoside, 5, 7, 8, 3′, 4′, 5′-hexamethoxyflavone (6), hexamethoxyflavone (11), and 5, 6, 7, 4′-tetramethoxyflavone (7) were reported for the first time. Nobiletin (compound 8), 3, 5, 6, 7, 8, 3′, 4′-heptamethoxyflavone (9) and tangeretin (10) were isolated and purified by countercurrent chromatography combined with preparative liquid chromatography. Antioxidant activity evaluation indicated that the three isolated polymethoxylated flavones owned similar antioxidant activity. This study indicated that MSPD combined with micro-fractionation bioactive evaluation was efficient in screening bioactive compounds for rapid extraction and effective pinpointing bioactive substances in natural products.     

Electrospun Fibrous Membranes of Modified Polystyrene and its Copolymer With Butyl Acrylate and Their Respective Adsorption Capabilities for Cationic Blue and Copper Ions

Cationic dyes and metal ions in wastewater are considered as environmental pollutants. In order to treat these pollutants individually polystyrene (PS) and poly (styrene-co-butyl acrylate) (P(St-co-BA)) were first electrospun into fibrous membranes with a porous structure and then two simple modification methods were adopted to introduce -SO₃H and -COO^? groups into the PS fibrous membranes' and the P(St-co-BA) fibrous membranes' surfaces, respectively; finally the modified samples were used individually to adsorb either cationic blue dyes or copper ions, respectively. The results showed that the PS fibrous membranes were hydrophobic before modification but they became hydrophilic after modification due to the introduction of -SO₃H. Then the modified PS fibrous membranes had the capability to adsorb cationic blue dyes from water, and their adsorption efficiency, with an adsorption time of 300 min, reached 68.1%. For the P(St-co-BA) fibrous membranes, the -COO^? groups were introduced into their surfaces after hydrolysis in alkali lye; however, they showed very weak adsorption capability for copper ions due to the loss of the fiber-web structure. In addition, the thermal properties of the fibrous membranes before and after modification were analyzed, and the morphology was also observed by field emission scanning electron microscopy.     

Sum of divisors of a quaternary quadratic form with almost equal variables

In this paper, we obtain an asymptotic formula of the sum

$$\begin{aligned} \sum _{|m_i-x|\le x^{\theta }}d\big (m_1^2+m_2^2+m_3^2+m_4^2\big ) \quad (i=1,2,3,4) \end{aligned}$$

with \(\theta =\frac{1}{3}+\epsilon \). Moreover, if \(\theta =\frac{4}{5}+\epsilon \), we obtain a more refined asymptotic formula of this sum.