Steam‐Induced Coarsening of Single‐Unit‐Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis

Commonly used methods to assess crystallinity, micro‐/mesoporosity, Brønsted acid site density and distribution (in micro‐ vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two‐dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro‐ and mesoporosity, and micropore reaction rates.     

Break-Up of Aerosol Agglomerates in Highly Turbulent Gas Flow

Agglomerate aerosols in a turbulent flow may be subjected to very high turbulent shear rates which through the generation of lift and drag can overcome the adhesive forces binding the constituents of an agglomerate together and cause it to break-up. This paper presents an analysis of the experimental measurements of the breakup of agglomerates between 0.1?C10???m in size, in a turbulent pipe flow followed by an expansion zone with a Reynolds numbers in the range 10⁵ to 10⁷. The analysis shows that even in wall bounded turbulence, the high turbulent shear stresses associated with the small scales of turbulence in the core can be the main source of breakup preceding any break-up that may occur by impaction at the wall. More importantly from these results, a computationally fast and efficient solution is obtained for the General Dynamic Equation (GDE) for agglomerate transport and breakup in highly turbulent flow. Furthermore the solution for the evolution of the aerosol size distribution is consistent with the experimental results. In the turbulent pipe flow section, the agglomerates are exposed continuously to turbulent shear stresses and experience more longer term breakup than in the expansion zone (following the pipe flow) where the exposure time is much less and break-up occurs instantaneously under the action of very high local turbulent shear stresses. The validity of certain approximations made in the model is considered. In particular, the inertia of the agglomerates characterised by a Stokes Number from 0.001 for the smallest particles up to 10 for 10???m particles and the fluctuations of the turbulent shear stresses are important physical phenomena which are not accounted for in the model.     

Effects of hydrolysis conditions on the morphology,crystallinity, and thermal stability of cellulose nanocrystals extracted from kenaf bast fibers

Cellulose nanocrystals (CNC) were first isolated from kenaf bast fibers and then characterized. The raw fibers were subjected to alkali treatment and bleaching treatment and subsequent hydrolysis with sulfuric acid. The influence of the reaction time on the morphology, crystallinity, and thermal stability of CNC was investigated. Fourier transform infrared spectroscopy showed that lignin and hemicellulose were almost entirely removed during the alkali and bleaching treatments. The morphology and dimensions of the fibers and acid-released CNC were characterized by field emission scanning electron microscopy and transmission electron microscopy. X-Ray diffraction analysis revealed that the crystallinity first increases upon hydrolysis and then decreases after long durations of hydrolysis. The optimal extraction time was found to be around 40 min during hydrolysis at 45 °C with 65% sulfuric acid. The thermal stability was found to decrease as the hydrolysis time increased. The electrophoretic mobility of the CNC suspensions was measured using the zeta potential, and it ranged from −8.7 to −95.3 mV.     

Pupils,tools and the Zone of Proximal Development

In this article, I use the Vygotskian concept of the Zone of Proximal Development (ZPD) to examine the learning experience of two grade seven pupils as they attempted to solve an addition of fractions problem using fraction strips. The aim is to highlight how tools can facilitate the enactment of a ZPD, within which the tool provides the guidance. Viewing the ZPD as a zone that allows for the emergence of various forms of guided talk and actions, I present a detailed analysis of a short video-recording of the pupils’ participation in a tool-mediated problem-solving activity. I show how their knowing of the concept of fractions and their perceptions of the affordances of the fraction strips marked what they said and did. I conclude by suggesting that the ZPD emerges through participation and interaction, not only between individuals but also between individuals and tools.     

Antigen binding forces of single antilysozyme Fv fragments explored by atomic force microscopy

We used atomic force microscopy (AFM) to explore the antigen binding forces of individual Fv fragments of antilysozyme antibodies (Fv). To detect single molecular recognition events, genetically engineered histidine-tagged Fv fragments were coupled onto AFM tips modified with mixed self-assembled monolayers (SAMs) of nitrilotriacetic acid- and tri(ethylene glycol)-terminated alkanethiols while lysozyme (Lyso) was covalently immobilized onto mixed SAMs of carboxyl- and hydroxyl-terminated alkanethiols. The quality of the functionalization procedure was validated using X-ray photoelectron spectroscopy (surface chemical composition), AFM imaging (surface morphology in aqueous solution), and surface plasmon resonance (SPR, specific binding in aqueous solution). AFM force-distance curves recorded at a loading rate of 5000 pN/s between Fv- and Lyso-modified surfaces yielded a distribution of unbinding forces composed of integer multiples of an elementary force quantum of approximately 50 pN that we attribute to the rupture of a single antibody-antigen pair. Injection of a solution containing free Lyso caused a dramatic reduction of adhesion probability, indicating that the measured 50 pN unbinding forces are due to the specific antibody-antigen interaction. To investigate the dynamics of the interaction, force-distance curves were recorded at various loading rates. Plots of unbinding force vs log(loading rate) revealed two distinct linear regimes with ascending slopes, indicating multiple barriers were present in the energy landscape. The kinetic off-rate constant of dissociation (k(off) approximately = 1 x 10(-3) s(-1)) obtained by extrapolating the data of the low-strength regime to zero force was in the range of the k(off) estimated by SPR.     

微塑料:生物效应、分析和降解方法综述

微塑料(MPs)的出现引起了全球的广泛关注,它们遍布海洋和陆地的各个环境介质中,造成了严重的环境污染。微塑料通常被定义为粒径小于5 mm的塑料纤维、颗粒或者薄膜,可被生物吸收积累,产生生态风险和健康风险。实际上很多微塑料可达微米乃至纳米级别,肉眼是不可见的,因此也被形象地比作海洋中的“PM2.5”。作为目前学术界和社会各界争论的热点问题,本篇综述旨在系统地介绍环境中微塑料的来源与分布、生物效应以及分析鉴定方法,并重点介绍了微塑料污染的降解策略和研究成果,为今后微塑料降解方法的研究提供了参考。     

An exploration of ferrocenyl ureas as enantioselective electrochemical sensors for chiral carboxylate anions

The syntheses of a series of chiral ureas containing the redox-active ferrocene group are described. Each of these bind chiral carboxylates in organic solvents through hydrogen-bonding interactions, as evidenced by spectroscopic and cyclic voltammetry measurements, the latter allowing these guests to be electrochemically sensed in solution. The enantioselectivity in the complexation of the protected amino acid N-benzenesulfonylproline by a ferrocenylbenzyl host is high enough to allow opposite enantiomers to be distinguished by electrochemical means.     

Design of 1D and 2D molecule-based magnets with the ligand 4,5-dimethyl-1,2-phenylenebis(oxamato)

Three new bimetallic oxamato-based magnets with the proligand 4,5-dimethyl-1,2-phenylenebis(oxamato) (dmopba) were synthesized using water or dimethylsulfoxide (DMSO) as solvents. Single crystal X-ray diffraction provided structures for two of them: [MnCu(dmopba)(H(2)O)(3)](n)·4nH(2)O (1) and [MnCu(dmopba)(DMSO)(3)](n)·nDMSO (2). The crystalline structures for both 1 and 2 consist of linearly ordered oxamato-bridged Mn(II)Cu(II) bimetallic chains. The magnetic characterization revealed a typical behaviour of ferrimagnetic chains for 1 and 2. Least-squares fits of the experimental magnetic data performed in the 300-20 K temperature range led to J(MnCu) = -27.9 cm(-1), g(Cu) = 2.09 and g(Mn) = 1.98 for 1 and J(MnCu) = -30.5 cm(-1), g(Cu) = 2.09 and g(Mn) = 2.02 for 2 (H = -J(MnCu)∑S(Mn),(i)(S(Cu,i) + S(Cu),(i-1))). The two-dimensional ferrimagnetic system [Me(4)N](2n){Co(2)[Cu(dmopba)](3)}(n)·4nDMSO·nH(2)O (3) was prepared by reaction of Co(II) ions and an excess of [Cu(dmopba)](2-) in DMSO. The study of the temperature dependence of the magnetic susceptibility as well as the temperature and field dependences of the magnetization revealed a cluster glass-like behaviour for 3.     

Electrocatalytic redox neutral [3 + 2] annulation of N-cyclopropylanilines and alkenes

Although synthetic organic electrochemistry (EC) has advanced significantly, net redox neutral electrosynthesis is quite rare. Two approaches have been employed to achieve this type of electrosynthesis. One relies on turnover of the product by the reactant in a chain mechanism. The other involves both oxidation on the anode and reduction on the cathode in which the radical cation or the radical anion of the product has to migrate between two electrodes. Herein, a home-built electrochemistry/mass spectrometry (EC/MS) platform was used to generate an N-cyclopropylaniline radical cation electrochemically and to monitor its reactivity toward alkenes by mass spectrometry (MS), which led to the discovery of a new redox neutral reaction of intermolecular [3 + 2] annulation of N-cyclopropylanilines and alkenes to provide an aniline-substituted 5-membered carbocycle via direct electrolysis (yield up to 81%). A chain mechanism, involving the regeneration of the substrate radical cation and the formation of the neutral product, is shown to be responsible for promoting such a redox neutral annulation reaction, as supported by experimental evidence of EC/MS.

We report the use of an online electrochemistry/mass spectrometry platform to develop a redox neutral electrosynthesis of 5-membered rings via [3 + 2] annulation of N-cyclopropylanilines and alkenes, without additional oxidant, reductant or catalyst.     

Crystallography,Molecular Modeling,and COX-2 Inhibition Studies on Indolizine Derivatives

The cyclooxygenase-2 (COX-2) enzyme is an important target for drug discovery and development of novel anti-inflammatory agents. Selective COX-2 inhibitors have the advantage of reduced side-effects, which result from COX-1 inhibition that is usually observed with nonselective COX inhibitors. In this study, the design and synthesis of a new series of 7-methoxy indolizines as bioisostere indomethacin analogues (5a–e) were carried out and evaluated for COX-2 enzyme inhibition. All the compounds showed activity in micromolar ranges, and the compound diethyl 3-(4-cyanobenzoyl)-7-methoxyindolizine-1,2-dicarboxylate (5a) emerged as a promising COX-2 inhibitor with an IC₅₀ of 5.84 µM, as compared to indomethacin (IC₅₀ = 6.84 µM). The molecular modeling study of indolizines indicated that hydrophobic interactions were the major contribution to COX-2 inhibition. The title compound diethyl 3-(4-bromobenzoyl)-7-methoxyindolizine-1,2-dicarboxylate (5c) was subjected for single-crystal X-ray studies, Hirshfeld surface analysis, and energy framework calculations. The X-ray diffraction analysis showed that the molecule (5c) crystallizes in the monoclinic crystal system with space group P 2₁/n with a = 12.0497(6)Å, b = 17.8324(10)Å, c = 19.6052(11)Å, α = 90.000°, β = 100.372(1)°, γ = 90.000°, and V = 4143.8(4)ų. In addition, with the help of Crystal Explorer software program using the B3LYP/6-31G(d, p) basis set, the theoretical calculation of the interaction and graphical representation of energy value was measured in the form of the energy framework in terms of coulombic, dispersion, and total energy.