A new phenanthrene-based bis-oxime chemosensor for Fe(III) and Cr(III) discrimination

The synthesis of two new 2,7-disubstituted phenanthrene-based bis oximes is described. The ability of these two compound for complexing heavy metal cations have been studied and complexation constants and complex stoichiometry for Cr³⁺ and Fe³⁺ complex have been determined. The fluorescent properties of ligand 2 make this compound able to act as a sensor able to discriminate between Cr³⁺ and Fe³⁺. Detection limits for these two cations have been evaluated.     

Interfacial energy exchange and reaction dynamics in collisions of gases on model organic surfaces

Molecular beam scattering experiments and molecular dynamics simulations have been combined to develop an atomic-level understanding of energy transfer, accommodation, and reactions during collisions between gases and model organic surfaces. The work highlighted in this progress report has been motivated by the scientific importance of understanding fundamental interfacial chemical reactions and the relevance of reactions on organic surfaces to many areas of environmental chemistry. The experimental investigations have been accomplished by molecular beam scattering from ω-functionalized self-assembled monolayers (SAMs) on gold. Molecular beams provide a source of reactant molecules with precisely characterized collision energy and flux; SAMs afford control over the order, structure, and chemical nature of the surface. The details of molecular motion that affect energy exchange and scattering have been elucidated through classical-trajectory simulations of the experimental data using potential energy surfaces derived from ab initio calculations. Our investigations began by employing rare-gas scattering to explore how alkanethiol chain length and packing density, terminal group relative mass, orientation, and chemical functionality influence energy transfer and accommodation at organic surfaces. Subsequent studies of small molecule scattering dynamics provided insight into the influence of internal energy, molecular orientation, and gas–surface attractive forces in interfacial energy exchange. Building on the understanding of scattering dynamics in non-reactive systems, our work has recently explored the reaction probabilities and mechanisms for O₃ and atomic fluorine in collisions with a variety of functionalized SAM surfaces. Together, this body of work has helped construct a more comprehensive understanding of reaction dynamics at organic surfaces.     

(N,N-Diisopropylcarbamoyloxy)-methyl p-tolyl sulfone: preparation and application for the syntheses of 1,2-diols

1-(N,N-Diisopropylcarbamoyloxy)-1-tosyl-methane (CbOCH₂Ts, Cb=N,N-diisopropylcarbamoyl) was readily prepared from p-TolSH, paraformaldehyde and CbCl. With the dual activation of CbO- and Ts-substitutions, deprotonation of CbOCH₂Ts could be effected not only by n-BuLi, but also by Grignard reagents. Upon deprotonation, the title compound adds to various carbonyl structures. By choosing proper organometallic reagents for consecutive steps, the addition intermediate undergoes in situ conversions to efficiently yield regioselectively O-Cb protected and unprotected 1,2-diols.     

Micellization of anionic gemini surfactants and their interaction with polyacrylamide

A series of anionic gemini surfactants have been synthesized. The surface properties and micellization process of as-prepared sulfonate gemini surfactants (SGS) and carboxylate gemini surfactant (CGS) have been studied by surface tension measurement and isothermal titration microcalorimetry. Meanwhile, the interaction of these five surfactants with polyacrylamide (PAM) was investigated using surface tension, steady-state fluorescence measurement, and isothermal titration microcalorimetry. The results show that the critical micelle concentrations (CMCs) of above-mentioned surfactants are more than 1 order of magnitude lower than those of corresponding single chain surfactants. Moreover, the enthalpy of micelle formation (ΔH _mic) for the investigated gemini surfactants is negative. In the surfactant–PAM systems, the thermodynamic parameters of binding have also been determined. The conclusion may be drawn that the binding strength of SGS onto PAM is stronger than that of CGS, resulting from more compact structure of SGS aggregates. With increasing surfactant hydrophobicity, the values of ΔH _agg become more exothermic and a ΔS _agg decrease was observed. Therefore, the interaction between SGS and PAM is enthalpy-driven.     

Comparing study on hydration properties of various cementitious systems

The hydration properties of slag sulfate cement (SSC), slag Portland cement (PSC), and ordinary Portland cement (POC) were compared in this study by determining the compressive strength of pastes, the hydration heat of binders within 72 h, the pore structure, the hydration products, and the hydration degree. The results indicated that main hydration products of PSC paste and POC paste are calcium hydroxide and C–S–H gel, while those of SSC paste are ettringite and C–S–H gel from the analyses of XRD, TG–DTA, and SEM. At the early curing age, the compressive strength depends on the clinker content in the cementitious system, while at the late curing age, which is related to the potential reactivity of slag. From hydration heat analysis, the cumulative hydration heat of PSC is lower than that of POC, but higher than that of SSC. Slag can limit chemical reaction and the delayed coagulation of gypsum, which also plays a role in the early hydration. So SSC shows the lowest heat release and slag can’t be simulated without a suitable alkaline solution. Based on MIP analysis, the porosity of POC paste is the smallest while the average pore size is the biggest. At the age of 90 days, the compressive strength of SSC can get higher development because of its relative smaller pore size than that of PSC and POC paste.     

Morphology and Growth Process of Bat-like ZnO Crystals by Thermal Evaporation

A novel bat-like ZnO nanostructure was synthesized on the silicon substrate by simple ther-mal evaporation of zinc powders without any catalyst. Each bat-like nanorod ("nanobat") is composed of a hexagonal head, a continuous neck and a thin handle. High-resolution transmission electron microscopy and selected area electron di raction results reveal the single-crystalline feature and the growing direction along [0001] of the nanobat. The vapor-solid mechanism was found suitable to explain the growth process of the nanobat and a schematic model was proposed in detail based on the experimental results.     

Highly Efficient Far Red/Near‐Infrared Solid Fluorophores: Aggregation‐Induced Emission,Intramolecular Charge Transfer,Twisted Molecular Conformation,and Bioimaging Applications

The development of organic fluorophores with efficient solid‐state emissions or aggregated‐state emissions in the red to near‐infrared region is still challenging. Reported herein are fluorophores having aggregation‐induced emission ranging from the orange to far red/near‐infrared (FR/NIR) region. The bioimaging performance of the designed fluorophore is shown to have potential as FR/NIR fluorescent probes for biological applications.     

Palladium‐Catalyzed Intermolecular Acylation of Aryl Diazoesters with ortho‐Bromobenzaldehydes

In this work, we describe a palladium‐catalyzed intermolecular O acylation of α‐diazoesters with ortho‐bromobenzaldehydes. The C(sp²)?H bond activation of the aldehyde is enabled by migratory insertion of a palladium carbene intermediate. The diazoesters act as modular three‐atom units to build up key seven‐membered palladacycles, which are transformed into a variety of isocoumarin derivatives upon reductive elimination. Mechanistic experiments and DFT calculations provide insight into the reaction pathway.     

A Microporous Covalent–Organic Framework with Abundant Accessible Carbonyl Groups for Lithium‐Ion Batteries

A key challenge faced by organic electrodes is how to promote the redox reactions of functional groups to achieve high specific capacity and rate performance. Here, we report a two‐dimensional (2D) microporous covalent–organic framework (COF), poly(imide‐benzoquinone), via in situ polymerization on graphene (PIBN‐G) to function as a cathode material for lithium‐ion batteries (LIBs). Such a structure favors charge transfer from graphene to PIBN and full access of both electrons and Li⁺ ions to the abundant redox‐active carbonyl groups, which are essential for battery reactions. This enables large reversible specific capacities of 271.0 and 193.1 mAh g^?1 at 0.1 and 10 C, respectively, and retention of more than 86 % after 300 cycles. The discharging/charging process successively involves 8 Li⁺ and 2 Li⁺ in the carbonyl groups of the respective imide and quinone groups. The structural merits of PIBN‐G will trigger more investigations into the designable and versatile COFs for electrochemistry.