Design and build an elastic crosslinked network to strengthen and toughen soybean-meal based bioadhesive using organo-sepiolite and greener crosslinker triglycidylamine

Poor water resistance and curing layer brittleness are significant challenges of greener soybean meal (SM) adhesive promotion and application. In this study an elastic network was built to crosslink the SM adhesive and improve the cured layer toughness of the resultant adhesive. Long-chain organo-sepiolite (OSEP) was first prepared by compound modification using KH-560 and KH-602 silane coupling agents. Triglycidylamine (TGA), a greener crosslinking agent with a large number of effective epoxy functional groups, was then synthesized. SM-based adhesives were fabricated using SM, OSEP and TGA. Results indicated that an elastic network was fabricated by the cross-linked reaction of SM, OSEP, and TGA. The elastic network effectively improved the toughness of the resultant adhesive. The wet shear strength of the plywood (PlyW) bonded by SM with 1% OSEP (SM/TGA/OSEP-1 adhesive) increased by 60% to 1.25 MPa relative to that of the SM/TGA adhesive. This study provided a greener, simple and cheap method improving the toughness and wet shear strength of SM-based adhesive, which contributes to the industrialized application of the product.     

Facile amidation of esters with aromatic amines promoted by lanthanide tris (amide) complexes

The development of catalysts capable of catalyzing amidation of esters with amines to construct amides under mild conditions is of great importance. Compared to aliphatic amines, the direct catalytic amidation of esters with less nucleophilic aromatic amines is rather difficult. Employing simple lanthanide tris (amide) complexes Ln[N (SiMe₃)₂]₃(μ-Cl)Li (THF)₃ as the catalysts, it was found a broad range of aromatic amines and esters were efficiently converted into various amides in good yields under mild conditions. A plausible mechanism for this transformation was experimentally supported as starting from an amide exchange reaction between the lanthanide tris (amide) complex and the substrate amine.     

Stereoselectivity and nonmigratory insertion mechanism of dimethylacetylene dicarboxylate into metallocene-hydride of Cp2M(L)H [Cp = η5-C5H5; M = Nb,V; L = CO,P (OMe)3]: A DFT study

The insertion of an alkyne into transition metal–hydrogen bonds is a key elementary step in catalytic polymerization and hydrogenation processes. It was found that a (Z)- or (E)-type alkyenyl complex can be formed through trans/cis stereospecific processes. In this work, the reaction mechanism of Cp₂M(L)H [Cp = η⁵-C₅H₅; M = Nb, V; L = CO, P (OMe)₃] with dimethylacetylene dicarboxylate (DMAD), and the factors influencing the stereoselectivity have been investigated based on density functional theory calculations. The calculated results show that all of the reactions are exothermic. For L = CO, the Z-isomer product forms first even at low temperatures because of the low Gibbs free energy barrier (ΔG^#). Then the Z-pro converts to E-pro , while for L = P (OMe)₃, the exclusive product is the E-isomer. For different metal centers, the reaction mechanisms of the Cp₂M(CO)H + DMAD (M = Nb and V) reaction are similar, while their products are different at room temperature. For M = Nb, because the energy barrier of the isomerization from Z-pro to E-pro is low and the relative free energies of Z-pro and E-pro are almost equal, both Z-pro and E-pro can be obtained. While for the Cp₂V(CO)H + DMAD reaction, only the Z-pro can be obtained under mild conditions, E-pro can be obtained only at high temperatures. For the Cp₂M(CO)H+DMAD(M=V and Nb) reactions, the formation of E-isomer products proceeds via two five-membered ring transition states. The calculated results provide an reasonable explanation for the experimental results and predict a new insertion reaction.     

Amphiphilic poly(ionic liquid)/Wells–Dawson-type phosphovanadomolybdate ionic composites as efficient and recyclable catalysts for the direct hydroxylation of benzene with H2O2

Three novel amphiphilic poly(ionic liquid) (PIL)/Wells–Dawson-type phosphovanadomolybdate (V-POM) ionic composites with tunable oxidative catalytic activity and unique nanostructure were synthesized using carboxylic acid-functionalized PIL and H₇[P₂Mo₁₇VO₆₂], H₈[P₂Mo₁₆V₂O₆₂] and H₉[P₂Mo₁₅V₃O₆₂] as synthetic units via self-assembly in water. The results of characterization indicated that V-POM anions were finely dispersed in the PIL cation framework, and their structures were well preserved. The three composites are amorphous V-POM salts of PIL cation with a considerable thermal stability, and an open three-dimensional network structure with hierarchical porosity. The as-synthesized composites were found to be efficient heterogeneous catalysts for the direct hydroxylation of benzene to phenol with H₂O₂ in the liquid phase. Under optimum conditions, a phenol yield of 37.3% was achieved with selectivity of 100%. The high catalytic performance could be attributed to the synergistic catalytic effect between V-POM anion and carboxylic acid-functionalized PIL cation framework, and good benzene adsorption and phenol desorption ability of amphiphilic micropores in the structure of the composites. Additionally, these composites exhibited high stability under the reaction conditions and could be easily recovered and reused at least six times without noticeably loss of activity.     

Recent advances in round-the-clock photocatalytic system: Mechanisms,characterization techniques and applications

Solar energy-driven semiconductor photocatalysis has gathered increasing interest in the field of energy and environmental applications. However, a vital problem that limits its application is that photocatalysis requires a continuous light source to perform redox reaction. The ability of keeping catalytic activity in the dark has been the ultimate goal for the wide application of photocatalysis. More and more efforts have been paid to develop photocatalysts to perform photocatalytic reactions under both light and dark conditions, which is so called “round-the-clock photocatalytic system” (RTCPS). RTCPS with an ability of energy storage can work well under both daytime and nighttime, which widely used in the removal of heavy metal ion, the degradation of organic pollutant, disinfection and hydrogen generation. The important potential of RTCPS necessitate timely reviews of the recent advances to streamline efforts. Thus, this review aimed to summarize the recent advances in RTCPS, including the mechanism, characterization techniques and applications. Moreover, future challenge and research direction on the mechanistic study, material design and potential applications are also discussed.     

Regulating PdC3/PtC3···thiophene interaction by small molecule doping (AgOTf,CuBr, CuI,CuBr2, PdCl2)

Structural Chemistry - The influences of small molecule doping on PdC3/PtC3···thiophene interaction have been investigated by atoms in molecules (AIM) theory, electron location...     

Microscopic insight into the quasi-particle structure of odd-mass terbium isotopes

The present work has been focussed on the application of Projected Shell Model to study the negative parity rotational band structure up to the high spin states of the neutron-rich odd mass Terbium isotopes with neutron numbers ranging from 90 to 98. The structure evolution in these nuclei has been made on the basis of various nuclear structure properties like energy spectra, transition energies, wave functions and electromagnetic transition probabilities (B(E2) and B(M1)). Besides, the occurrence of back bending has also been reported in the present work.     

Advanced Li-Ion Batteries with High Rate,Stability, and Mass Loading Based on Graphene Ribbon Hybrid Networks

To optimize the cycle life and rate performance of lithium-ion batteries (LIBs), ultra-fine Fe₂O₃ nanowires with a diameter of approximately 2 nm uniformly anchored on a cross-linked graphene ribbon network are fabricated. The unique three-dimensional structure can effectively improve the electrical conductivity and facilitate ion diffusion, especially cross-plane diffusion. Moreover, Fe₂O₃ nanowires on graphene ribbons (Fe₂O₃/GR) are easily accessible for lithium ions compared with the traditional graphene sheets (Fe₂O₃/GS). In addition, the well-developed elastic network can not only undergo the drastic volume expansion during repetitive cycling, but also protect the bulk electrode from further pulverization. As a result, the Fe₂O₃/GR hybrid exhibits high rate and long cycle life Li storage performance (632 mAh g⁻¹ at 5 A g⁻¹, and 471 mAh g⁻¹ capacity maintained even after 3000 cycles). Especially at high mass loading (≈4 mg cm⁻²), the Fe₂O₃/GR can still deliver higher reversible capacity (223 mAh g⁻¹ even at 2 A g⁻¹) compared with the Fe₂O₃/GS (37 mAh g⁻¹) for LIBs.     

Organocatalytic double arylation of 3-isothiocyanato oxindoles: Stereocontrolled synthesis of complex spirooxindoles

Quinones, precursors of aromatic structures, were firstly employed as the electrophiles for the organocatalytic Michael addition/cyclization cascade reaction with versatile 3-isothiocyanato oxindoles. Chiral bifunctional organocatalyst was appropriate for this enantioselective transformation to afford a variety of novel spirooxindoles, possessing a spirocyclic stereocenter adjacent to the aromatic ring, via asymmetric double arylation. These synthesized spirooxindoles are very difficult to access by the reported methods and were obtained in excellent chemical yields with excellent enantioselectivities.     

Ultrasonic assisted functionalization of MWCNT and synergistic electrocatalytic effect of nano-hydroxyapatite incorporated MWCNT-chitosan scaffolds for sensing of nitrofurantoin

In the present work, we report the fabrication of stable composite of chitosan hydrogels (CHI) on multiwalled carbon nanotubes (MWCNT) using a simple ultrasonic-assisted method. Also, rod-like hydroxyapatite nanoparticles (HA NPs) were synthesised using a hydrothermal route and were incorporated into the highly conductive MWCNT-CHI scaffolds using an ultrasonication method. The functionalization of MWCNT and preparation of HA NPs on MWCNT-CHI nanocomposite were done using the sonication over the frequency of 37 kHz with the ultrasonic power capable of 150 W (Elmasonic Easy 60H bath sonicator). The resulting hybrid HA NPs/MWCNT-CHI nanocomposites have an excellent surface area and high surface to volume ratio, which leads to the sensitive detection of nitrofurantoin than pristine MWCNT and HA NPs. The complete elemental and morphological analyses of the HA NPs/MWCNT-CHI nanocomposites were characterised by XRD, FTIR, RAMAN, FESEM, TEM, EDX, and elemental mapping techniques. Electrochemical analysis of the HA NPs/MWCNT-CHI nanocomposites was carried out by cyclic voltammetry, electrochemical impedance spectroscopy and amperometry methods. The modified glassy carbon electrode (GCE) of HA NPs/MWCNT-CHI nanocomposites exhibit the nitrofurantoin detection activity at the linear range of 0.005–982.1 µM with the detection limit of 1.3 nM. The synergistic electrocatalytic activity of HA NPs/MWCNT-CHI nanocomposites modified GCE is correlated to the sensitivity of 0.16 µAµM⁻¹ cm⁻² with excellent precision and accuracy towards the sensing of nitrofurantoin.