Synthesis,crystal structures and DNA/human serum albumin binding of ternary Cu(II) complexes containing amino acids and 6‐(pyrazin‐2‐yl)‐1,3,5‐triazine‐2,4‐diamino

Two water‐soluble 6‐(pyrazin‐2‐yl)‐1,3,5‐triazine‐2,4‐diamino (pzta)‐based Cu(II) complexes, namely [Cu(l ‐Val)(pzta)(H₂O)]ClO₄ ( 1 ) and [Cu(l ‐Thr)(pzta)(H₂O)]ClO₄ ( 2 ) (l ‐Val: l ‐valinate; l ‐Thr: l ‐threoninate), were synthesized and characterized using elemental analyses, molar conductance measurements, spectroscopic methods and single‐crystal X‐ray diffraction. The results indicated that the molecular structures of the complexes are five‐coordinated and show a distorted square‐pyramidal geometry, in which the central copper ions are coordinated to N,N atoms of pzta and N,O atoms of amino acids. The interactions of the complexes with DNA were investigated using electronic absorption, competitive fluorescence titration, circular dichroism and viscosity measurements. These studies confirmed that the complexes bind to DNA through a groove binding mode with certain affinities (K_b = 4.71 × 10³ and 1.98 × 10³ M^?1 for 1 and 2 , respectively). The human serum albumin (HSA) binding properties of the complexes were also evaluated using fluorescence and synchronous fluorescence spectroscopies, indicating that the complexes could quench the intrinsic fluorescence of HSA in a static quenching process. The relevant thermodynamic parameters revealed the involvement of van der Waals forces and hydrogen bonds in the formation of complex–HSA systems. Finally, molecular docking technology was also used to further verify the interactions of the complexes with DNA/HSA.     

The time-dependent cellular response mechanism upon exposure to zinc oxide nanoparticles

Zinc oxide nanoparticle is one of the nanomaterials people engaged most in their life and its health effect has been taken into concern. In this work, A549 cell line was used as cell model, and the cytotoxicity of zinc oxide nanoparticles was revealed to be concentration-dependent. Through the measurement of cellular proteome, much more differentially expressed proteins were observed after the cells being treated for 9 h than 24 h. Also, most of these proteins expressed in the pattern which showed a significant decrease after exposure to zinc oxide nanoparticles and then an increase at 24 h. Intracellular reactive oxygen species and glutathione determination indicated that high level of oxidative stress was presented in cell after treatment with zinc oxide nanoparticles for 9 h. It can be observed from western blot analysis that the expression of NF-κB p65, PNPase, and HSP90 rose significantly after 9 h of exposure. Thus, a deduction was reached that toxicity of nanoparticles consists both of particle toxicity and ion toxicity, and a long-time treatment may conceal the toxicity induced by particles. The conclusion we made highlighted the importance of exposure time in the study of nanoparticle toxicity and would provide a new perspective for studying toxicity mechanism of nanoparticles.     

Rapid Interception of CnF2n+1(O)SO. Radical with Copper-Based Carbene: A Novel Access to Perfluoroalkanesulfinate Ester

In this communication, an unprecedented interception of C_nF_2n+1(O)SO^. radical with a copper-based carbene has been established. Distinguished by wide substrate scopes and mild reaction conditions, this novel radical–carbene coupling reaction (RCC reaction) provides a fundamentally different and mechanistically interesting strategy for the synthesis of perfluoroalkanesulfinate esters.     

An Intrinsic Photothermal Liquid for Light Detection and Energy Storage

Photothermal materials (PTMs) have been intensively investigated in the fields of photothermal conversion. Superior to solid PTMs, liquid PTMs are leading the trends in satisfying the demands of high flexibility and easy recycling. Successful examples of liquid PTMs are mostly formulated by dispersing solid PTMs in solvents, but suffer from the problems of phase segregation and solvent pollution. In this work, a low-cost formulation is proposed, which involves an oxidative product of ethyl oleate by iodine. It is an intrinsic liquid PTM, preserving the fluidic nature as well as possessing considerable ability for photothermal conversion. In addition to understanding the mechanism of light absorption in the visible and even near infrared windows, two examples are presented to demonstrate the great potential of liquid PTMs in broad areas such as light sensing and energy storage.     

Highly efficient and thermal stable guanidinium-based two-dimensional perovskite solar cells via partial substitution with hydrophobic ammonium

Layered two-dimensional(2D)perovskite solar cells(PVSCs)with a chemical formula of C(NH_2)_3(CH_3NH_3)_3Pb_3I_(10)(n=3)have been fabricated through additive engineering,wherein stoichiometrically equivalent guanidinium(GA~+)and methylammonium(MA~+)serve as spacer cations.The crystallinity of the perovskite films is dramatically enhanced with proper amount of methylammonium thiocyanate(MASCN)added into the precursor solution.In addition,we substitute a small amount of MA~+with hydrophobic phenylethylammonium(PEA~+),which can passivate trap states of the perovskite films.As a result,the open circuit voltage increases to 1.1 V and the best power conversion efficiency(PCE)of 10.12%is yielded.Furthermore,superior thermal stability and balanced moisture stability of the PEA-substituted GA-based PVSCs are demonstrated,compared to the popular 3D MAPbI_3and 2D PEA-based PVSCs.They retain approximately 80%of the original PCE after 30 d at 20%relative humidity(RH),and 50%of the original PCE after 3200 min at 85°C without any encapsulation.This work suggests a new route to achieve both heat and humidity stable PVSCs by simply mixing different spacer cations.     

Visible-Light-Induced Vicinal Dichlorination of Alkenes through LMCT Excitation of CuCl2

This work demonstrates photoredox vicinal dichlorination of alkenes, based on the homolysis of CuCl₂ in response to irradiation with visible light. This catalysis proceeds via a ligand to metal charge transfer process and provides an exciting opportunity for the synthesis of 1,2-dichloride compounds using an inexpensive, low-molecular-weight chlorine source. This new process exhibits a wide substrate scope, excellent functional group tolerance, extraordinarily mild conditions and does not require external ligands. Mechanistic studies show that the ready formation of chlorine atom radicals is responsible for the facile formation of C−Cl bonds in this synthetic process.     

Divergent Synthesis of Vinyl‐, Benzyl‐, and Borylsilanes: Aryl to Alkyl 1,5‐Palladium Migration/Coupling Sequences

Organosilicon compounds have been extensively utilized both in industry and academia. Studies on the syntheses of diverse organosilanes is highly appealing. Through‐space metal/hydrogen shifts allow functionalization of C?H bonds at a remote site, which are otherwise difficult to achieve. However, until now, an aryl to alkyl 1,5‐palladium migration process seems to have not been presented. Reported herein is the remote olefination, arylation, and borylation of a methyl group on silicon to access diverse vinyl‐, benzyl‐, and borylsilanes, constituting a unique C(sp³)?H transformation based on a 1,5‐palladium migration process.     

Shape morphing and topology optimization of fluid channels by explicit boundary tracking

An integrated shape morphing and topology optimization approach based on the deformable simplicial complex methodology is developed to address Stokes and Navier‐Stokes flow problems. The optimized geometry is interpreted by a set of piecewise linear curves embedded in a well‐formed triangular mesh, resulting in a physically well‐defined interface between fluid and impermeable regions. The shape evolution is realized by deforming the curves while maintaining a high‐quality mesh through adaption of the mesh near the structural boundary, rather than performing global remeshing. Topological changes are allowed through hole merging or splitting of islands. The finite element discretization used provides smooth and stable optimized boundaries for simple energy dissipation objectives. However, for more advanced problems, boundary oscillations are observed due to conflicts between the objective function and the minimum length scale imposed by the meshing algorithm. A surface regularization scheme is introduced to circumvent this issue, which is specifically tailored for the deformable simplicial complex approach. In contrast to other filter‐based regularization techniques, the scheme does not introduce additional control variables, and at the same time, it is based on a rigorous sensitivity analysis. Several numerical examples are presented to demonstrate the applicability of the approach.     

Peptide dendrimer-crosslinked inorganic-organic hybrid supramolecular hydrogel for efficient anti-biofouling

A novel kind of inorganic-organic hybrid supramolecular hydrogel with excellent anti-biofouling capability was developed. The hydrogel was formed via ionic interaction between the negative-charged sodium polyacrylate (SPA) entwined clay nanosheets (CNS) and positive-charged polyhedral oligomeric silsesquioxane (POSS) core-based generation one (L-Arginine) dendrimer (POSS-R).