New organoruthenium metallates containing ferrocenecarboxalidine thiosemicarbazones and their nucleic acid/albumin binding and in vitro cytotoxicity

A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh₃]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh₃]Cl was the most active on HT-29 cells.     

Preparation of modified MFI (ZSM-5 and silicalite-1) zeolites for potassium extraction from seawater

Modified nanosized MFI (ZSM-5 and silicalite-1) zeolites were successfully synthesized by a hydrothermal method using aluminum isopropoxide and tetraethylorthosilicate as the raw materials. The synthetic zeolites were characterized by X-ray diffraction, energy dispersion spectroscopy, and scanning electron microscopy. The ZSM-5 and silicalite-1 zeolites exhibited ellipse-like and cubic columns, respectively. The K⁺ ion-exchange equilibrium and ion-exchange capacity of the synthetic zeolites in seawater were investigated. The K⁺ ion-exchange of synthetic zeolites was rapid and reached an ion-exchange balance in approximately 20 min. The K⁺ ion-exchange capacity of ZSM-5 and silicalite-1 in seawater was 56.7 and 48.7 mg/g, respectively. The synthetic zeolites have high selectivity toward K⁺, and therefore, they can be used to selectively extract potassium from seawater.     

Influence of Potassium Metal-Support Interactions on Dendrite Growth

Combined synchrotron X-ray nanotomography imaging, cryogenic electron microscopy (cryo-EM) and modeling elucidate how potassium (K) metal-support energetics influence electrodeposit microstructure. Three model supports are employed: O-functionalized carbon cloth (potassiophilic, fully-wetted), non-functionalized cloth and Cu foil (potassiophobic, nonwetted). Nanotomography and focused ion beam (cryo-FIB) cross-sections yield complementary three-dimensional (3D) maps of cycled electrodeposits. Electrodeposit on potassiophobic support is a triphasic sponge, with fibrous dendrites covered by solid electrolyte interphase (SEI) and interspersed with nanopores (sub-10 nm to 100 nm scale). Lage cracks and voids are also a key feature. On potassiophilic support, the deposit is dense and pore-free, with uniform surface and SEI morphology. Mesoscale modeling captures the critical role of substrate-metal interaction on K metal film nucleation and growth, as well as the associated stress state.     

Synthetic K+ Channels Constructed by Rebuilding the Core Modules of Natural K+ Channels in an Artificial System

Different types of natural K⁺ channels share similar core modules and cation permeability characteristics. In this study, we have developed novel artificial K⁺ channels by rebuilding the core modules of natural K⁺ channels in artificial systems. All the channels displayed high selectivity for K⁺ over Na⁺ and exhibited a selectivity sequence of K⁺≈Rb⁺ during the transport process, which is highly consistent with the cation permeability characteristics of natural K⁺ channels. More importantly, these artificial channels could be efficiently inserted into cell membranes and mediate the transmembrane transport of K⁺, disrupting the cellular K⁺ homeostasis and eventually triggering the apoptosis of cells. These findings demonstrate that, by rebuilding the core modules of natural K⁺ channels in artificial systems, the structures, transport behaviors, and physiological functions of natural K⁺ channels can be mimicked in synthetic channels.     

基于DNA酶催化增敏的微流控顺序注射化学发光法检测钾离子的研究

基于G-四联体/血红素形成的DNA酶催化增敏鲁米诺-H2O2发光反应原理,建立了微流控顺序注射化学发光检测K+的新方法。在K+的促进作用下,富含鸟嘌呤的寡核苷酸PS5.M折叠成G-四联体,并对血红素表现出较高的亲合力,形成DNA酶,显著地增强血红素的类辣根过氧化物酶活性,催化鲁米诺-H2O2化学发光反应。在优化的实验条件下,化学发光检测K+的线性范围为1.0~700μmol·L-1,检出限为0.54μmol·L-1,用100μmol·L-1的K+形成的DNA酶连续测定10次,相对标准偏差(RSD)为1.61%。常见的碱金属和碱土金属离子均无显著干扰。该方法可用于真实水样中K+的分析,测定结果与原子吸收法一致。     

Improved hydrogen evolution on glassy carbon electrode modified with novel Pt/cetyltrimethylammonium bromide nanoscale aggregates

A novel, cost‐effective, and simple electrocatalyst based on a Pt‐modified glassy carbon electrode (GCE), using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, is reported. Am‐phiphilic...     

Regioselective One‐pot Synthesis of New Unsymmetric Spiro Dihydrofurans in the Reaction of Mixed Two Different Cyclic β‐Dicarbonyl Compounds with BrCN and Aldehydes in the Presence of Et3N

Crossed one‐pot reaction of mixed cyclic β‐dicarbonyl with various aldehydes in the presence of cyano gen bromide and triethylamine leads to the selective and efficient formation of crossed new unsymmetri cal spiro dihydrofurans at room temperature. The products were obtained in good to excellent yields. Structure elucidation was carried out by ¹H NMR, ¹³C NMR, FT‐IR spectroscopy, Mass analyses and X‐ray crystallography technique. A proposed mechanism was discussed for the formation of products.     

Novel and Stereospecific Synthesis of (2S)‐3‐(2,4,5‐Trifluorophenyl)propane‐1,2‐diol from D‐Mannitol

A stereospecific synthesis of (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol from D ‐mannitol has been developed. The reaction of 2,3‐O‐isopropylidene‐D ‐glyceraldehyde with 2,4,5‐trifluorophenylmagnesium bromide gave [(4R)‐2,2‐dimethyl‐1,3‐dioxolan‐4‐yl](2,4,5‐trifluorophenyl)methanol in 65% yield as a mixture of diastereoisomers (1 : 1). The Ph₃P catalyzed reaction of the latter with C₂Cl₆ followed by reduction with Pd/C‐catalyzed hydrogenation gave (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol with >99% ee and 65% yield.     

Sulfonyl Ketenimines as Key Intermediates in One‐Pot Synthesis of N‐Sulfonyl‐2‐alkaneimidoyl Selenocyanates

Sulfonyl‐ketenimine intermediates, generated by the addition of Cu acetylides to sulfonyl azides, are trapped by KSeCN to afford N‐sulfonyl‐2‐alkaneimidoyl selenocyanates in moderate‐to‐good yields.     

On solubility of europium monoxide in melts of (NaBr + NaI) system at T = 973 K

Equilibria of EuO dissolution and dissociation in molten (NaBr + NaI) mixtures of 0.77:0.23 and 0.31:0.69 compositions at T = 973 K were studied by potentiometric titration method using Pt(O₂)|ZrO₂(Y₂O₃) indicator electrode. The solubility product indices of EuO are (7.81 ± 0.08) and (8.43 ± 0.16) in the melts of 0.77:0.23 and 0.31:0.69 compositions. The corresponding dissociation constant indices are (4.96 ± 0.04) and (5.54 ± 0.06), respectively (all the parameters are in molality). Non-dissociated EuO is the prevailing form in all the saturated solutions of europium monoxide. The decrease of the iodide ion concentration in the melts results in strengthening of EuO dissociation that is explained by introduction of harder Pearson’s base (Br⁻) in sodium iodide melt. In its turn this increases the fixation degree of Eu²⁺ in mixed halide complexes. The total solubility of EuO decreases going from NaI melt to the (bromide + iodide) mixtures that is caused by the decrease of ‘physical’ solubility of non-dissociated oxide which occupies hollow spaces of enough large size in the ionic solvents. The quantity of these hollow spaces diminishes at the sequential Br⁻ → I⁻ substitution.