Synthesis of 29H,31H-phthalocyanine and chloro (29H,31H-phthalocyaninato) aluminum derivatives showed anti-cancer and anti-bacterial actions

Continuous administration of most chemotherapeutic drugs can induce different types of side effects. There has been growing interest in exploring an alternative approach to synthesizing compounds that are most effective and have fewer side effects. We synthesized 29H,31H-Phthalocyanine, and Chloro (29H,31H- phthalocyaninato) aluminum at low temperatures using lithium in the present study with diisopropylamide as the nucleophile. The physical characteristics of 29H,31H-Phthalocyanine, and Chloro (29H,31H- phthalocyaninato) aluminum were confirmed by FT-IR method, XRD, SEM, and the impact of these compounds on human colorectal carcinoma (HCT-116) and human cervical cells (HeLa) was examined. Treatment with 29H,31H-Phthalocyanine significantly decreased cancer cell growth and proliferation, as determined by MTT and DAPI staining analysis. In contrast, Chloro (29H,31H- phthalocyaninato) aluminum treatment did not show any inhibitory action on colon or cervical cancer cells. We also calculated the inhibitory concentration (IC50) of 29H,31H-Phthalocyanine, which was 30 µg/ml (HCT-116) and 33 µg/ml (HeLa cells). The antibacterial effectiveness of 29H,31H-Phthalocyanine, and chloro (29H,31H- phthalocyaninato) aluminum was studied using Enterococcus faecalis (E. faecalis). The CFU (colony frequency unit) assay confirmed significant activity against the test bacterium after treatment with 29H,31H-Phthalocyanine. However, no activity was seen upon treatment with chloro (29H,31H- phthalocyaninato) aluminum against E. faecalis.     

19F-detected dual-optimized inverted 1JCC 1,n-ADEQUATE

Modification of the recently reported ¹⁹F-detected 1,1-ADEQUATE experiment that incorporates dual-optimization to selectively invert a wide range of ¹J_CC correlations in a 1,n-ADEQUATE experiment is reported. Parameters for the dual-optimization segment of the pulse sequence were modified to accommodate the increased size of ¹J_CC homonuclear coupling constants of poly- and perfluorinated molecules relative to protonated molecules to allow broadband inversion of the ¹J_CC correlations. The observation and utility of isotope shifts are reported for the first time for 1,1- and 1,n-ADEQUATE correlations.     

Palladium-catalyzed vinylation of cyclohexenes using a directing-group strategy

Palladium-promoted vinylation of cyclohexenes via employment of a directing-group strategy to yield the coupled vinyl cyclohexenes with excellent regio- and stereoselectivity was studied. Typically, reaction of 2-(cyclohex-2-en-1-yl)-N-tosylacetamide ( 1a ) with (Z)-styryl bromides ( 2 ) gave cis-2-[(E)-styryl]cyclopent-3-en-1-yl-N-tosylacetamides in good to excellent yields. It is noticed that (Z)-styryl moiety was inverted into (E)-form in products. Unfortunately, (E)-styryl bromide substrates were not suitable for this reaction under the condition investigated. Further studies on norbornene system, we found that palladium-catalyzed reaction of endo-N-tosylbicyclo[2.2.1]hept-5-ene-2-carboxamide ( 6 ) with styryl bromides gave the Aza-Heck type products.     

环境响应性微胶囊及其在农业领域中应用的研究进展

在传统农业中,如何高效率地使用农药,提高其利用率,一直是一大难题。环境响应性微胶囊是一类在外界环境的刺激下,可以相适应地改变其表面结构的物质。这一类微胶囊具有智能、可控、精准、高效等特点。目前,这一项技术已经被广泛地应用于农业生产中。本文主要综述了环境中pH、温度、光以及磁场四大因素对响应性微胶囊的影响,并且简要介绍了该类微胶囊的制备技术、形成机理、主要材料以及在农业领域的应用。     

Mobility of Li+, Na+, and Cs+ cations in Nafion membrane,as studied by NMR techniques

The local mobility and diffusion of Li⁺, Na⁺, and Cs⁺ cations in Nafion 117 membrane were explored by ⁷Li, ²³Na, and ¹³³Cs spin relaxation and pulsed field gradient NMR techniques. It was shown that the macroscopic mass transfer of cations is controlled by ion motion near sulfonate groups. Lithium and sodium cations, whose hydrated energy is higher than the water hydrogen bond energy, are moving together with water molecules, but cesium cations possessing a low hydrated energy are jumping directly between the neighboring sulfonate groups.     

Sensitive Electrochemical Quantification of Proanthocyanidins in Grapevine (Vitis vinifera) by Utilizing Disposable Screen-printed Carbon Electrodes

This work presents quantification of proanthocyanidins (PAs) isolated from grapevine using disposable screen-printed carbon electrodes (SPCE). Procyanidin B2 (B2) used as a model to investigate the electrochemical characteristics of complicated PAs structures in Britton Robinson buffer solution using cyclic voltammetry and square wave voltammetry. B2 exhibits a well-defined reversible redox wave at +0.49 V vs. Ag/AgCl. Significantly, the B2 was determined over a linear concentration range of 3.45–34.6 μM with a detection limit of 2.07 μM. The SPCE was used to analyze PAs in grapevine samples, and the results were consistent with those obtained using Folin-Ciocalteu standard method.     

Enabling the Operation of Highly Compatible LiI-3-Hydroxypropionitrile Small-Molecule Solid-State Electrolytes in Lithium Metal Batteries via Stepped-Amorphization Strategy

Integrating the advantages of both inorganic ceramic and organic polymer solid-state electrolytes, small-molecule solid-state electrolytes represented by LiI-3-hydroxypropionitrile (LiI-HPN) inorganic–organic hybrid systems possess good interfacial compatibility and high modulus. However, their lack of intrinsic Li⁺ conduction ability hinders potential application in lithium metal batteries until now, despite containing LiI phase composition. Herein, inspired by evolution tendency of ionic conduction behaviors together with first-principles molecular dynamics simulations, we propose a stepped-amorphization strategy to break the Li⁺ conduction bottleneck of LiI-HPN. It involves three progressive steps of composition (LiI-content increasing), time (long-time standing), and temperature (high-temperature melting) regulations, to essentially construct a small-molecule-based composite solid-state electrolyte with intensified amorphous degree, which realizes efficient conversion from an I⁻ to Li⁺ conductor and improved conductivity. As a proof, the stepped-optimized LiI-HPN is successfully operated in lithium metal batteries cooperated with Li₄Ti₅O₁₂ cathode to deliver considerable compatibility and stability over 250 cycles. This work not only clarifies the ionic conduction mechanisms of LiI-HPN inorganic–organic hybrid systems, but also provides a reasonable strategy to broaden the application scenarios of highly compatible small-molecule solid-state electrolytes.     

Efficient Reverse Intersystem Crossing in Carbene-Copper-Amide TADF Emitters via an Intermediate Triplet State

The mechanism behind reverse intersystem crossing (rISC) in metal-based TADF emitters is still under debate. Thermal rISC necessitates small singlet/triplet energy gaps as realized in donor-acceptor systems with charge-transfer excited states. However, their associated spin-orbit couplings are too small to account for effective rISC. Here, we report the first nonadiabatic dynamics simulation of the rISC process in a carbene-copper(I)-carbazolyl TADF emitter. Efficient rISC on a picosecond time scale is demonstrated for an initial triplet minimum geometry that exhibits a perpendicular orientation of the ligands. The dynamics involves an intermediate higher-lying triplet state of metal-to-ligand charge transfer character (³MLCT), which enables large spin-orbit couplings with the lowest singlet charge transfer state. The mechanism is completed in the S₁ state, where the complex can return to a co-planar coordination geometry that presents high fluorescence efficiency.     

Enantioselective De Novo Synthesis of α,α-Diaryl Ketones from Alkynes

Chiral α,α-diaryl ketones are structural motifs commonly present in bioactive molecules, and they are also valuable building blocks in synthetic organic chemistry. However, catalytic asymmetric synthesis of α,α-diaryl ketones bearing a tertiary stereogenic center remains largely unsolved. Herein, we report a catalytic de novo enantioselective synthesis of α,α-diaryl ketones from simple alkynes via chiral phosphoric acid (CPA) catalysis. A broad range of enolizable α,α-diaryl ketones are prepared in good yields and with excellent enantioselectivities. The described protocol also serves as an efficient deuteration method for the preparation of enantiomerically enriched deuterated α,α-diaryl ketones. Using the methodology reported, bioactive molecules, including one of the best-selling anti-breast cancer drugs, tamoxifen, are readily synthesized.     

Palladium-Catalyzed Skeletal Rearrangement of Substituted 2-Silylaryl Triflates via 1,5-C−Pd/C−Si Bond Exchange

A palladium-catalyzed skeletal rearrangement of 2-(2-allylarylsilyl)aryl triflates has been developed to give highly fused tetrahydrophenanthrosilole derivatives via unprecedented 1,5-C−Pd/C−Si bond exchange. The reaction pathways can be switched toward 4-membered ring-forming C(sp²)−H alkylation by tuning the reaction conditions to give completely different products, fused dihydrodibenzosilepin derivatives, from the same starting materials. The inspection of the reaction conditions revealed the importance of carboxylates in promoting the C−Pd/C−Si bond exchange.