Tetraphenylene-based semiconductive metal-organic framework crystals for direct X-ray detection and imaging.

MOFs have good potential for X-ray detection, but direct X-ray detection in single crystal form is rarely reported. In this work, we successfully synthesized Pb-TCPE, and the single crystal achieves a low detection limit and high detection sensitivity of 4812.6 μC Gy cm, which exhibits great potential for X-ray detection and imaging.

Highly Efficient Luminescence from a Red Thermally Activated Delayed Fluorescence Emitter with Flexible Conformation of Ancillary Groups.

Robust scaffolds were typically applied in thermally activated delayed fluorescence (TADF) molecules to suppress the non-radiative decay, trigger the fast spin-flipping, and enhance the light out-coupling efficiency. Herein, we disclosed for the first time the positive effect of flexible conformation of ancillary groups on the photophysical properties of TADF emitter. The red TADF emitter Ph-TPA with flexible conformation demonstrated small excited-state structural distortion and low reorganization energy compared to the counterpart Mc-TPA with a rigid macrocycle.

Intramolecular charge transfer effect for highly efficient deep red and near infrared thermally activated delayed fluorescence.

Thermally activated delayed fluorescence (TADF) materials with emission in the deep red and near infrared (DR/NIR) region are underresearched due to the limited choice of strong donor/acceptor units. The current mainstream strategy for the design of DR/NIR TADFs is to increase the acceptor strength the introduction of multiple sub-acceptor units, thereby narrowing the bandgap. In this work, the intramolecular charge transfer (ICT) effect was applied for the development of acceptor units to achieve efficient DR/NIR TADFs.

Using azaacene as an acceptor unit to construct an ultraefficient red fluorophore with an EQE over 40.

Azaacenes, which have been known for a long time, are of scientific and practical importance in organic electronics. Azaacenes once shone as the luminophore in organic light-emitting diodes (OLEDs). However, due to the low exciton utilization efficiency and/or the aggregation induced quenching (ACQ) effect, N-heteroacene based OLEDs generally showed inferior device performance.

Synthesis of novel nicotinamide susbstituted phthalocyanine and photodynamic antomicrobial chemotherapy evaluation potentiated by potassium iodide against the gram positive S. aureus and gram negative E. coli.

In the present work, we propose the synthesis of novel nicotinamide subsituted phthlocyanine photosensitizer (PS) and characterized by FTIR, UV-visible, H-NMR and MALDI Toff spectroscopy. Nicotinamide plays a vital rule in the central nervous system and its potential as a therapeutic for neurodegenerative disease. Nicotinamide substituted PS (3) efficiently produced ROS via type-1 process as measured by DCF assay.

Electrochemically Enabled Carbohydroxylation of Alkenes with HO and Organotrifluoroborates.

Unprecedented hydroxy-alkynylation and -alkenylation reactions of arylalkenes have been developed through electrochemically enabled addition of an organotrifluoroborate reagent and HO across the double bond of the alkene. The use of electrochemistry to promote these oxidative alkene 1,2-difunctionalization reactions not only obviates the need for transition-metal catalysts and oxidizing reagents but also ensures high regio- and chemoselectivity to afford homopropargylic or homoallylic alcohols. The possibility of extending the electrochemical alkene difunctionalization strategy to other alkene carbo-heterofunctionalization reactions has been demonstrated.

Cathode Material Determines Product Selectivity for Electrochemical C-H Functionalization of Biaryl Ketoximes.

The synthesis of polycyclic N-heteroaromatic compounds and their corresponding N-oxides has been developed through electrochemical C-H functionalization of biaryl ketoximes. The oxime substrates undergo dehydrogenative cyclization when a Pt cathode is used, resulting in unprecedented access to a wide range of N-heteroaromatic N-oxides. The products of the electrosynthesis are switched to the deoxygenated N-heteroaromatics by employing a Pb cathode through sequential anode-promoted dehydrogenative cyclization and cathodic cleavage of the N-O bond in the initially formed N-oxide.

Electrochemical Difluoromethylarylation of Alkynes.

An unprecedented radical difluoromethylarylation reaction of alkynes has been developed by discovering a new difluoromethylation reagent, CFHSONHNHBoc. This air-stable and solid reagent can be prepared in one step from commercially available reagents CFHSOCl and NHNHBoc. The CFH radical, generated through ferrocene-mediated electrochemical oxidation, participates in an unexplored alkyne addition reaction followed by a challenging 7-membered ring-forming homolytic aromatic substitution step to afford fluorinated dibenzazepines.

Reagent-Free C-H/N-H Cross-Coupling: Regioselective Synthesis of N-Heteroaromatics from Biaryl Aldehydes and NH.

An unprecedented synthesis of N-heteroaromatics from biaryl aldehydes and NH through reagent-free C-H/N-H cross-coupling has been developed. The electrosynthesis uses NH as an inexpensive and atom-economic nitrogen donor, requires no oxidizing agents, and allows efficient and regioselective access to a wide range of phenanthridines and structurally related polycyclic N-heteroaromatic products.

Amidinyl Radical Formation through Anodic N-H Bond Cleavage and Its Application in Aromatic C-H Bond Functionalization.

We report herein an atom-economical and sustainable approach to access amidinyl radical intermediates through the anodic cleavage of N-H bonds. The resulting nitrogen-centered radicals undergo cyclizations with (hetero)arenes, followed by rearomatization, to afford functionalized tetracyclic benzimidazoles in a highly straightforward and efficient manner. This metal- and reagent-free C-H/N-H cross-coupling reaction exhibits a broad substrate scope and proceeds with high chemoselectivity.

Electrochemical C-H/N-H Functionalization for the Synthesis of Highly Functionalized (Aza)indoles.

Indoles and azaindoles are among the most important heterocycles because of their prevalence in nature and their broad utility in pharmaceutical industry. Reported herein is an unprecedented noble-metal- and oxidant-free electrochemical method for the coupling of (hetero)arylamines with tethered alkynes to synthesize highly functionalized indoles, as well as the more challenging azaindoles.

Copper-Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes.

A copper-catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker-type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β-hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes.

Removal of Congo Red from Aqueous Solution by Anion Exchange Membrane (EBTAC): Adsorption Kinetics and Themodynamics.

The adsorption behavior of anionic dye congo red (CR) from aqueous solutions using an anion exchange membrane (EBTAC) has been investigated at room temperature. The effect of several factors including contact time, membrane dosage, ionic strength and temperature were studied. Kinetic models, namely pseudo-first-order and pseudo-second-order, liquid film diffusion and Elovich models as well as Bangham and modified freundlich Equations, were employed to evaluate the experimental results.

[Effect of PLGA nanoparticles conjugated with anti-OX40/anti-AFP mAbs on cytotoxicity of CTL cells against hepatocellular carcinoma].

Objective: To evaluate the effect of anti-OX40 and anti-AFP antibodies conjugated onto poly(DL-lactide-co-glycolide)-nanoparticles (PLGA-NPs) on the cytotoxic activity of AFP158-166; -specific cytotoxic T lymphocyte (CTL) against hepatocellular carcinoma cells in vitro.

Methods: PLGA-NPs were prepared by oil-in-water single emulsion solvent evaporation method and covalently conjugated with anti-OX40 and anti-AFP monoclonal antibodies. Scanning electron microscopy (SEM) was utilized for the characterization of the surface morphology and estimation of the size of the PLGA-NPs.

PANC-1 pancreatic cancer cell growth inhibited by cucurmosin alone and in combination with an epidermal growth factor receptor-targeted drug.

Objectives: To investigate the inhibition of PANC-1 pancreatic cancer cell growth by cucurmosin (CUS) and its possible mechanism.

Methods: We observed the inhibition of PANC-1 cell growth by sulforhodamine B and colony-forming experiments in vitro and established nonobese diabetic/severe combined immunodeficiency mouse subcutaneous tumor models in vivo. We used Western blot to analyze protein levels related to apoptosis and epidermal growth factor receptor (EGFR) signaling pathways after drug intervention, whereas the messenger RNA expression of EGFR was analyzed by quantitative real-time polymerase chain reaction.

Surface doping for photocatalytic purposes: relations between particle size, surface modifications, and photoactivity of SnO(2):Zn2+ nanocrystals.

Highly crystalline SnO(2) nanocrystals with and without Zn(2+) doping were directly prepared by a solvothermal method. By systematic characterizations using x-ray diffraction, transmission electron microscopy, infrared spectra, and UV-vis spectra, it is demonstrated that all samples crystallized in a single phase of rutile structure, and that upon Zn(2+) doping particle sizes closer to the exciton Bohr radius (2.7 nm) of SnO(2) were achieved, while the particle size of SnO(2) nanoparticles was as large as about 12 nm without Zn(2+) doping.

Preparation, characterization, and photophysical properties of Pt-M (M = Ru, Re) heteronuclear complexes with 1,10-phenanthrolineethynyl ligands.

When 3-ethynyl-1,10-phenanthroline (HCCphen) or 3,8-diethynyl-1,10-phenanthroline (HCCphenCCH) is utilized as a bifunctional bridging ligand via stepwise molecular fabrication, a series of Pt-Ru and Pt-Re heteronuclear complexes composed of both platinum(II) terpyridyl acetylide chromophores and a Ru(phen)(bpy)2/Re(phen)(CO)3Cl subunit were prepared by complexation of one or two Pt((t)Bu3tpy)(2+) units to the mononuclear Ru(II) or Re(I) precursor through platinum acetylide sigma coordination. These Pt-Ru and Pt-Re complexes exhibit intense low-energy absorptions originating from both Pt- and Ru (Re)-based metal-to-ligand charge-transfer (MLCT) states in the near-visible region. They are strongly luminescent in both solid states and fluid solutions with a submicrosecond range of lifetimes and 0.

Diiron models for the active site of Fe-only hydrogenase with terminal organosulfur ligation: synthesis, structures and electrochemistry.

Diiron model complexes (micro-SCH(2)CH(2)CH(2)S)Fe(2)(CO)(5)L with thioether-substitution, L=S(CH(2)CH(3))(2) (2), S(CH(2)CH(3))(CH(2)CH(2)Cl) (3), S(CH(2)CH(3))(C(6)H(5)) (4), or sulfoxide-substitution, L=SO(CH(2)CH(2)CH(3))(2) (5), SO(CH(3))(2) (6), were synthesized as active site analogues of Fe-only hydrogenase. The organosulfur ligands were introduced into the diiron centers via moderately stable intermediates following two routes. The X-ray crystallographic structures of complexes 2-6 show the apical positions of terminal organosulfur ligands.