Synthesis of 6-trifluoromethylindolo[1,2-c]quinazolines and related heterocycles using N-(2-iodophenyl)trifluoroacetimidoyl chlorides as starting material via C-H bond functionalization

A mild, two-step reaction for the synthesis of 6-trifluoromethylindolo[1,2-c]quinazolines from readily available indoles and N-(2-iodophenyl)trifluoroacetimidoyl chlorides via addition-elimination/arylation is described. An array of aza-fused trifluoromethylated heterocycles can be easily assembled via Friedel-Crafts reaction/C-H bond activation by this methodology.     

N-acylsulfonamide assisted tandem C-H olefination/annulation: synthesis of isoindolinones

A tandem C-H olefination/annulation sequence directed by N-acylsulfonamides affords a variety of isoindolinones. This transformation is compatible with aliphatic alkenes as well as conjugated alkenes. Notably, molecular oxygen can be used as the sole, eco-friendly oxidant.     

A simple solution combustion route for the preparation of metal-doped TiO2 nanoparticles and their photocatalytic degradation properties

In this paper, we report the successful synthesis of metal ion-doped TiO(2) nanoparticles via a simple solution combustion method employing a mixture of ethanol and ethyleneglycol (v/v = 30/20) as the solvent, tetra-n-butyl titanate [Ti(OC(4)H(9))(4), TBOT] as the titanium source and oxygen gas in the atmosphere as the oxygen source, in the presence of small amounts of metal ions such as Cu(2+), Mn(2+), Ce(3+) and Sn(4+). The as-obtained products were characterized by means of powder X-ray diffraction (XRD), energy dispersive X-ray spectrometry (EDS) and scanning electron microscopy (SEM). The UV-vis diffuse reflectance spectra (DRS) and photoluminescence (PL) spectra of various metal ion-doped products were investigated. Experiments showed that the metal ion-doped TiO(2) nanoparticles presented a stronger photocatalytic ability for the degradation of organic dyes, including Pyronine B, Safranine T and Methylene blue (MB), under visible light/254 nm UV light irradiation than commercial P25 within the same time.     

Molecular dynamics simulation of ionic transport on molten Li–KCl interface

A molecular dynamics study is performed to determine the dynamics and transport properties of the ions on the molten interface between anode metal Li and electrolyte KCl. Radial distribution function of the ionic pair and the behavior of the mean‐square displacement (MSD) as a function of time (t) indicate that KCl and metal Li are in the molten state at 2,200 K in the canonical ensemble. The dynamics of the ionic transport are characterized by studying MSD for the centers of mass of the ions at different temperatures. Diffusion coefficient is evaluated from the linear slope of the MSD (t) function in the range of 0–500 ps. The MSD and diffusion coefficient of the Li⁺ ions are much larger than those of the Cl^? and K⁺ ions due to the difference in ionic characteristic. The transport process has been dominated by the Li⁺ ions on the molten interface and the Li⁺ ions are main charge carriers. The energy barrier of the Li⁺ ions transporting into the molten KCl is fitted to be 5.28 kcal/mol in the light of the activation model. The electrical conductivity of the Li⁺ ions transporting into the molten KCl are calculated from the Nernst–Einstein formula to be in the range of 0.2–0.3 S cm^?1. The current density resulted from the Li⁺ ions through the interface are estimated to be an order of 10⁶ A cm^?2, which may be the value corresponding to a larger concentration gradient of the Li⁺ ions. Simulated results at different temperatures show that the diffusion coefficient, conductivity and current density have increased with the temperature. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Inclusion Complexes of Coenzyme Q10 with Polyamine‐Modified β‐Cyclodextrins: Characterization,Solubilization, and Inclusion Mode

The inclusion‐complexation behavior of coenzyme Q10 (CoQ10) with the three polyamine‐modified β‐cyclodextrins (CDs) 1 – 3 was investigated in both solution and the solid state by means of NMR, XRD, and FT‐IR spectroscopy. The results showed that the apparent solubility of CoQ10 increased linearly upon addition of hosts 1 – 3 , giving A_L‐type phase‐solubility curves. These hosts 1 – 3 were able to solubilize CoQ10 to high levels, up to 1.35, 1.52, and 1.44 mg/ml (calculated as CoQ10), respectively. The host 2 with a moderate‐length chain is the most suitable for inclusion complexation of CoQ10. Accroding to the ROESY experiments, the MeO groups of CoQ10 and the tether of 2 can be co‐included into the cavity of β‐CD through the induced‐fit interaction between host and guest. The binding ability of modified β‐CDs 1 – 3 upon complexation with CoQ10 are discussed from the viewpoints of the size/shape‐matching relationship and the induced‐fit concept between host CDs and guest CoQ10 molecule.     

Mechanistic Insights into the Ni‐Catalyzed Reductive Carboxylation of C−O Bonds in Aromatic Esters with CO2: Understanding Remarkable Ligand and Traceless‐Directing‐Group Effects

The mechanism of the Ni⁰‐catalyzed reductive carboxylation reaction of C(sp²)?O and C(sp³)?O bonds in aromatic esters with CO₂ to access valuable carboxylic acids was comprehensively studied by using DFT calculations. Computational results revealed that this transformation was composed of several key steps: C?O bond cleavage, reductive elimination, and/or CO₂ insertion. Of these steps, C?O bond cleavage was found to be rate‐determining, and it occurred through either oxidative addition to form a Ni^II intermediate, or a radical pathway that involved a bimetallic species to generate two Ni^I species through homolytic dissociation of the C?O bond. DFT calculations revealed that the oxidative addition step was preferred in the reductive carboxylation reactions of C(sp²)?O and C(sp³)?O bonds in substrates with extended π systems. In contrast, oxidative addition was highly disfavored when traceless directing groups were involved in the reductive coupling of substrates without extended π systems. In such cases, the presence of traceless directing groups allowed for docking of a second Ni⁰ catalyst, and the reactions proceed through a bimetallic radical pathway, rather than through concerted oxidative addition, to afford two Ni^I species both kinetically and thermodynamically. These theoretical mechanistic insights into the reductive carboxylation reactions of C?O bonds were also employed to investigate several experimentally observed phenomena, including ligand‐dependent reactivity and site‐selectivity.     

11.2% Efficiency all-polymer solar cells with high open-circuit voltage

Herein,we fabricated all-polymer solar cells(all-PSCs)based on a fluorinated wide-bandgap p-type conjugated polymer PM6 as the donor,and a narrow bandgap n-type conjugated polymer PZ1 as the acceptor.In addition to the complementary absorption and matching energy levels,the optimized blend films possess high cystallinity,predominantly face-on stacking,and a suitable phase separated morphology.With this active layer,the devices exhibited a high V_(oc)of 0.96 V,a superior J_(sc)of 17.1 mA cm~(-2),a fine fill factor(FF)of 68.2%,and thus an excellent power conversion efficiency(PCE)of 11.2%,which is the highest value reported to date for single-junction all-PSCs.Furthermore,the devices showed good storage stability.After 80 d of storage in the N_2-filled glovebox,the PCE still remained over 90%of the original value.Large-area devices(1.1 cm~2)also demonstrated an outstanding performance with a PCE of 9.2%,among the highest values for the reported large-area all-PSCs.These results indicate that the PM6:PZ1 blend is a promising candidate for scale-up production of large area high-performance all-PSCs.     

2—氨基—9,10—蒽醌及其衍生物的光谱电化学研究

用循环伏安法研究了２－氨基－９，１０－蒽醌及其衍生物在ＤＭＦ－０．１ｍｏｌ／ＬＴＢＡＰ溶液中的电化学行为，结果表明它们在铂电极上均发生两步连续的单电子还原过程，取代基Ｒ及水和苯甲酸等质子性试剂的加对伏安曲线有很大的影响。     

Design,Synthesis, and Evaluation of Novel L-Pyroglutamic Acid Derivatives as Potent Antifungal Agents

Chemistry of Natural Compounds - A series of novel L-pyroglutamate containing 1,2,3-triazole ring substructures was synthesized and characterized by adopting an appropriate synthetic scheme. The...     

A family of single-isomer,sulfated gamma-cyclodextrin chiral resolving agents for capillary electrophoresis: octa(6-O-sulfo)-gamma-cyclodextrin

The second member of the single-isomer, sulfated gamma-cyclodextrin family, the sodium salt of octa(6-O-sulfo)-gamma-cyclodextrin (OS) has been synthesized, characterized and used to separate the enantiomers of nonelectrolyte, acidic, basic, and ampholytic analytes by capillary electrophoresis in acidic aqueous background electrolytes. The anionic effective mobilities of the nonelectrolyte and anionic analytes increased with increasing concentration of OS. The effective mobilities of strongly complexing cationic analytes became anionic with very low OS concentrations and passed local anionic effective mobility maxima as the OS concentration, and along with it, the ionic strength, of the background electrolyte increased. The effective mobilities of the weakly binding cationic analytes became only slightly anionic at high OS concentration values and did not show the local anionic effective mobility maxima. For nonelectrolyte analytes, separation selectivities decreased with increasing OS concentration. For cationic analytes, separation selectivities were highest where the effective mobilities of the less mobile enantiomers approached zero. OS proved to be a broadly applicable chiral resolving agent.