Friedel–Crafts alkylation between chalcone epoxides and heteroarenes induced by triarylaminium salt

Triarylaminium salt was disclosed as a highly efficient nonmetallic initiator for the Friedel–Crafts reaction between chalcone epoxides and heteroarenes to construct a series of complex β-heteroaryl α-ketols in mild conditions and with good yields. Chalcone epoxides were presented as valuable halogen-free pre-electrophile in Friedel–Crafts alkylation through the formation of the stabilized benzylic cation intermediates. A plausible radical cation chain mechanism was also proposed.     

Building 2D classification models and 3D CoMSIA models on small-molecule inhibitors of both wild-type and T790M/L858R double-mutant EGFR

Molecular Diversity - Epidermal growth factor receptor (EGFR) has received widespread attention because it is an important target for anticancer drug design. Mutations in the EGFR, especially the...     

A wide dynamic range laser rangefinder with cm-level resolution based on AGC amplifier structure

A pulsed time-of-flight (TOF) laser rangefinder with a pulsed laser diode and an avalanche photo diode (APD) receiver is constructed and tested. Trigged by an avalanche transistor, the laser diode can emit a periodic pulse with rise time of ～2 ns. A new structure with auto gain control (AGC) circuits both in the pre-amplifier and the post-amplifier is presented. Through this technology, not only the dynamic range of the receiver is extended, but also the walk error of timing discriminators is reduced. Large measurement range from 5 m to 500 m is achieved without any cooperative target. The single-shot precision is 3 cm for the weakest signal. Compared with previous laser rangefinders, the complexity of this system is greatly simplified.     

Synthesis of phosphates and phosphates-acetates hybrids of green tea polyphenol (−)-epigallocatechine-3-gallate (EGCG) and its G ring deoxy analogs as potential anticancer prodrugs

A series of phosphate or phosphate-acetate hybrid modified EGCG or EGCG G ring deoxy analogs were synthesized by a convenient semi-synthesis strategy from the abundant natural compound EGCG.     

Kinetics and mechanism of oxidation of <Emphasis Type="Italic">N</Emphasis>-methylethylamine by bis(hydrogenperiodato)argentate(III) complex anion

Oxidation of N-methylethylamine by bis(hydrogenperiodato)argentate(III) ([Ag(HIO₆)₂]⁵⁻) in alkaline medium results in demethylation, giving rise to formaldehyde and ethylamine as the oxidation products. The oxidation kinetics has been followed spectrophotometrically in the temperature range of 20.0–35.0 °C, and shows an overall second-order character: being first-order with respect to both Ag(III) and N-methylethylamine. The observed second-order rate constants k′ increase with increasing [OH⁻] of the reaction medium, but decrease with increasing the total concentration of periodate. An empirical rate expression for k′ has been derived as: k′ = (k _a + k _b[OH⁻])K ₁/{f([OH⁻])[IO₄ ⁻]_tot + K ₁}, where k _a and k _b are rate parameters, and K ₁ is an equilibrium constant. These parameters have been evaluated at all the temperatures studied, enabling calculation of activation parameters. A reaction mechanism is suggested to involve two pre-equilibria, leading to formation of an intermediate Ag(III) complex, namely [Ag(HIO₆)(OH)(MeNHEt)]²⁻. In the subsequent rate-determining steps, this intermediate undergoes inner-sphere electron transfer from the coordinated amine to the metal center via two distinct routes, one of which is spontaneous while the other is mediated by a hydroxide ion.     

Synthesis and characterization of novel conjugated polymers based on 3-cyclobutene-1,2-dione moiety

Three novel conjugated polymers bearing 3,4-bis（4-hexylthiophen-2-yl）-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,¹H NMR and ¹³C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers have good thermostability and solubility in common organic solvents.Moreover,all these objective macromolecules possess high electron affinity of～3.8 eV determined from cyclic voltammetry measurement,implying that they are potential n-type polymeric photovoltaic materials.     

Production of formic and acetic acids from phenol by hydrothermal oxidation

Hydrothermal technology is a core environmental-protection technique which can be used for waste water treatment and biomass conversion. In this paper a novel idea, alkaline hydrothermal oxidation, is proposed for producing formic and acetic acids from wastewater containing phenolic compounds. The effects of the most important conditions??reaction temperature, reaction time, oxygen supply, and type of alkaline catalyst??on yields of formic and acetic acids were investigated. The results indicated that the optimum conditions for production of formic and acetic acids were: reaction temperature 300???C, reaction time 90?s, H₂O₂ equivalent to 60% oxygen, and NaOH concentration 1.5?mmol. Under the optimum conditions the yields of formic and acetic acids reached 4.8 and 23.5%, respectively. In addition, the effect of different alkalis on yields of formic and acetic acids was also investigated. The results showed that compared with use of NaOH addition of KOH had a more pronounced effect on improving the yield of acetic acid. This research indicated that high-value-added formic and acetic acids can be recovered as resources by hydrothermal oxidation of phenolic wastewater, and thus hydrothermal oxidation has high potential for converting phenolic compounds in wastewater into value-added products.     

Two-Coordinate Copper(I)/NHC Complexes: Dual Emission Properties and Ultralong Room-Temperature Phosphorescence

As a kind of photoluminescent material, Cu^I complexes have many advantages such as adjustable emission, variable structures, and low cost, attracting attention in many fields. In this work, two novel two-coordinate Cu^I-N-heterocyclic carbene complexes were synthesized, and they exhibit unique dual emission properties, fluorescence and phosphorescence. The crystal structure, packing mode, and photophysical properties under different conditions were systematically studied, proving the emissive mechanism to be the locally excited state of the carbazole group. Based on this mechanism, ultralong room-temperature phosphorescence (RTP) with a lifetime of 140 ms is achieved by selective deuteration of the carbazole group. These results deepen the understanding of the luminescence mechanism and design strategy for two-coordinate Cu^I complexes, and prove their potential in applications as ultralong RTP materials.     

Oxidative Dehydrogenative Silylation‐Alkenation Reaction of Alkyl Aromatics with Silanes

A Cu(OAc)₂/DDQ/DTBP/Py system catalyzed oxidative dehydrogenative silylation‐alkenation tandem reaction of readily available alkyl aromatic compounds with silanes was established. A variety of functionalized alkenyl organosilicon compounds were provided in good to high yields with a total β‐(E) selectivity. The control experiments revealed that the transformation might proceed through a radical pathway.     

Self‐Assembly of Five 8‐Hydroxyquinolinate‐Based Complexes: Tunable Core,Supramolecular Structure,and Photoluminescence Properties

Five new Zn^II complexes, namely [Zn₃(L)₆] ( 1 ), [Zn₂(Cl)₂(L)₂(py)₂] ( 2 ), [Zn₂(Br)₂(L)₂(py)₂] ( 3 ), [Zn(L)₂(py)] ( 4 ), and [Zn₂(OAc)₂(L)₂(py)₂] ( 5 ), were prepared by the solvothermal reaction of ZnX₂ (X^?=Cl^?, Br^?, F^?, and OAc^?) salts with a 8‐hydroxyquinolinate ligand (HL) that contained a trifluorophenyl group. All of the complexes were characterized by elemental analysis, IR spectroscopy, and powder and single‐crystal X‐ray crystallography. The building blocks exhibited unprecedented structural diversification and their self‐assembly afforded one mononuclear, three binuclear, and one trinuclear Zn^II structures in response to different anions and solvent systems. Complexes 1 – 5 featured four types of supramolecular network controlled by non‐covalent interactions, such as π???π‐stacking, C? H???π, hydrogen‐bonding, and halogen‐related interactions. Investigation of their photoluminescence properties exhibited disparate emission wavelengths, lifetimes, and quantum yields in the solid state.