Enhancement of photoinduced intramolecular cross-cycloaddition of α-(9-anthryl)-ω-(1-naphthoyl) end-labeled poly(ethylene glycol) via lipophobic interactions and complexation with metal cations

The fluorescence spectra and photocycloadditions of poly(ethylene glycol) labeled at the chain termini with one 9-anthryl and one 1-naphthoyl group (N-P_n-A) both in non-polar and polar solvents in the presence of alkali-metal cations have been investigated. Lipophobic interactions in non-polar solvents and complexation of the polyether with cations in polar solvents force the two terminal groups of N-P_n-A into proximity, and irradiation of the solutions produces intramolecular photocyclomers to the exclusion of intermolecular products.     

Facile photoreduction of graphene oxide by an NAD(P)H model: Hantzsch 1,4-dihydropyridine

To make "clean" reduced GO sheets in high quality and in large scale, a natural reduced nicotinamine adenine dinucleotide NAD(P)H model, Hantzsch 1,4-dihydropyridine (HEH), is used as a mild organic photoreductant in this work. Benefiting from the intense absorption of HEH in the range of 300-420 nm, the graphene oxide (GO) can be readily reduced by HEH under UV light irradiation (λ > 320 nm) to afford single or few-layer reduced graphene oxide at room temperature. Studies on reduction extent reveal that both irradiation time and concentration ratio of HEH to GO are important for effective reduction of GO under UV light. The as-prepared photochemically reduced graphene oxide (PRGO) dispersion is stable without the need for any polymeric or surfactant stabilizers. Simply by extraction treatment, the "clean" PRGO sheets can be obtained in large quantities, and its conductivity approaches to 4680 S·m(-1) that is the highest value reported by photochemical approaches so far.     

Reactivity and mechanistic insight into visible-light-induced aerobic cross-dehydrogenative coupling reaction by organophotocatalysts

With visible-light irradiation, a mild, simple, and efficient metal-free photocatalytic system for the facile construction of sp(3)-sp(3) C-C bonds between tertiary amines and activated C-H bonds has been achieved. Spectroscopic study and product analysis demonstrate for the first time that photoinduced electron transfer from N-aryl tetrahydroisoquinolines to eosin Y bis(tetrabutylammonium salt) (TBA-eosin Y) takes place to generate TBA-eosin Y radical anion, which can subsequently react with nucleophiles and molecular oxygen. More strikingly, electron spin resonance (ESR) measurements provide direct evidence for the formation of superoxide radical anions (O(2)(-.)) rather than singlet oxygen ((1)O(2)) during visible-light irradiation. This active species is therefore believed to be responsible for the large rate of acceleration of the aerobic photocatalytic reactions.     

Synthesis of 3-acylindoles via decarboxylative cross-coupling reaction of free(N–H) indoles with α-oxocarboxylic acids

A convenient and general method for acylation of free(N–H) indoles via palladium-catalyzed decarboxylative cross-coupling reaction was developed. This process provided a useful method for the preparation of diverse 3-acylindoles in high yields utilizing a reaction with readily accessible reactants under mild conditions.     

化学源金属诱导多晶硅研究

以硝酸镍溶液为化学源，对于用不同方法沉积得到的非晶硅膜作晶化前驱物，都能予以不同程度的晶化.用VHF-PECVD方法获得的非晶硅膜作前驱物，易于去氢并更容易晶化.当化学源浓度不同时，晶化效果会存在一定差别，在一定的范围内，溶液浓度越高，晶化后形成的晶粒越大.退火气氛对晶化结果产生某些影响，可以发现，在N₂气氛下退火，比在大气下有更好的晶化效果.最后对物理源与化学源作诱导金属的晶化结果进行了比较，结果表明，对诱导金属源而言，化学源显示出更为有效的晶化趋势. 关键词： 金属诱导晶化 多晶硅薄膜 低温制备 退火处理     

Photoelectric properties of Cz-Py-MV2+ monolayer films

Diaza-18-crown-6-ethers appending two pyrenyl (Py-C) or two carbazolyl (Cz-C) groups form 1 : 1 host–guest complexes with methyl viologen chloride (MV²⁺). These complexes were assembled into monolayers by Langmuir-Blodgett (L-B) technique. The generated assembly involves the general structure of donor-sensitizer-acceptor (Cz-Py-MV²⁺) in space, although any of the photo- and redox-active components are not covalently bonded. This assembly was transferred on an indiumtin oxide (ITO) glass to fabricate an electrode. The photoinduced voltage of this electrode was measured with a saturated calomel reference electrode in hydroquinone (H₂Q) solution to be ca. 168 mV with the light intensity of ca. 218 mW/cm². This electrode was used as the light electrode to construct a photogalvanic cell with a platinum electrode as the dark electrode. Irradiation of the light electrode resulted in anodic photocurrent. The effects of light intensity, bias voltage, concentration of H₂Q and oxygen on the photocurrent were investigated.     

Multistimuli responsive micelles formed by a tetrathiafulvalene-functionalized amphiphile

An electroactive tetrathiafulvalene (TTF)-functionalized amphiphile 1 was designed and synthesized to investigate its self-assembling behavior in water. Dynamic light scattering (DLS), (1)H NMR, fluorescence spectrum, and cryogenic transmission electron microscopy (cryo-TEM) studies revealed that amphiphile 1 can form micelle-like aggregates via direct dissolution into water, and the micellar architectures could be disrupted either by addition of chemical oxidant Fe(ClO(4))(3) or by complexation with electron-deficient cyclobis(paraquat-p-phenylene) tetracation cyclophane (CBPQT(4+)) to release encapsulated hydrophobic dye Nile Red from the interior of micelles.     

Cumulants in the 3-dimensional Ising,O（2） and O（4） spin models

Based on the universal properties of a critical point in different systems and that the QCD phase transitions fall into the same universality classes as the 3-dimensional Ising, O（2） or O（4） spin models, the critical behavior of cumulants and higher cumulant ratios of the order parameter from the three kinds of spin models is studied. We found that all higher cumulant ratios change dramatically the sign near the critical temperature. The qualitative critical behavior of the same order cumulant ratio is consistent in these three models.     

Photoredox Catalysis of Aromatic β-Ketoesters for in Situ Production of Transient and Persistent Radicals for Organic Transformation

Radical formation is the initial step for conventional radical chemistry. Reported herein is a unified strategy to generate radicals in situ from aromatic β-ketoesters by using a photocatalyst. Under visible-light irradiation, a small amount of photocatalyst fac-Ir(ppy)₃ generates a transient α-carbonyl radical and persistent ketyl radical in situ. In contrast to the well-established approaches, neither stoichiometric external oxidant nor reductant is required for this reaction. The synthetic utility is demonstrated by pinacol coupling of ketyl radicals and benzannulation of α-carbonyl radicals with alkynes to give a series of highly substituted 1-naphthols in good to excellent yields. The readily available photocatalyst, mild reaction conditions, broad substrate scope, and high functional-group tolerance make this reaction a useful synthetic tool.