Photoinduced intramolecular electron transfer and triplet energy transfer in a steroid-linked norbornadiene-carbazole dyad

Bichromophoric compound 3 beta-((2-(methoxycarbonyl)bicyclo[2.2.1]hepta-2,5-diene-3-yl)carboxy)androst-5-en-17 beta-yl-[2-(N-carbazolyl)acetate] (NBD-S-CZ) was synthesized and its photochemistry was examined by fluorescence quenching, flash photolysis, and chemically induced dynamic nuclear polarization (CIDNP) methods. Fluorescence quenching measurements show that intramolecular electron transfer from the singlet excited state of the carbazole to the norbornadiene group in NBD-S-CZ occurs with an efficiency (Phi SET) of about 14 % and rate constant (kSET) of about 1.6 x 10(7) s-1. Phosphorescence and flash photolysis studies reveal that intramolecular triplet energy transfer and electron transfer from the triplet carbazole to the norbornadiene group proceed with an efficiency (TET + TT) of about 52 % and rate constant (kTET + kTT) of about 3.3 x 10(5) s-1. Upon selective excitation of the carbazole chromophore, nuclear polarization is detected for protons of the norbornadiene group (emission) and its quadricyclane isomer (enhanced absorption); this suggests that the isomerization of the norbornadiene group to the quadricyclane proceeds by a radical-ion pair recombination mechanism in addition to intramolecular triplet sensitization. The long-distance intramolecular triplet energy transfer and electron transfers starting both from the singlet and triplet excited states are proposed to proceed by a through-bond mechanism.     

Magnetic bead-based approach to monitoring of cigarette smoke-induced DNA oxidation damage and screening of natural protective compounds

Cigarette smoking can damage DNA and induce spontaneous mutagenesis or carcinogenesis. Here, we describe a novel strategy for in situ monitoring of cigarette smoke-induced DNA oxidation damage and offer a method for screening natural compounds that protect DNA against tobacco smoke. The present protocol takes advantage of a fast and simple magnetic separation/mixing method and a highly sensitive chemiluminescence (CL) ELISA. The DNA immobilized on the magnetic beads was oxidized by the smoke in the absence or presence of natural compounds, and then oxidative DNA was conveniently held by magnetic force, whereas the complex tobacco smoke matrix and any remaining compounds were completely eliminated by extensive washing, and possible interferences were thus removed and oxidative damage was then sensitively monitored by CL ELISA. A library of 32 natural products was then screened and three were found to protect DNA from oxidative damage and thus may be promising compounds for the development of new drugs. Moreover, the protection effect of these three natural compounds against DNA oxidation damage was successfully classified by directly spiking them in the reference cigarettes. In addition, the potential to screen a mixture in a complex sample matrix, such as crude extracts, was also demonstrated, and hence the proposed technique can screen compounds within a complex matrix and enhance the screening throughput.     

RbEuI3和CsEuI3的合成及结构与性质研究

本文用一步法合成了新合物ＲｂＥｕＩ３与ＣｓＥｕＩ３，测定了化合物的组成，结构，熔点，密度，荧光光谱，极谱电位及磁矩，确定了化合物中Ｅｕ的价态为正二价。     

Negative‐pressure‐induced collector for a self‐balance free‐flow electrophoresis device

Uneven flow in free‐flow electrophoresis (FFE) with a gravity‐induced fraction collector caused by air bubbles in outlets and/or imbalance of the surface tension of collecting tubes would result in a poor separation. To solve these issues, this work describes a novel collector for FFE. The collector is composed of a self‐balance unit, multisoft pipe flow controller, fraction collector, and vacuum pump. A negative pressure induced continuous air flow rapidly flowed through the self‐balance unit, taking the background electrolyte and samples into the fraction collector. The developed collector has the following advantages: (i) supplying a stable and harmonious hydrodynamic environment in the separation chamber for FFE separation, (ii) effectively preventing background electrolyte and sample flow‐back at the outlet of the chamber and improving the resolution, (iii) increasing the preparative scale of the separation, and (iv) simplifying the operation. In addition, the cost of the FFE device was reduced without using a multichannel peristaltic pump for sample collection. Finally, comparative FFE experiments on dyes, proteins, and cells were carried out. It is evident that the new developed collector could overcome the problems inherent in the previous gravity‐induced self‐balance collector.     

Synthesis of mesoporous-silica coated multi-branched gold nanoparticles for surface enhanced Raman scattering evaluation of 4-bromomethcathinone

Mesoporous silica-coated multi-branched gold nanoparticles (bAu@mesoSiO₂) aiming for enhanced Raman sensing for 4-bromomethcathinone (4-BMC) detection is reported. In this work, we present an effective strategy to probe the Raman signal of 4-MBC. Morphologies and optical properties of the synthesized materials with different [Au³⁺]/[Au⁰] ratios are characterized utilizing transmission electron microscopy (TEM), UV–vis and mid-infrared spectroscopy. Both experimental and theoretical (simulation) studies were investigated. Taking advantages of gold core branches that provide highly localized and strongly enhanced electromagnetic fields due to plasmon resonance, surface-enhanced Raman scattering (SERS) is observed. The experimental results show that the SERS intensity exhibits a 100-fold increase with the increased average length and quantity of gold branches (nano tips). The analytical performance yielded a detection limit of 0.1?mg/ml for the 4-MBC target within 5?mins. The sensing method will likely find further improvement and broad use in the forensic science. Besides rapid detection and portability, the combination of the Raman effect and enhanced materials imparts other notable advantages, such as its non-contact and free of reagents.     

Facile fabrication of metallic nanostructures by tunable cracking and transfer printing

You crack me up: A topographically patterned PDMS stamp was coated with thin metal film and swelled under organic vapor to induce the tunable cracking of the brittle film into metallic nanostructures (see SEM images, scale bars 1?μm). UV/Vis spectra, OLED efficiency, and SERS spectra demonstrate the fine controllability of the metallic nanostructures, the well-ordered and highly regulable surface plasmons, and the facile fabrication process.     

A High Sensitivity Electrochemical Sensor Based on Fe3+‐Ion Molecularly Imprinted Film for the Detection of T‐2 Toxin

The excellent detection sensitivity in various matrices of T‐2 toxin (T‐2), which has cytotoxic and immunosuppressive effects in DNA and RNA synthesis, is a highly desirable characteristic. A sensitive molecularly imprinted electrochemical sensor was constructed for the selective detection of T‐2. In this study, iron ions (Fe³⁺) were introduced to increase the chelation of the metal ions and templates for preparing molecularly imprinted polymers (MIPs). With the increased chelation of the metal ions and templates, the selectivity and sensitivity of the MIPs were effectively improved. The imprinted sensor was successfully employed to detect T‐2 in cereals and human serum samples.     

SYNTHESIS AND CHARACTERIZATION OF A NOVEL BLUE LIGHT EMITTING ROD-COIL DIBLOCK OLIGOMER

Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl toquinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M_w ca. 750) as flexible segments, were synhesized. Thechemical structure and the number of repeating unit in PEO coil and PPP rod were characterized by ~1H-NMR and MALDI-TOF mass spectromeny. The diblock oligomers showed good solubility in common organic solvents and aggregated in wateras characterized by a blue shift in UV-vis absorption spectra, a red shift in emission spectra, quenching of the fluorescenceand formation of the microfibrilla and fractal-like structures. The formation of different supramolecular structures meant thatthis effort might lead to commercial important highly organized functional materials.     

K-g-框架扰动的稳定性

在Hilbert空间中定义了K-g-框架,研究了Hilbert空间中K-g-框架扰动的稳定性,利用分析与框架理论上的方法和技巧,得到了K-g-框架满足扰动稳定性的一些充分条件,所得的结论推广了g-框架扰动稳定性的相关结果.     

Direct C(sp3)−H difluoroallylation of diarylmethanes with α-(trifluoromethyl) styrenes at room temperature

A rapid and convenient method for the synthesis of 3,3-difluoroallylated diarylmethanes by reactions of diarylmethanes with α-(trifluoromethyl)styrenes in the presence of LiHMDS at room temperature was developed.