囊泡型荧光纳米界面的构建及其对CD44蛋白的比例型传感

本文设计合成了两亲性Eu(Ⅲ)配合物(Eu L^3+)、两亲性香豆素衍生物(CA)以及荧光素修饰的透明质酸(HA-FA).Eu L^3+和CA可在水中共组装形成带正电荷的囊泡型荧光纳米界面(Eu L^3+/CA).HA-FA可通过静电引力络合在Eu L^3+/CA表面,促使CA与FA之间发生有效的荧光共振能量转移,体系的荧光发射以荧光素的绿色荧光为主.当肿瘤细胞标识物CD44蛋白与络合在囊泡表面上的透明质酸发生特异相互作用后,降低了CA与FA之间的能量转移效率,体系的荧光发射从绿色转变为蓝色.据此,实现了对CD44的高灵敏检测(DL=1.79×10^-7g/m L),而所测试的氨基酸、蛋白质等生物分子几乎不对荧光纳米界面的荧光性质产生影响.基于此,我们成功地将Eu L^3+/CA/HA-FA用于人乳腺癌细胞MCF-7和MDA-MB-231悬浮液中CD44蛋白的高效检测,该工作为构建新型CD44蛋白荧光探针提供了思路,为癌症早期诊断和治疗奠定了基础.     

Electrochemistry in Carbon‐based Quantum Dots

Electrochemistry belongs to an important branch of chemistry that deals with the chemical changes produced by electricity and the production of electricity by chemical changes. Therefore, it can not only act a powerful tool for materials synthesis, but also offer an effective platform for sensing and catalysis. As extraordinary zero‐dimensional materials, carbon‐based quantum dots (CQDs) have been attracting tremendous attention due to their excellent properties such as good chemical stability, environmental friendliness, nontoxicity and abundant resources. Compared with the traditional methods for the preparation of CQDs, electrochemical (EC) methods offer advantages of simple instrumentation, mild reaction conditions, low cost and mass production. In return, CQDs could provide cost‐effective, environmentally friendly, biocompatible, stable and easily‐functionalizable probes, modifiers and catalysts for EC sensing. However, no specific review has been presented to systematically summarize both aspects until now. In this review, the EC preparation methods of CQDs are critically discussed focusing on CQDs. We further emphasize the applications of CQDs in EC sensors, electrocatalysis, biofuel cells and EC flexible devices. This review will further the experimental and theoretical understanding of the challenges and future prospective in this field, open new directions on exploring new advanced CQDs in EC to meet the high demands in diverse applications.     

Two new NiII and ZnII metal–organic frameworks of glutarate and 1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene ligands: syntheses,structures and luminescence sensing properties

Two new metal–organic frameworks (MOFs), namely, three‐dimensional poly[diaquabis{μ₂‐1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene}bis(μ₂‐glutarato)dinickel(II)] monohydrate], {[Ni₂(C₅H₆O₄)₂(C₁₆H₁₈N₄)₂(H₂O)₂]·H₂O}_n or {[Ni₂(Glu)₂(1,4‐mbix)₂(H₂O)₂]·H₂O}_n, ( I ), and two‐dimensional poly[[{μ₂‐1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene}(μ₂‐glutarato)zinc(II)] tetrahydrate], {[Zn(C₅H₆O₄)(C₁₆H₁₈N₄)]·4H₂O}_n or {[Zn(Glu)(1,4‐mbix)]·4H₂O}_n ( II ), have been synthesized hydrothermally using glutarate (Glu^2?) mixed with 1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene (1,4‐mbix), and characterized by single‐crystal X‐ray diffraction, IR and UV–Vis spectroscopy, powder X‐ray diffraction, and thermogravimetric and photoluminescence analyses. Ni^II MOF ( I ) shows a 4‐connected 3D framework with point symbol 6⁶, but is not a typical dia network. Zn^II MOF ( II ) displays a two‐dimensional 4⁴‐ sql network with one‐dimensional water chains penetrating the grids along the c direction. The solid‐state photoluminescence analysis of ( II ) was performed at room temperature and the MOF exhibits highly selective sensing toward Fe³⁺ and Cr₂O₇^2? ions in aqueous solution.     

A Computational Study of CIONO2H+: Structure and Vibrations

Two protonated forms of chlorine nitrate, HClONO⁺ ₂ and ClONO₂H⁺, are treated ab initio by the Hartree-Fock and the second order Møller-Plesset perturbation approach with the standard 6–31G* basis set. Both minimum energy structures are planar (C ₃ symmetry) and their structural, energy, and vibrational parameters are reported. The computations conclude that the proton attacks the chlorine nitrate at its central, not end, oxygen atom. The protonation causes a considerable elongation of the central ON bond which becomes most probable place of cleavage. The dissociation should yield the neutral HOCl and NO⁺ ₂. These quantum-chemical findings well agree with the previous experimental indications.

     

5-(Perfluorooctylthio)acetamidofluorescein (5-FOAF) as a convenient tag for inspecting the surface coverage of fluorinated coatings

Fluorinated compounds are commonly used for anti-stick coating but it is difficult to inspect the coverage of the coating without expensive instruments. Herein, we demonstrated that the 5-(perfluorooctylthio)acetamidofluorescein (5-FOAF) probe can be synthesized in one step and used as a testing reagent to inspect the fluorinated coating on silica- or metal-based surfaces. 5-FOAF is composed of a perfluoroalkyl domain, which has high specific affinity towards fluorinated compounds, and a fluorophore domain, which exhibits fluorescence emission visible by naked eyes. Thus, 5-FOAF will retain on the surface coated with fluorinated compounds but not on the un-coated surface and the emitted fluorescence from the retained tags serves as a semi-quantitative measure of the fluorine coverage across the surface. For this study, silica-based or metal-based surfaces were activated by silane chemistry and then coated with fluorinated compounds. The coating procedure was judiciously optimized to achieve a homogeneous coating. 5-FOAF probe was synthesized in-house and shown to retain on the fluorinated surface 2-5 times stronger than the bare surface. Moreover, by studying the retention on a non-fluoro hydrophobic substrate made of polydimethylsiloxane, the affinity of 5-FOAF with the fluorinated coating was confirmed to be specific and distinguishable from nonspecific hydrophobic interaction. In conclusion, we synthesized a novel chemical, 5-FOAF, and demonstrated its usefulness as a simple testing reagent for fluorinated coatings.     

Single image non-uniformity correction using compressive sensing

A non-uniformity correction (NUC) method for an infrared focal plane array imaging system was proposed. The algorithm, based on compressive sensing (CS) of single image, overcame the disadvantages of “ghost artifacts” and bulk calculating costs in traditional NUC algorithms. A point-sampling matrix was designed to validate the measurements of CS on the time domain. The measurements were corrected using the midway infrared equalization algorithm, and the missing pixels were solved with the regularized orthogonal matching pursuit algorithm. Experimental results showed that the proposed method can reconstruct the entire image with only 25% pixels. A small difference was found between the correction results using 100% pixels and the reconstruction results using 40% pixels. Evaluation of the proposed method on the basis of the root-mean-square error, peak signal-to-noise ratio, and roughness index (ρ) proved the method to be robust and highly applicable.     

Improvements for ground-based remote sensing of atmospheric aerosol properties by additional polarimetric measurements

We discuss the improvements in the aerosol properties characterization resulting from the additional multi-wavelength polarization measurements measured by a new CIMEL polarized sun/sky-photometer, CE318-DP. In order to process direct-sun, sky and polarization measurements in a wide spectral range (340–1640 nm), we developed new calibration methods and strategies, e.g. using the Langley plot method to calibrate both direct-sun irradiance and sky radiance, as well as combining laboratory facilities with a vicarious method to calibrate the polarized sky measurements. For studying the impact of new polarimetric measurements on the retrievals of aerosol properties, we have processed an extensive record of field measurements using an updated Dubovik and King retrieval algorithm [Dubovik O, Sinyuk A, Lapyonok T, Holben BN, Mishchenko MI, et al. Application of spheroid models to account for aerosol particle nonsphericity in remote sensing of desert dust. J Geophys Res 2006;111:D11208.]. A preliminary analysis shows that adding polarization in the inversion can reduce possible errors (notably for about 30% of our field cases) in the fine mode size distribution, real part of refractive index and particle shape parameter retrievals, especially for small particles.     

Light‐Activated Sensitive Probes for Amine Detection

Our new, simple, and accurate colorimetric method is based on diarylethenes (DAEs) for the rapid detection of a wide range of primary and secondary amines. The probes consist of aldehyde‐ or ketone‐substituted diarylethenes, which undergo an amine‐induced decoloration reaction, selectively to give the ring‐closed isomer. Thus, these probes can be activated at the desired moment by light irradiation, with a sensitivity that allows the detection of amines at concentrations as low as 10⁻⁶ m in solution. In addition, the practical immobilization of DAEs on paper makes it possible to detect biogenic amines, such as cadaverine, in the gas phase above a threshold of 12 ppbv within 30 seconds.     

Anion exchange in trimethyl‐ and triphenyltin complexes with chromogenic ligands: solution equilibria and colorimetric anion sensing

A series of organotin(IV) compounds R₃Sn(A) where R = Me or Ph and A is a chromogenic nitrophenolate ligand were prepared and studied as possible colorimetric sensors for anions (F⁻, Cl⁻, Br⁻, AcO⁻, H₂PO₄⁻). Equilibrium constants for a complete set of reactions between R₃Sn(A) with A = 2‐amino‐4‐nitrophenolate (ANP) or 4‐nitrophenolate and anions (X⁻) involving formation of complexes R₃Sn(A)(X)⁻ and substitution products R₃Sn(X) and R₃Sn(X)₂⁻ were determined by UV‐vis and ¹H NMR titrations in MeCN and DMSO. The binding selectivity was AcO⁻ > F⁻ > H₂PO₄⁻ > Cl⁻ ≫ Br⁻ in both solvents and both for R = Me and Ph with higher affinity for R = Ph. Compounds with A = ANP were found to have the optimum properties as anion sensors allowing optical detection of F⁻, AcO⁻ and H₂PO₄⁻ anions in the 5–100 µM range by appearance of an intense absorption band of free ANP resulting from its substitution with the analyte. Selectivity and affinity of anion interactions with R₃Sn(ANP) are similar to those for thiourea receptors, but the organotin receptor produces a much larger naked eye detected optical signal, operates equally well in nonpolar and polar solvents and tolerates the presence of up to 20% vol. of water in DMSO. Copyright © 2011 John Wiley & Sons, Ltd.     

基于腔辅助相互作用的远距离信息传递

提出了一种基于腔辅助相互作用的远距离信息传递的方案.在该方案中,通过让一束相干光和一个囚禁在腔里面的原子进行相互作用,可以使相干光产生一个可控的相位偏移.用这种腔辅助相互作用完成了原子态和光场态之间信息的相互转移.最后我们演示了远距离信息传递方案,该方案在当前实验条件下是可行的,并且在理想条件下,成功的概率几乎为1.