HCl/NH_3敏感的卟啉-二氧化硅反蛋白石光子晶体荧光传感器

将反蛋白石结构的光子晶体引入到腐蚀性气体检测体系,制备得到卟啉-二氧化硅反蛋白石光子晶体(TPP-SiO_2IOPCs)荧光传感器。相对于空白样,TPP-SiO_2IOPCs传感器实现了氯化氢(HCl)气体检测信号200倍的增强,这主要归因于反蛋白石型光子晶体的大孔结构和慢光子效应。同时,TPP-SiO_2IOPCs传感器对于HCl气体的猝灭效率可达75%,比空白样的提高了25%,而且经HCl气体处理后的传感器通入氨气(NH_3)后,初始的荧光强度几乎完全恢复。在HCl和NH_3条件下进行5个循环后,TPP-SiO_2IOPCs传感器表现出良好的可重复使用性。该研究对于发展高效的荧光传感器提供了新的思路。     

The Naked‐Eye Detection of NH3–HCl by Polyaniline‐Infiltrated TiO2 Inverse Opal Photonic Crystals

A reversible color change of a polyaniline‐infiltrated TiO₂ inverse opal photonic crystal (PC) film can be obtained when the PC is switched from an acidic to alkali vapor environment. In a saturated NH₃ environment, the stopband of the as‐prepared PCs changes from 556 to 688 nm; such large shift of 132 nm could be observed, corresponding to a clear color change from green to red. After placing in HCl vapor, the stopband undergoes a blue‐shift and the color turns back to green. The result is ascribed to PANI being doped or dedoped by acid or base and the effective refractive index of the PC film varying accordingly. The naked‐eye detection of NH₃ and HCl vapors can be realized by the reversible color change of the PC film, which is of importance for chemical and biological sensors.     

Bio‐Inspired Photonic‐Crystal Microchip for Fluorescent Ultratrace Detection

Ultratrace detection attracts great interest because it is still a challenge to the early diagnosis and drug testing. Enriching the targets from highly diluted solutions to the sensitive area is a promising method. Inspired by the fog‐collecting structure on Stenocara beetle’s back, a photonic‐crystal (PC) microchip with hydrophilic–hydrophobic micropattern was fabricated by inkjet printing. This device was used to realize high‐sensitive ultratrace detection of fluorescence analytes and fluorophore‐based assays. Coupled with the fluorescence enhancement effect of a PC, detection down to 10^?16 mol L^?1 was achieved. This design can be combined with biophotonic devices for the detection of drugs, diseases, and pollutions of the ecosystem.     

三联噻吩衍生物功能化SiO2反蛋白石光子晶体荧光薄膜的制备及应用

将单分散聚苯乙烯微球乳液与SiO₂溶胶均匀混合后, 于恒温恒湿条件下, 竖直沉积共组装制备得到蛋白石型光子晶体薄膜, 然后利用牺牲模板法制得SiO₂反蛋白石光子晶体薄膜. 该薄膜依次经过浓硫酸与过氧化氢混合液、 3-氨丙基三甲氧基硅烷的甲苯溶液、 三联噻吩的三氯甲烷溶液和硼氢化钠的甲醇溶液处理后, 得到三联噻吩衍生物功能化的SiO₂反蛋白石光子晶体. 结果表明, 制备得到的光子晶体薄膜在512 nm处有荧光发射, 经紫外辐射后荧光猝灭, 甲醛气氛下458 nm处又出现新的荧光发射峰. 在甲醛气氛下20 s即可观察到荧光发射, 空气氛围下可恢复, 10次循环仍可保持强的荧光发射, 可重复性良好. 以无反蛋白石光子晶体结构的三联噻吩衍生物的平滑膜与甲醛作用的体系作为参比, 以330和400 nm聚苯乙烯微球为模板制备的三联噻吩功能化反蛋白石光子晶体, 在甲醛气氛中发射的荧光分别增强47.5和78.6倍. 这是由于光子晶体光子禁带的红带边和蓝带边与荧光发射波长相重叠, 产生了慢光子效应, 极大地增强了发射的荧光强度.     

Exciton Migration and Surface Trapping for a Photonic Crystal Displaying Charge‐Recombination Fluorescence

A compact donor–acceptor molecular dyad has been synthesized by attaching an N,N‐dimethylamino fragment to a naphthalic anhydride residue. The dyad shows fluorescence from an intramolecular charge‐transfer state (i.e., charge‐recombination fluorescence) in solution, with the photo‐physical properties being strongly dependent on the solvent polarity. Similar emission is seen for single crystals of the target compound, the molecules being aligned head‐to‐head, although time‐resolved emission profiles display dual‐exponential kinetics. A second polymorph with the head‐to‐tail alignment also gives rise to two lifetimes that differ somewhat from those of the first structure, which are assigned to bulk and surface‐bound molecules. Growing the crystal in the presence of Rhodamine B localizes the dye around the surface. Excitation of the crystal is followed by sub‐ps exciton migration along the aligned stacks, with occasional crossing to adjacent stacks and trapping at the surface. Rhodamine B present at very low levels acts as the acceptor for excitons entering the surface layer. Crystals embedded in a polyester resin form an artificial light‐harvesting antenna able to sensitize an amorphous silicon solar cell.     

Highly Selective Anionic Counterion‐based Fluorescent Sensor for Hg2+ by Grafted Conjugated Polyelectrolytes

Grafted conjugated polyelectrolytes were synthesized for the first time and characterized. The polymers demonstrated properties of a convenient and efficient protocol for creating Hg²⁺ sensors. The unique character of the new material comes from an anionic counterion nature with no external cofactors, and imparts high selectivity and fast detection for mercury ion in a fluorescence probe. The concept may be potentially applied to create new sensors for monitoring other ions.

     

Directional Study of the Optical Properties of Tb3+‐ and Eu3+‐Doped Nanoparticles Embedded in Silica Photonic Crystals

The effects of the stop band (SB) in colloidal photonic crystals composed of silica spheres containing Eu³⁺‐ and Tb³⁺‐doped yttria nanoparticles are analysed. Reflection and transmission spectra indicate movement of the stop band, due to the 111 series of planes, towards shorter wavelengths with increasing angle of observation. The profile of the emission spectra is modified by the presence of the SB depending on the angle of measurement. Such a modification is more effective for a narrow emission band and it is thus more evident in the case of Tb³⁺ than Eu³⁺. An angular effect is also observed in the lifetime, which presents two maxima and one minimum. In the case of Tb³⁺ the maxima are at observation angles of 35 and 50°, and the minimum at 45°. We attribute this behaviour to penetration of the excitation beam at 475 nm modulated by the stop band. The ions excited in this way emit from different depths in the crystal, and therefore their lifetime will be affected differently by the same stop band, depending on the thickness of the crystal that must be crossed. Eu³⁺ shows a similar but less pronounced effect for two reasons: first, the main stop band (due to the 111 planes) is not effective at the excitation wavelength of 392 nm; second, the broadness of the Eu³⁺ emission is comparable to the width of the SB, and a decrease in the transition rate at the wavelength of the SB maximum is compensated by an increase at the sides of the SB.     

Selective Detection of Hg2+ Ions with Boron Dipyrromethene‐Based Fluorescent Probes Appended with a Bis(1,2,3‐triazole)amino Receptor

By using a copper‐promoted alkyne–azide cycloaddition reaction, two boron dipyrromethene (BODIPY) derivatives bearing a bis(1,2,3‐triazole)amino receptor at the meso position were prepared and characterized. For the analogue with two terminal triethylene glycol chains, the fluorescence emission at 509 nm responded selectively toward Hg²⁺ ions, which greatly increased the fluorescence quantum yield from 0.003 to 0.25 as a result of inhibition of the photoinduced electron transfer (PET) process. By introducing two additional rhodamine moieties at the termini, the resulting conjugate could also detect Hg²⁺ ions in a highly selective manner. Upon excitation at the BODIPY core, the fluorescence emission of rhodamine at 580 nm was observed and the intensity increased substantially upon addition of Hg²⁺ ions due to inhibition of the PET process followed by highly efficient fluorescence resonance energy transfer (FRET) from the BODIPY core to the rhodamine moieties. The Hg²⁺‐responsive fluorescence change of these two probes could be easily seen with the naked eye. The binding stoichiometry between the probes and Hg²⁺ ions in CH₃CN was determined to be 1:2 by Job′s plot analysis and ¹H NMR titration, and the binding constants were found to be (1.2±0.1)×10¹¹ m ^?2 and (1.3±0.3)×10¹⁰ m ^?2, respectively. The overall results suggest that these two BODIPY derivatives can serve as highly selective fluorescent probes for Hg²⁺ ions. The rhodamine derivative makes use of a combined PET‐FRET sensing mechanism which can greatly increase the sensitivity of detection.     

An Ultra‐High Fluorescence Enhancement and High Throughput Assay for Revealing Expression and Internalization of Chemokine Receptor CXCR4

Revealing chemokine receptor CXCR4 expression, distribution, and internalization levels in different cancers helps to evaluate cancer progression or prognosis and to set personalized treatment strategy. We here describe a sensitive and high‐throughput immunoassay for determining CXCR4 expression and distribution in cancer cells. The assay is accessible to a wide range of users in an ordinary lab only by dip‐coating poly(styrene‐co‐N‐isopropylacrylamide) spheres on the glass substrate. The self‐ assembled spheres form three‐dimensional photonic colloidal crystals which enhance the fluorescence of CF647 and Alexa Fluor 647 by a factor of up to 1000. CXCR4 in cells is detected by using the sandwich immunoassay, where the primary antibody recognizes CXCR4 and the secondary antibody is labeled with CF647. With the newly established assay, we quantified the total expression of CXCR4, its distribution on the cell membrane and cytoplasm, and revealed their internalization level upon SDF‐1α activation in various cancer cells, even for those with extremely low expression level.     

A Naphthalimide‐Based Cd2+ Fluorescent Probe with Carbamoylmethyl Groups Working as Chelators and PET‐Promoters under Neutral Conditions

We have developed a novel naphthalimide‐based Cd²⁺ fluorescent probe ( 1 ), featuring almost no background response, high sensitivity and selectivity toward Cd²⁺ through its high association constant [K=(2.10±0.423)×10⁶], and a practical working pH range. Membrane‐permeability was conferred on 1 by replacing the imide and amide substituents with n‐butyl groups, and hence the derivative ( 4 ) has found practical utility on fluorescent imaging of Cd²⁺ in HeLa cells. Comparison of fluorescent properties between various compounds derived from 1 has demonstrated that the carbamoylmethyl groups in 1 function not only as Cd²⁺ chelators but also as promoters for photoinduced electron transfer (PET) by lowering the basicity of the two tertiary amino groups. As a result, 1 and 4 exhibited highly practical performance as Cd²⁺ probes under neutral conditions.     

Coumarin‐3‐Aldehyde as a Scaffold for the Design of Tunable PET‐Modulated Fluorescent Sensors for Neurotransmitters

NeuroSensor 521 (NS521) is a fluorescent sensor for primary‐amine neurotransmitters based on a platform that consists of an aryl moiety appended to position C4 of the coumarin‐3‐aldehyde scaffold. We demonstrate that sensors based on this platform behave as a directly linked donor–acceptor system that operates through an intramolecular acceptor‐excited photoinduced electron transfer (a‐PET) mechanism. To evaluate the PET process, a series of benzene‐ and thiophene‐substituted derivatives were prepared and the photophysical properties, binding affinities, and fluorescence responses toward glutamate, norepinephrine, and dopamine were determined. The calculated energy of the highest occupied molecular orbital (E_HOMO) of the pendant aryl substituents, along with oxidation and reduction potential values derived from the calculated molecular orbital energy values of the platform components, allowed for calculation of the fluorescence properties of the benzene sensor series. Interestingly, the thiophene derivatives did not fit the typical PET model, highlighting the limitations of the method. A new sensor, NeuroSensor 539, displayed enhanced photophysical properties aptly suited for biological imaging. NeuroSensor 539 was validated by selectively labeling and imaging norepinephrine in secretory vesicles of live chromaffin cells.     

Hg2+‐Induced In Situ Generated Radical Cation of (S)‐BINOL‐Based Polymer for Highly Enantioselective Recognition of Phenylalaninol

Phenylalaninol enantiomers are one of the most important chiral compounds due to its presence in biologically active molecules and pharmaceutical products. In this paper, a novel chiral fluorescence polymer sensor incorporating (S)‐BINOL and oligomeric aniline via a nucleophilic addition–elimination reaction is designed and synthesized. Polymer sensor exhibits “turn‐off” fluorescence quenching response upon the addition of Hg²⁺, and “turn‐on” moderate fluorescence enhancement behavior towards phenylalaninol enantiomers. Meanwhile, this kind of (S)‐BINOL‐based polymer sensor can exhibit highly selective enantioselective recognition response towards (L)‐phenylalaninol upon the addition of Hg²⁺ and the value of ef can reach as high as 5.4, which can be attributed to the formation of in situ generated radical cation arisen from oligomeric aniline moiety by Hg²⁺ induction.

     

A Highly Sensitive and Selective Fluorescence Chemosensor for Cu2+ and Zn2+ Based on Solvent Effect

A novel fluorescence chemosensor 1 based on (R)‐binaphthyl‐salen can exhibit highly sensitive and selective recognition responses toward Cu²⁺ by "turn‐off" fluorescence quench type in THF/H₂O, and Zn²⁺ by "turn‐on" fluorescence enhancement type in CHCl₃/CH₃CN, respectively, suggesting that solvents can dramatically affect the responsive properties of salen‐based chemosensor. In addition, Cu²⁺ can lead to the most pronounced changes of CD spectra without the influence of solvents, which indicates this kind chemosensor can also be used as a sole Cu²⁺ probe based on CD spectra.     

2-萘-(OCH2CH2)n-金刚胺与6-单取代环糊精衍生物的光诱导电子转移反应

A number of naphthalene donor compounds that possess an adamantanamine binding moiety and an (OCH2CH2)n (nn1, 2, 3, 4, 6, 8) spacer were synthesized. The fluorescence quenching between these donor substrates and mono-6-O-p-nitrobenzoyl-β-cyclodextrin (pNBCD) and mono-6-O-m-nitrobenzoyl-β-cyclodextrin(mNBCD) was studied in detail. It was found that very efficient fluorescence quenching could occur in these supramolecular systems. This quenching was attributed to the photoinduced electron transfer inside the supramolecular assembly between the naphthalene donors and cyclodextrin acceptors. Detailed Stern-Volmer constants were measured and they were partitioned into dynamic Stern-Volmer quenching constants and static binding constants. It was demonstrated that the binding constants between all the naphthalene compounds and cyclodextrins are the same as they possess the same binding site, i.e., adamantanamine.     

Inner‐sphere reorganization for redox pairs M(NH3)62+/3+ (M=Mn,Fe, and Co): Models and calculations

The inner‐shell reorganization and activation models of the electron‐transfer reactions of transition‐metal hexammine complexes are presented. The inner‐shell reorganization and activation energies of several hexammine redox pairs M(NH₃)₆^2+/3+ (M=Mn, Fe, and Co) in self‐exchange reactions are studied by different formalisms. The extent of the anharmonicities in the vibration between the metal–ion and the ligands in the reorganization process of these complexes is determined. The inner‐shell barriers of these redox pairs are dependent on reorganization model used. The contribution of the individual reactants to the inner‐shell barrier is sensitive to the model used. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Detection of Hg2+ and F− Ions by Using Fluorescence Switching of Quantum Dots in an Au‐Cluster–CdTe QD Nanocomposite

A single probe of an Au nanocluster–CdTe quantum dots nanocomposite has been developed by using tripeptide‐capped CdTe quantum dots (QD) and bovine serum albumin (BSA) protein‐conjugated Au₂₅ nanocluster (NC) for detection of both Hg²⁺ ion and F^? ion. The formation of Au‐NC–CdTe QD nanocomposite has been confirmed by TEM, steady state and time resolved spectroscopy, CD and FTIR studies. A significant signal off (74 % PL quenching at 553 nm) phenomenon of this nanocomposite is observed in presence of 6.56×10^?7 M Hg²⁺ ion, due to salt‐induced aggregation. However, a dramatic PL enhancement (128 %) of the Au‐NC–CdTe QD nanocomposite is observed in presence of 8.47×10^?7 M F^? anion. The calculated limit of detections (LOD) of Hg²⁺ ion concentration and F^? ion concentration are found to be 9 and 117 nM , respectively, which are within the safety range set by the United States Environment Protection Agency. Thus, the simple Au‐NC–CdTe QD optical‐based sensor is very useful to detect both toxic cations and anions.