Exploring anionic emission of 2-benzoyl benzimidazole in micellar environments

In this paper, an interesting transformation of the emission of anionic conformer of 2-benzoyl bezimidazole in ionic and non-ionic micelles is reported. Deprotonation is hindered in cationic and non-ionic micelles owing to probe molecule's passage deep inside positive ion-rich Stern-layer in contrast with anionic micelle. The orientation of probe molecule in the two ionic micelles, as determined from the spectral properties is opposite in nature. Micellar environment shields the formation of mono- and di-cationic species at very low pH. Three decay times of the probe in different time domains were attributed to three possible anionic species and they are modified differently in ionic and neutral micelles. Quantum chemical calculations also predict the existence of three different possible anionic species.     

脱氢枞酸基D-A型分子的合成、空间构型及光谱性能

对三苯胺进行溴代和C-N偶联反应合成4-萘基三苯胺(a),对脱氢枞酸进行酯化、溴代、硝化、还原和C-N偶联反应合成13-[N,N-(4-萘基苯基)-苯基]胺基-脱异丙基脱氢枞酸甲酯(b)及13-[N,N-双(4-萘基苯基)]胺基-脱异丙基脱氢枞酸甲酯(c)两个化合物,通过1H MNR,13C MNR及MS对化合物的结构进行表征。为了研究化合物结构与光谱性能之间的关系,首先利用Gaussian 09程序采用密度泛函DFT/B3LYP方法,对三个化合物的空间构型进行全优化,得到它们的键长、键角和二面角,对比发现脱氢枞酸骨架和萘环的引入会影响化合物的共平面性,而萘环的引入会增大化合物的共轭程度。光谱性能方面,研究了三种化合物在甲醇、二氧六环、四氢呋喃、二氯甲烷和环己烷这5种极性逐渐减小的溶剂中的荧光发射光谱和紫外吸收光谱。结果表明,在荧光光谱中,化合物a,b和c在不同极性溶剂中最大荧光发射波长均有不同程度位移,在甲醇中最大,在环己烷中最小,但是位移并非随着极性的增大而只发生红移,在二氯甲烷、四氢呋喃和二氧六环3种极性依次增大的溶剂中,a,b,c的荧光发射波长均随着溶剂极性的增大而发生较大程度的蓝移;在同一溶剂中,化合物b和c相对于a的荧光发射波长依次发生红移,c的红移程度与b差距不大。紫外吸收光谱中,三个化合物在不同极性溶剂中的最大吸收波长也有差异,在200～250 nm区间,三个化合物均在二氯甲烷中有较大位移,在300～350 nm区间,在甲醇中位移较大,而在250～300 nm区间,最大吸收波长差别不大;在同一溶剂中,它们在300～350 nm区间的最大吸收波长差别较大,化合物c较a红移26 nm。结合结构优化所得数据可以证明,化合物的共轭程度对荧光发射光谱和紫外吸收光谱均有影响,而共平面性对荧光发射光谱影响较大。化合物a,b和c在不同极性溶剂中荧光发射光谱和紫外吸收光谱的较大变化,表明它们有明显的溶致变色行为,具有作为分子探针探测外部环境极性大小的潜能。     

Spectroscopic and theoretical evidence for the photoinduced twisted intramolecular charge transfer state formation in N,N-dimethylaminonaphthyl-(acrylo)-nitrile

The phenomenon of excited state twisted intramolecular charge transfer (TICT) process in N,N-dimethylaminonaphthyl-(acrylo)-nitrile (DMANAN) has been reported on the basis of steady-state absorption and fluorescence spectroscopy in combination with quantum chemical calculations. The absorption and fluorescence characteristics of DMANAN in solvents of different polarity reveal the presence of a single species in the ground state which forms the intramolecular charge transfer state upon photoexcitation. The observed dual fluorescence is assigned to a high-energy emission from the locally excited or the Franck-Condon state and the red-shifted emission from the charge transfer (CT) state. In polar protic solvents, hydrogen-bonding interaction on CT emission has been established from the linear dependency of the position of the low-energy emission maxima on hydrogen-bonding parameter (α). The experimental findings have been correlated with the theoretical results based on TICT model obtained at density functional theory (DFT) level. The theoretical potential energy surface for the first excited state along both the donor and acceptor twist coordinates in the gas phase obtained by time dependent density functional theory (TDDFT) method and in polar solvent by time dependent density functional theory-polarized continuum model (TDDFT-PCM) method predicts well the experimental spectral properties.     

Polymer-doped ferroelectric liquid crystal: UV absorbance,fluorescence and electro-optical study

In this study, UV absorption, fluorescence and electro-optical study have been performed for pure ferroelectric liquid crystal (FLC) and its three different concentrations, i.e. 1%, 3% and 5% of fluorescent polymer in the pure FLC. We observed that there is higher value of UV absorption for fluorescent polymer-doped system in comparison to the pure system. We have found excitation wavelength, emission wavelength and quantum yield for all the mixtures. Quantum yield shows the probability of excited state being deactivated by fluorescence rather than non-radiative mechanism. The higher value of spontaneous polarization and faster response has been observed for fluorescent polymer-doped system compared to the pure FLC system. The electro-optical study also suggests that there exists an optimum concentration of fluorescent polymer for which we have found highest spontaneous polarization and least response time.     

Photophysics of 2-(4′-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dimethylaminophenyl)imidazo[4,5-b]pyridine in Micelles: Selective Dual Fluorescence in Sodium dodecylsulphate and Triton X-100

The photophysical behavior of 2-(4′-N,N-dimethylaminophenyl)imidazo[4,5-b]pyridine (DMAPIP-b) has been studied in nonionic triton X-100 (TX-100), cationic cetyltrimethylammonium bromide (CTAB) and anionic sodium dodecylsulfate (SDS) micelles using steady state and time resolved fluorescence techniques. The molecule emits both normal and TICT fluorescence in SDS and TX-100 but emits only normal fluorescence in CTAB. This difference in behavior of the fluorophore is due to varying extent of hydrogen bonding experience by it in different micelles. Of the three possible monocations, only two kinds of monocations, MC1 (formed by protonation of pyridine ring nitrogen) and MC2 (formed by the protonation of imidazole nitrogen) are present in all the micelles (Scheme 1). DFT calculations performed on the monocations reveal that MC1 and MC2 are more stable than MC3, the monocation formed by the protonation of dimethylamino nitrogen.      

Modulation of Intramolecular Charge Transfer Emission Inside Micelles: A Fluorescence Probe for Studying Microenvironment of Micellar Assemblies

Modulation of intramolecular charge transfer reaction of ethyl ester of N,N-Dimethylaminonaphthyl-(acrylic)-acid (EDMANA) in anionic sodium dodecyl sulfate (SDS), cationic cetyltrimethylammonium bromide (CTAB) and non-ionic p-tert-octylphenoxy polyoxyethanol (Triton-X 100, TX-100) micelles has been addressed using steady state and time resolved spectroscopy. The interaction of the CT probe EDMANA with micelles and its location inside the micelles have been investigated by the study of fluorescence spectral band position of EDMANA in micelle, the effective polarity of micelle-water interface and cetyl pyridinium chloride induced fluorescence quenching measurement. The effects of urea on the properties of the micelles such as Critical Micelle Concentration and the interaction between EDMANA and micelles have been explored using EDMANA as emission probe.     

A new pH fluorescent molecular switch by modulation of twisted intramolecular charge transfer with protonation

A pH fluorescent molecular switch, BOPIM‐dma, a boron 2‐(2′‐pyridyl) imidazole complex derivatives, was investigated in aqueous system. BOPIM‐dma shows weak or no fluorescence in conventional solvents due to twisted intramolecular charge transfer (TICT). Upon protonation of the dimethylamino groups in BOPIM‐dma, its fluorescence was turned on ascribed to the inhibition of TICT. Its emission can be switched ‘on’ or ‘off’ between pH 2.4 and 4.0, and it undergoes a reversible protonation–deprotonation reaction with a pKa of 3.12. Copyright © 2013 John Wiley & Sons, Ltd.     

Photophysical parameters and fluorescence quenching of 7-diethylaminocoumarin (DEAC) laser dye

The optical properties including electronic absorption spectrum, emission spectrum, fluorescence quantum yield, and dipole moment of electronic transition of 7-diethylaminocoumarin (DEAC) laser dye have been measured in different solvents. Both electronic absorption and fluorescence spectra are red shifted as the polarity of the medium increases, indicating that the dipole moment of molecule increases on excitation. The fluorescence quantum yield of DEAC decreases as the polarity of solvent increases, a result of the role of solvent polarity in stabilization of the twisting of the intramolecular charge transfer (TICT) in excited state, which is a non-emissive state, as well as hydrogen bonding with the hetero-atom of dye. The emission spectrum of DEAC has also been measured in cationic (CTAC) and anionic (SDS) micelles, the intensity increases as the concentration of surfactant increases, and an abrupt change in emission intensity is observed at critical micelle concentration (CMC) of surfactant. 2×10⁻³ mol dm⁻³ of DEAC gives laser emission in the blue region on pumping with nitrogen laser (λ_ex=337.1 nm). The laser parameters such as tuning range, gain coefficient (α), emission cross section (σ_e), and half-life energy have been calculated in different solvents, namely acetone, dioxane , ethanol, and dimethyforamide (DMF). The photoreactivity of DEAC has been studied in CCl₄ at a wavelength of 366 nm. The values of photochemical yield (?_c) and rate constant (k) are determined. The interaction of organic acceptors such as picric acid (PA), tetracyanoethylene (TCNE), and 7,7,8,8-tetracynoquinonedimethane (TCNQ) with DEAC is also studied using fluorescence measurements in acetonitrile (CH₃CN); from fluorescence quenching study we assume the possible electron transfer from excited donor DEAC to organic acceptor forming non-emissive exciplex.     

Confinement of 4,4-Diaminodiphenyl Sulfone by γ –CD in Micellar Environment: A Spectroscopic Investigation

This paper reports the double confinement of 4,4-diaminodiphenyl sulfone (Dapsone) inside γ–cyclodextrin (CD) in presence of surfactants (cationic, anionic and nonionic) using steady-state and time-resolved fluorescence spectroscopy. Interpretation of fluorescence spectra, fluorescence anisotropy and time resolved fluorescence decay of the γ-CD?Dapsone?micellar system hints at lesser microviscosity and the partial release of the probe molecule from the supramolecular host–guest complex in ionic micelles, of which greater in cationic micelles, but due to greater restriction and rigidity in presence of non-ionic micelle makes the probe more rigidly inside CD. Changes in computed rotational decay also corroborate the above findings.

Characterization of photoluminescence spectra from poly allyl diglycol carbonate (CR-39) upon excitation with the ultraviolet radiation of various wavelengths

The induced photoluminescence (PL) from the π-conjugated polymer poly allyl diglycol carbonate (PADC) (CR-39) upon excitation with the ultraviolet radiation of different wavelengths was investigated. The absorption and attenuation coefficients of PADC (CR-39) were recorded using a UV–visible spectrometer. It was found that the absorption and attenuation coefficients of the PADC (CR-39) exhibit a strong dependence on the wavelength of ultraviolet radiation. The PL spectra were measured with a Flormax-4 spectrofluorometer (Horiba). PADC (CR-39) samples were excited by ultraviolet radiation with wavelengths in the range from 260 to 420 nm and the corresponding PL emission bands were recorded. The obtained results show a strong correlation between the PL and the excitation wavelength of ultraviolet radiation. The position of the fluorescence emission band peak was red shifted starting from 300 nm, which was increased with the increase in the excitation wavelength. The PL yield and its band peak height were increased with the increase in the excitation wavelength till 290 nm, thereafter they decreased exponentially with the increase in the ultraviolet radiation wavelength. These new findings should be considered carefully during the use of the PADC (CR-39) in the scientific applications and in using PADC (CR-39) in eyeglasses.     

Influence of surfactants on the fluorescence and absorption spectra of erythrosin in aqueous solution

The effect of certain non-ionic, anionic and cationic surfactants on the fluorescence and absorption spectra of erythrosin has been studied. Shifts towards longer wavelengths in absorption and fluorescence peaks have been observed. Also, there appears to be a marked enhancement in the fluorescence intensity of erythrosin on adding small amounts of surfactants. The shift in the absorption peak wavelength appears to be due to the binding of the surfactant with dye molecules. The enhancement in the fluorescence intensity is attributed to the disaggregation of erythrosin dye dimer and multimer forms into the monomeric form. The change in the geometry of dye molecules in the presence of cationic surfactants has also been discussed. Enhancement in the fluorescence intensity on the addition of ethanol has been observed.     

激发态质子转移分子2-(2'-羟基苯基)苯并噻唑在不同溶剂中的光谱特性

观测了2-(2’-羟基苯基)苯并噻唑(HBT)在不同极性溶剂中的吸收光谱和荧光光谱,详细研究了溶剂极性对HBT发生激发态分子内质子转移(ESIPT)影响的机制。吸收光谱表明在常态条件下,HBT在各种溶剂中都以烯醇式构型和酮式构型共同存在,但以烯醇式构型占绝大多数。荧光光谱表明在纯环己烷溶剂中,HBT被紫外光激发时,绝大多数烯醇式构型发生ESIPT转变为酮式构型,分子的ESIPT效率最大。在含有乙醇的极性溶剂中,HBT烯醇式会形成溶剂化的烯醇式构型,阻碍分子发生ESIPT反应。溶剂中乙醇含量愈多极性愈强,溶剂化烯醇式的成份就愈多,HBT的ESIPT效率就愈低。以400 nm光激发HBT溶液时,在510 nm处发现酮式构型荧光,从而确认了400 nm处的弱吸收是酮式构型的吸收;且在436和456nm处还有新的荧光峰,分析其可能来源于酮式构型去质子化阴离子的发射。     

Fluorescence Probes for Cyclodextrin Interiors

6-Propionyl-2-(dimethylamino)naphthalene (PRODAN) emits two fluorescence bands, at 510 and 435 run, when dissolved in -cyclodextrin (CD) aqueous solutions. The relative contributions of these two bands were found to depend on time and temperature. These emissions are attributed to the inclusion of PRODAN with the dimethylamino group toward the larger and smaller rims inside the -CD cavities, respectively. The first position corresponds to a slightly polar and slightly rigid environment, while the second corresponds to a hydrophobic and rigid environment relative to the aqueous polar bulk. In contrast, PRODAN in either -CD or -CD aqueous solutions emits a single fluorescence band at 525 and 510 nm, respectively. The emission of PRODAN in -CD is similar to that in water and indicates no inclusion at all. In -CD, only one kind of inclusion is possible with the dimethylamino group of PRODAN toward the larger rims of -cavities. These results are supported by fluorescence decay lifetime measurements and are consistent with our previous observations made for 4-dimethylaminobenzonitrile (DMABN) and 4-diethylaminobenzonitrile (DEABN) in - and -CD aqueous solutions [23,24]. Therefore the possibility of twisted intramolecular charge transfer (TICT) state formation in PRODAN in terms of environmental polarity and local free volume of CD cavities is discussed. These observations put PRODAN, DMABN, and other TICT compounds as fluorescence probes for CD interiors.     

Solvent Polarity and Excitation Wavelength Dependence of the Dual Fluorescence in N,N-Diethyl-4-Nitrosoaniline

Dual fluorescence in N,N-Diethyl-4-nitrosoaniline (DENA) has been studied employing absorption, excitation and emission spectroscopic techniques and computational methods. The absorption and fluorescence spectra of DENA were measured in solvents of various polarities at room temperature. The emission spectra of DENA were found to exhibit a single emission band in non polar solvent (cyclohexane) and in a highly polar solvent (acetonitrile). In the contrary, two emission bands were observed in medium polar solvents (tetrahydrofuran, 1,2-dichloroethane and dichloromethane) whereby the short (local excited; LE) and long (charge transfer; CT) emission maxima correspond to the emission maxima of the compound observed in cyclohexane and acetonitrile solutions, respectively. Moreover, the two emission bands have shown strong excitation wavelength dependence, and area normalization resulted in an iso-emissive point. The two emission maxima were in addition found to correspond to two excitation maxima in 3D fluorescence spectra. Further, two minima were obtained in potential energy surface calculation of DENA. From the experimental and computational results it was concluded that the dual fluorescence may be attributed to the presence of two different ground state structural conformers of DENA in equilibrium that are stabilized through solute-solvent interaction.     

荧光探针技术研究阿特拉津与ct-DNA的相互作用

利用分子荧光探针和紫外吸收光谱技术研究了阿特拉津（Atrazine）与小牛胸腺DNA（ct-DNA）之间的相互作用。实验中选用溴化乙锭（EB）为荧光探针,考察了阿特拉津浓度、磷酸盐、离子强度以及碘化钾对系统荧光的影响。结果表明,阿特拉津对ct-DNA-EB体系的荧光存在猝灭现象,并同时存在静态和动态两种猝灭方式。KI对ct-DNA-Atrazine体系的荧光猝灭及阿特拉津使ct-DNA紫外吸收的增色和红移现象表明阿特拉津与ct-DNA之间存在嵌插作用。磷酸盐、离子强度对ct-DNA-EB-Atrazine体系的荧光强度影响表明,阿特拉津与ct-DNA的磷酸基之间存在非特征性的静电作用,并且高离子强度不利于这种作用。     

一种新型芴类衍生物的光谱及光限幅性能分析

利用Heck反应合成了一种新型的共轭长链的芴类衍生物,研究了它的线性和非线性光学特性。测试了它在石油醚、二氯甲烷、乙酸乙酯和二甲基甲酰胺(DMF)四种不同极性溶剂中的紫外吸收和荧光光谱特性,结果表明溶剂极性对新物质紫外吸收光谱和荧光光谱有一定程度的影响,随着溶剂极性的增加,吸收光谱和荧光光谱均红移。在激发波长为1064nm皮秒激光器作用下,测试了新物质的光学非线性——光限幅效应,结果显示其透射率随入射光强的变化呈现非线性降低,限幅效应明显。根据分析得出,此光限幅效应是由三光子吸收引起。通过数据拟合,得出了新物质的三光子吸收系数γ为5.4×10-21 cm3/W2及相应的三光子吸收截面σ′3为7.3×10-77 cm6.s2。     

Emissive Properties and Intramolecular Charge Transfer of Pyrazoloquinoline Derivatives

The fluorescence properties of several pyrazoloquinoline derivatives were performed by stationary as well as by time-resolved spectrosopy. Non-donor-substituted compounds show a high quantum yield; transition dipole moments of absorption and fluorescence as well as experimental and calculated lifetimes are in excellent agreement. The donor-substituted compound DMA-DPPQ exhibits a charge transfer fluorescence in polar solvents. Additionally, dual fluorescence appears in polar protic solvents. The nature of the charge transfer state is discussed with respect to the the TICT model.     

激发态质子转移分子2-（2′-羟基苯基）苯并噻唑在不同溶剂中的光谱特性

观测了2-（2′-羟基苯基）苯并噻唑（HBT）在不同极性溶剂中的吸收光谱和荧光光谱,详细研究了溶剂极性对HBT发生激发态分子内质子转移（ESWT）影响的机制。吸收光谱表明在常态条件下,HBT在各种溶剂中都以烯醇式构型和酮式构型共同存在,但以烯醇式构型占绝大多数。荧光光谱表明在纯环己烷溶剂中,HBT被紫外光激发时,绝大多数烯醇式构型发生ESIPPT转变为酮式构型,分子的ESIPT效率最大。在含有乙醇的极性溶剂中,HBT烯醇式会形成溶剂化的烯醇式构型,阻碍分子发生ESIPT反应。溶剂中乙醇含量愈多极性愈强,溶剂化烯醇式的成份就愈多,HBT的ESIPT效率就愈低。以400nm光激发HBT溶液时,在510nm处发现酮式构型荧光,从而确认了400nm处的弱吸收是酮式构型的吸收;且在436和456nm处还有新的荧光峰,分析其可能来源于酮式构型去质子化阴离子的发射。     

Encapsulation of Labetalol, Pseudoephedrine in β-cyclodextrin Cavity: Spectral and Molecular Modeling Studies

The absorption and fluorescence spectra of labetalol and pseudoephedrine have been studied in different polarities of solvents and β-cyclodextrin (β-CD). The inclusion complexation with β-CD is investigated by UV-visible, steady state and time resolved fluorescence spectra and PM3 method. In protic solvents, the normal emission originates from a locally excited state and the longer wavelength emission is due to intramolecular charge transfer (TICT). Labetalol forms a 1:2 complex and pseudoephedrine forms 1:1 complex with β-CD. Nanosecond time-resolved studies indicated that both molecules show triexponential decay. Thermodynamic parameters (ΔG, ΔH, ΔS) and HOMO, LUMO orbital investigations confirm the stability of the inclusion complex. The geometry of the most stable complex shows that the aromatic ring is deeply self included inside the β-CD cavity and intermolecular hydrogen bonds were established between host and guest molecules. This suggests that hydrophobic effect and hydrogen bond play an important role in the inclusion process.     

Self-Aggregation Behavior of meso-Tetra-(4-trimethylaminophenyl)porphyrin Encapsulated in Reverse Micelles

The aggregation behavior of cationic meso-tetra-(4-trimethylaminophenyl)porphyrin (TAPP) was investigated in two reverse micelles (RM) of ionic surfactants, cetyltrimethylammonium bromide (CTAB) and bis(2-ethylhexyl)sulfosuccinate (AOT) using absorption spectroscopy, fluorescence spectroscopy, and resonance light scattering spectroscopy. TAPP showed different types of aggregation upon varying the ratio of water concentration to CTAB concentration, ω₀. The charge on the surfactant used to form reverse micelles determines the aggregation of porphyrin. The addition of hydrochloric acid can transform the H-aggregates of TAPP into monomers, while the addition of sodium hydroxide led to J-aggregation. Ionic strength had no significant influence on the aggregation of TAPP.