- Rational Design of Crystallization-Induced-Emission Probes To Detect Amorphous Protein Aggregation in Live Cells
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Unlike amyloid aggregates, amorphous protein aggregates with no defined structures have been challenging to target and detect in a complex cellular milieu. In this study, we rationally designed sensors of amorphous protein aggregation from aggregation-induced-emission probes (AIEgens). Utilizing dicyanoisophorone as a model AIEgen scaffold, we first sensitized the fluorescence of AIEgens to a nonpolar and viscous environment mimicking the interior of amorphous aggregated proteins. We identified a generally applicable moiety (dimethylaminophenylene) for selective binding and fluorescence enhancement. Regulation of the electron-withdrawing groups tuned the emission wavelength while retaining selective detection. Finally, we utilized the optimized probe to systematically image aggregated proteome upon proteostasis network regulation. Overall, we present a rational approach to develop amorphous protein aggregation sensors from AIEgens with controllable sensitivity, spectral coverage, and cellular performance.
- Bai, Yulong,Dong, Xuepeng,Gao, Zhenming,Huang, Yanan,Jin, Wenhan,Liu, Xiaojing,Liu, Yu,Lyu, Haochen,Piao, Hai-Long,Shen, Di,Tang, Yuqi,Wan, Wang,Wang, Mengdie,Zeng, Lianggang
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supporting information
p. 16067 - 16076
(2021/06/17)
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- A side-chain engineering strategy for constructing fluorescent dyes with direct and ultrafast self-delivery to living cells
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Organic fluorescent dyes with excellent self-delivery to living cells are always difficult to find due to the limitation of the plasma membrane having rigorous selectivity. Herein, in order to improve the permeability of dyes, we utilize a side-chain engineering strategy (SCES): adjusting the side-chain length of dyes to fine-tune the adsorption and desorption processes on the membrane-aqueous phase interfaces of the outer and inner leaflets of the plasma membrane. For this, a family of fluorescent derivatives (SPs) was prepared by functionalizing a styryl-pyridinium fluorophore with alkyl side-chains containing a different carbon number from 1 to 22. Systematic experimental investigations and simulated calculations demonstrate that the self-delivery rate of SPs with a suitable length side-chain is about 22-fold higher in SiHa cells and 76-fold higher in mesenchymal stem cells than that of unmodified SP-1, enabling cell-imaging at an ultralow loading concentration of 1 nM and deep penetration in turbid tissue and in vivo. Moreover, the SCES can even endow a membrane-impermeable fluorescent scaffold with good permeability. Further, quantitative research on the relationship between Clog?P and cell permeability shows that when Clog?P is in the range of 1.3-2.5, dyes possess optimal permeability. Therefore, this work not only systematically reports the effect of side-chain length on dye delivery for the first time, but also provides some ideal fluorescent probes. At the same time, it gives a suitable Clog?P range for efficient cellular delivery, which can serve as a guide for designing cell-permeant dyes. In a word, all the results reveal that the SCES is an effective strategy to dramatically improve dye permeability.
- Guo, Lifang,Li, Chuanya,Shang, Hai,Zhang, Ruoyao,Li, Xuechen,Lu, Qing,Cheng, Xiao,Liu, Zhiqiang,Sun, Jing Zhi,Yu, Xiaoqiang
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p. 661 - 670
(2020/01/31)
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- Combination of N-Arylstilbazolium Organic Nonlinear Optical Chromophores with Iodoargentates: Structural Diversities and Optical Properties
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A combination of N-arylstilbazolium organic nonlinear optical chromophores with iodoargentates results in five new hybrids, i.e., [(DAST)(Ag2I3)]n (1), [(DMAQS)(Ag2I3)]n (2), [(DPAS)(Ag2I3)]n (3), [(DPTAS)2(Ag5I7)]n (4), and [(CEMAS)2(Ag5I7)]n (5). Among them, the former four are centrosymmetric, and 5 is non-centrosymmetrical (space group Pna21) with the introduction of a cyano group in an organic chromophore. The (Ag5I7)n2n- chains in 4 and 5 are special, in which that of 4 is constructed from Ag5I10 building blocks with a μ6-I σ-bonding to six Ag ions, and that in 5 is the connection of a cubane-like Ag4I4 core with bridged AgI4 tetrahedra. UV/vis/near-IR adsorptions and near-IR photoluminescences have been observed. All the organic chromophores are stacked as head-to-tail arrangements, resulting in second harmonic generation (SHG) inactive in 1-4. But 5 is SHG active without J-aggregation of organic chromophore, whose symmetry break was driven by the formation of hydrogen bonds around the cyano group. The SHG activity of 5 originates from the polarizations of the asymmetric contribution of Ag5I94- unit mixing with non-centrosymmetrical (CEMAS)22+ pair. Theoretical calculations were carried out to disclose their electronic structures.
- Wang, Yu-Kang,Zhao, Li-Ming,Fu, Yu-Qing,Chen, Zhao,Lin, Xiao-Yan,Wang, Dao-Hua,Li, Yi,Li, Hao-Hong,Chen, Zhi-Rong
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p. 3827 - 3840
(2018/06/11)
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- Thermochromism to tune the optical bandgap of a lead-free perovskite-type hybrid semiconductor for efficiently enhancing photocurrent generation
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Thermochromic materials have recently attracted great attention due to their controllable and rich physicochemical properties. However, until now, no studies have been reported on thermochromic materials for photovoltaic and optoelectronic applications. Here we report a new lead-free hybrid semiconductor material, (C16H20N2)SbBr5 (1), which adopts the zero-dimensional (0-D) perovskite-type inorganic framework. Strikingly, the thermochromism in 1 leads to a wide tunable bandgap and superior photoelectric properties. Three distinct color-varying stages were first observed, i.e. colorless to yellow (I), yellow to red (II), and red to black brown (III). In particular, the figure-of-merits for thin-film photodetectors based on II-thermochromism were greatly improved, with the dark current lowered to one quarter and light photocurrent enhanced at least 12-fold. The photocurrent on/off switching ratio was thus improved by ～50 times through thermochromism. As a new conceptual strategy to engineer the optical bandgap and meet specific photoelectric functions, our study paves the way for building high-performance optoelectronic devices based on thermochromic materials.
- Zhang, Weichuan,Sun, Zhihua,Zhang, Jing,Han, Shiguo,Ji, Chengmin,Li, Lina,Hong, Maochun,Luo, Junhua
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supporting information
p. 9967 - 9971
(2017/10/13)
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- Synthesis, Crystal Structures, and Photophysical Properties Investigations of Two New Pyridinium Complexes Containing [Sm(TTA)4]- and [Eu(TTA)4]-
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Two new lanthanide(III) complexes were designed and synthesized: DAS[M(TTA)4]-, (M = Sm [1], M = Eu [2]), each of them contained one trans-4-[4'-(N, N-dimethylamino)styryl]-N-methyl pyridinium (DAS) cationic moiety, four 2-thenoyltrifluoroacetone anions (TTA-), and one cationic lanthanide(III). Herein, the structures were confirmed by single-crystal X-ray diffraction analysis. The results revealed that the central lanthanide(III) atom was fashionable eight-coordinated with square-antiprismatic coordination environment. Meanwhile, the photophysical properties of 1 and 2 were investigated by fluorescence spectra. It was proposed that there was an antenna effect and the energy transfer took place from the DAS cationic moiety to lanthanide(III) ions.
- Zhang, Guo-Cui,Li, Dan-Dan,Kong, Ming,Su, Jian,Zhou, Hong-Ping,Wu, Jie-Ying,Tian, Yu-Peng
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p. 1254 - 1259
(2016/03/30)
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- Design, synthesis and in vitro antitumour activity of new heteroaryl ethylenes
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Almond and VolSurf + modelling procedures allowed the structural design of new di- and mono-heteroaryl-ethylenes. The structural modifications suggested by the molecular modelling were verified by the synthesis of the designed molecules and by the evaluation of their in vitro activities against two lung tumour cell lines, A549 and H226. 2-{(E)-2-[5′-(Dibutylamino)-2,2′- bithien-5-yl]vinyl}-1-methylquinolinium iodide exhibited in vitro antiproliferative activity two orders of magnitude higher than that of the most active compound previously synthesized in our laboratory.
- Fortuna, Cosimo G.,Barresi, Vincenza,Bonaccorso, Carmela,Consiglio, Giuseppe,Failla, Salvatore,Trovato-Salinaro, Angela,Musumarra, Giuseppe
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experimental part
p. 221 - 227
(2012/02/15)
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- Distinct molecular motions in a switchable chromophore dielectric 4-N,N-dimethylamino-4'-N'-methylstilbazolium trifluoromethanesulfonate
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Molecular motion associated with rotational and orientational phase transitions is one of the prominent structural strategies for assembling the functional materials such as artificial motors and tunable molecular dielectrics. Here, a new organic chromophore molecule, 4-N,N-dimethylamino-4'- N'-methylstilbazolium trifluoromethanesulfonate (complex 1), which undergoes an exceptional order-disorder phase transition at 322 K, is successfully synthesized. The single crystal X-ray diffraction analysis, thermal analysis, and dielectric measurements are used to characterize its dielectric dynamic behaviors. The results reveal that 1 behaves as a molecular rotator with the obviously distorted bipyramidal geometry of trifluoromethanesulfonate anions. In addition to its disorderings, two very distinct motions of the anionic moieties are confirmed, namely the "earth rotation" of partial units and the "earth revolution" of the whole molecule. Such unique molecular motions are found to be mainly responsible for the order-disorder phase transition together with the abrupt dielectric anomaly and anisotropy. The charge-transfer cationic parts enhance the molecular motions behaving as the stator and give rise to its excellent third-order nonlinearities. The concept may allow for the remote control of molecular events to explore functional materials in organic chromophores.
- Sun, Zhihua,Luo, Junhua,Chen, Tianliang,Li, Lina,Xiong, Ren-Gen,Tong, Ming-Liang,Hong, Maochun
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p. 4855 - 4861
(2013/02/25)
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- Solute-solvent and solvent-solvent interactions in the preferential solvation of 4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide in 24 binary solvent mixtures
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The molar transition energy (ET) polarity values for the dye 4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide were collected in binary mixtures comprising a hydrogen-bond accepting (HBA) solvent (acetone, acetonitrile, dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF)) and a hydrogen-bond donating (HBD) solvent (water, methanol, ethanol, propan-2-ol, and butan-1-ol). Data referring to mixtures of water with alcohols were also analyzed. These data were used in the study of the preferential solvation of the probe, in terms of both solute-solvent and solvent-solvent interactions. These latter interactions are of importance in explaining the synergistic behavior observed for many mixed solvent systems. All data were successfully fitted to a model based on solvent-exchange equilibria. The ET values of the dye dissolved in the solvents show that the position of the solvatochromic absorption band of the dye is dependent on the medium polarity. The solvation of the dye in HBA solvents occurs with a very important contribution from ion-dipole interactions. In HBD solvents, the hydrogen bonding between the dimethylamino group in the dye and the OH group in the solvent plays an important role in the solvation of the dye. The interaction of the hydroxylic solvent with the other component in the mixture can lead to the formation of hydrogen-bonded complexes, which solvate the dye using a lower polar moiety, i.e. alkyl groups in the solvents. The dye has a hydrophobic nature and a dimethylamino group with a minor capability for hydrogen bonding with the medium in comparison with the phenolate group present in Reichardt's pyridiniophenolate. Thus, the probe is able to detect solvent-solvent interactions, which are implicit to the observed synergistic behavior.
- Bevilaqua, Tharly,Goncalves, Thaini F.,Venturini, Cristina de G.,Machado, Vanderlei G.
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p. 535 - 542
(2007/10/03)
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- Photophysical studies on the mono- and dichromophoric hemicyanine dyes I. Photoelectric conversion from the dye modified ITO electrodes
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Stilbazolium dimers were designed and synthesized in which methylene groups of different lengths link the two chromophores. The second-order nonlinear optical property has been detected from their Langmuir-Blodgett monolayers. Photocurrent generation as well as other photophysical properties such as absorption and fluorescence were investigated. Comparing the dimers with the stilbazolium monomer, we found strong second harmonic generation (SHG) signals and remarkable enhanced photoelectric conversion (PEC) quantum yields from 1,3-Bis [(E)- 4-(2-(4-(N-methyl, N-octadecylamino) phenyl) ethenyl) pyridinyl]-alkane dibromide (B3) and 1,5-Bis [(E)- 4-(2-(4-(N-methyl, N-octadecylamino) phenyl) ethenyl) pyridinyl]-alkane dibromide (B5). The structures of the Langmuir-Blodgett films of these dyes are assumed. Although these dimers are center-symmetric (or quasi-center-symmetric) molecules, they can form the ordered non-center-symmetric (in normal direction) monolayer by the compress force and the molecular interaction between the amphiphilic dye molecules and the water molecules at the air/water interface. The influences of bias, donor/acceptor, soluble oxygen, and light intensity to photocurrent generation were studied; our results provide a new perspective to improve the performance of functional molecular material without any change of the chemical structure of the chromophore itself.
- Huang, Yanyi,Cheng, Tianrong,Li, Fuyou,Huang, Chun-Hui,Hou, Tingjun,Yu, Anchi,Zhao, Xinsheng,Xu, Xiaojie
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p. 10020 - 10030
(2007/10/03)
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- X-ray crystallographic study of 1-methyl-4-(4-N,N-dimethylamino) styryl pyridinium iodide
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Styryl pyridinium iodide dye(C16H19N2I), is monoclinic P21/c, a= 6.3313(8)A, b= 7699(2) A, c = 32.119(7) A, β= 90.39(1)°, V= 1565.6(9) A3, Z= 4, D(c) = 1.544gcm-3, λ(MoKα)= 0.71073 A, μ = 20.12cm-1, F000 = 728, T = 298 °K. 4707 unique reflections measured; final R = 0.032 for 3959 reflections with I >1.0 σ(I). The three dimensional structure of the dye is presented. The structure analysis shows that the dye exist in trans form and is approximately planner.
- Mishra,Behera,Fronczek,Vidyasagar,Behera
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p. 982 - 985
(2007/10/03)
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- Molecular Association of Water-Soluble Calixarenes with Several Stilbene Dyes and Its Application to the Facile Determination of Cationic Surfactant Concentrations
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The molecular association of water-soluble p-sulfonatocalix[n]arenes (1n; n = 4, 6, and 8) with several stilbene dyes (D) has been studied by spectrophotometric and 1HNMR methods. It was found that 1n reacts in 1: 1 stoichiometry with, D such as 4-[(4-dimethylamino)styryl]-1-methylpyridinium (St-4Me), 2-[(4-dimethylamino)styryl]-1-methylpyridinium (St-2Me) and 2-[(4-dimethylamino)styryl]-1-ethylpyridinium (St-2Et) iodides to form their complexes (1nD). The apparent association constants for 18-complexes are larger by about ten times than those of 14- and 16-complexes. Examinations of the CPK molecular models and the spectrophotometric studies suggested that 14 complexes D mainly with its 1-methyl- or 1-ethylpyridinium group, whereas 16 complexes D either with its pyridinium ring or with its protonated dimethylamino group in a similar probability, and in 18-complexes the molecule is wholly incorporated into the cavity of 18. The absorbance of D, which was decreased by association with 1n, was regenerated by the addition of other colorless cationic surfactants (A) such as cetylethyldimethylammonium ion. Studies on the substitution reaction of 1nD with A indicated that a 1 : 1 complex (1nA) is formed by releasing a free dye molecule (D). This was applied to a convenient determination of the cationic surfactant concentration in water.
- Nishida, Masashi,Ishii, Daido,Yoshida, Isao,Shinkai, Seiji
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p. 2131 - 2140
(2007/10/03)
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- Interaction of Solvent with the Ground and Excited State of 2- and 4--1-alkylpyridinium Iodides: an Absorption and Fluorescence study
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The absorption and emission characteristics of four organic salts: 4--1-alkylpiridinium iodides 1-3 (alkyl: 1 = methyl, 2 = ethyl, 3 = isopropyl) and 2--1-methylpiridinium iodide 4, in various solvents have been studied.It was found that these salts emit a single emission band which is dependent on the solvent's hydrogen bonding and polarity.In polar solvents a marked hypsochromic shift in absorption was observed, while no solvatochromism was observed in the emission spectra.A mechanism is proposed to explain these observations.In the salts 1-3 alkyl substitution on the pyridinium ring d oes not produce significant changes in their spectral properties.Acceptable correlations were obtained for the singlet excitation energies with the redox-potential differences of dyes 1-4. - Keywords: Absorption; emission; hydrogen-bonding; solvatochromism; redox-potential.
- Al-Ansari, Ibrahim Az
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p. 593 - 600
(2007/10/03)
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- Dye-surfactant interaction: Role of an alkyl chain in the localization of styrylpyridinium dyes in a hydrophobic force field of a cationic surfactant (CTAB)
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The interaction of a number of cationic dyes (I) with a varying number of methylene groups (C(n)) in the alkyl chain attached to pyridyl nitrogen with a cationic surfactant (CTAB) assembly is reported. The binding constant of the dyes (Cs to C18) with the micelle have been calculated, and are found to increase with increasing carbon chain. A plot of the binding constant vs. the chain length shows a curve with a maximum for C16, which is attributed to a compatibility factor. From studies of the electronic and emission spectra it is proposed that a micelle has a hydrophobic force field and that the dyes are localized in various pockets of the field.
- Mishra, Amaresh,Patel, Sanjukta,Behera, Rajani K.,Mishra, Bijaya K.,Behera, Gopa B.
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p. 2913 - 2918
(2007/10/03)
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