- Synthesis, crystal structure and photochromism of a novel spiro[indoline-naphthaline]oxazine derivative
-
A new spiro[indoline-naphthaline]oxazine derivative, 12-methoxy-14,14-dimethyl-17-(piperidin-1-yl)-7,8,14,15a-tetrahydro-4bH-naphtho[1″,2″:5′,6′][1,4]oxazino[3′,2′:2,3][1,4]oxazino[4,3-a]indole (1), was successfully synthesized, and its structure was characterized by 1H NMR, 13C NMR, IR, HRMS and single-crystal X-ray diffraction method. X-ray diffraction indicates that benzene and naphthalene rings of compound 1 are almost perpendicular, and the piperidine ring at the 6′-C site is in a chair conformation. In the packing diagram, a couple of short intermolecular distances such as the intermolecular short contact are observed. The photochromic properties of compound 1 have been fully investigated in different solvents, it was found that it exhibited excellent photochromism properties in solvents.
- Li, Hong,Pang, Meili,Wu, Bianpeng,Meng, Jiben
-
-
Read Online
- Cyanine-Flavonol Hybrids for Near-Infrared Light-Activated Delivery of Carbon Monoxide
-
Carbon monoxide (CO) is an endogenous signaling molecule that controls a number of physiological processes. To circumvent the inherent toxicity of CO, light-activated CO-releasing molecules (photoCORMs) have emerged as an alternative for its administration. However, their wider application requires photoactivation using biologically benign visible and near-infrared (NIR) light. In this work, a strategy to access such photoCORMs by fusing two CO-releasing flavonol moieties with a NIR-absorbing cyanine dye is presented. These hybrids liberate two molecules of CO in high chemical yields upon activation with NIR light up to 820 nm and exhibit excellent uncaging cross-sections, which surpass the state-of-the-art by two orders of magnitude. Furthermore, the biocompatibility and applicability of the system in vitro and in vivo are demonstrated, and a mechanism of CO release is proposed. It is hoped that this strategy will stimulate the discovery of new classes of photoCORMs and accelerate the translation of CO-based phototherapy into practice.
- ?tacková, Lenka,Russo, Marina,Muchová, Lucie,Orel, Vojtěch,Vítek, Libor,?tacko, Peter,Klán, Petr
-
-
Read Online
- Photomodulation of the electrode potential of a photochromic spiropyran-modified Au electrode in the presence of Zn2+: A new molecular switch based on the electronic transduction of the optical signals
-
The electrode potential of a photochromic spiropyran-modified Au electrode could be reversibly modulated by UV/visible light irradiation in the presence of Zn2+, and a new molecular switch and an AND logic gate based on this electronic transduction of the optical signals were established. The Royal Society of Chemistry 2006.
- Wen, Guoyong,Yan, Jie,Zhou, Yucheng,Zhang, Deqing,Mao, Lanqun,Zhu, Daoben
-
-
Read Online
- The synthesis of 6-substituted pyrido[2,3-d]pyrimidine-2,4(1H,3H)-diones using aminomethylene malondialdehydes and 6-aminouracils
-
Variously substituted aminomethylene malondialdehydes (2-(3,3- dimethylindolin-2-ylidene)malondialdehydes) were reacted with some 6-aminouracils, to give 6-(3,3-dimethyl-3H-indol-2-yl)pyrido[2,3-d]pyrimidine-2, 4-(1H,3H)-diones in good yields.
- Rashidi,Baradarani,Joule
-
-
Read Online
- Newly synthesized indolium-based ionic liquids as unprecedented inhibitors for the corrosion of mild steel in acid medium
-
New indolium-based ionic liquids (IBILs) of chemical formula 5-methoxy-1,2,3,3-tetramethyl-3H-indolium iodide (IBIL-I), 1-(2-carboxyethyl)-2,3,3-trimethyl-3H-indolium iodide (IBIL-II), 2,3,3-trimethyl-1-(pyren-2-ylmthyl)-3H-indolium iodide (IBIL-III), 1-(3-ethoxy-3-oxopropyl)-2,3,3-trimethyl-3H-indolium bromide (IBIL-IV) and 1-(2-ethoxy-2-oxoethyl)-2,3,3-trimethyl-3H-indolium bromide (IBIL-V) have been synthesized and characterized. The adsorption and corrosion inhibition effect of those IBILs have been studied using polarization measurements and cyclic voltammetry. It has been found that the inhibitive effect of the corrosion of mild steel in 0.5 M H2SO4 is inherently dependent on the structure of the studied IBILs; IBILs with bromide as an anionic head are more efficient than those with iodide. Thermodynamic calculations indicated that the adsorption on steel surface accords with Langmuir adsorption isotherm. Electrochemical measurements showed that the IBIL-IV, with the highest inhibition efficiency, acted mainly as a mixed type inhibitor, albeit the inhibition of the anodic branch is larger than the cathodic one. Cyclic voltammetric measurements at polycrystalline gold electrode gave an insight into the mechanism of corrosion inhibition by the studied ionic liquids.
- Ahmed, Saleh A.,Awad, Mohamed I.,Althagafi, Ismail I.,Altass, Hatem M.,Morad, Moataz,Alharbi, Ahmed,Obaid, Rami J.
-
-
Read Online
- Kinetic competition in liquid electrolyte and solid-state cyanine dye sensitized solar cells
-
The photovoltaic performance of liquid electrolyte and solid-state dye sensitized solar cells, employing a squarilium methoxy cyanide dye, are evaluated in terms of interfacial electron transfer kinetics. Dye adsorption to the metal oxide film resulted in a mixed population of aggregated and monomeric sensitizer dyes. Emission quenching data, coupled with transient absorption studies, indicate that efficient electron injection was only achieved by the monomeric dyes, with the aggregated dye population having an injection yield an order of magnitude lower. In liquid electrolyte devices, transient absorption studies indicate that photocurrent generation is further limited by slow kinetics of the regeneration of monomeric dye cations by the iodide/iodine redox couple. The regeneration dynamics are observed to be too slow (? 100 s) to compete effectively with the recombination of injected electrons with dye cations. In contrast, for solid-state devices employing the organic hole conductor spiro-OMeTAD, the regeneration dynamics are fast enough (? 1 s) to compete effectively with this recombination reaction, resulting in enhanced photocurrent generation. The Royal Society of Chemistry.
- Tatay, Sergio,Haque, Saif A.,O'Regan, Brian,Durrant, James R.,Verhees,Kroon,Vidal-Ferran,Gavina, Pablo,Palomares, Emilio
-
-
Read Online
- Optimizing the framework of indolium hemicyanine to detect sulfur dioxide targeting mitochondria
-
Endogenous sulfur dioxide (SO2) is mainly produced by the enzymatic reaction of sulfur-containing amino acids in mitochondria, which has unique biological activity in inflammatory reaction, regulating blood pressure and maintaining the homeostasis of biological sulfur. It is more and more common to detect monitor SO2 levels by fluorescence probe. In recent years, the indolium hemicyanine skeleton based on the D-π-A structure has been widely used in the development of fluorescent sensors for the detection of SO2. However, subtle changes in the chemical structure of indolium may cause significant differences in SO2 sensing behavior. In this article, we designed and synthesized two probes with different lipophilicities to further study the relationship between the structure and optical properties of hemicyanine dyes. On the basis of previous studies, the structure of indolium hemicyanine skeleton was optimized by introducing –OH group, so that MC-1 and MC-2 had the best response to SO32- in pure PBS system. In addition, the lipophilicity of MC-2 was better than that of MC-1, which enabled it to respond quickly to SO32- and better target mitochondria for SO2 detection. Most importantly, the low detection limits of MC-1 and MC-2 conducive to the detection of endogenous SO2. This work provided an idea for developing SO2 fluorescent sensors with excellent water solubility and low detection limit.
- Chao, Jianbin,Huo, Fangjun,Wang, Zhuo,Zhang, Ting,Zhang, Yongbin
-
supporting information
(2021/10/04)
-
- Programmable Chromism and Photoluminescence of Spiropyran-Based Liquid Crystalline Polymer with Tunable Glass Transition Temperature
-
Spiropyran-based materials (SPBMs) can give responses to the stimulations induced by the light, heat, force, or pH, which have been used as triggers for many smart materials. Here, a cross-linkable SPBM containing mesogenic-units is synthesized, which is pale-colored, non-photoluminescent and non-mesogenic at a spiro form, but dark-colored, photoluminescent, and mesogenic at a merocyanine form. Moreover, the dynamic interconversion behavior of the form in the different chemical environments are distinct. Liquid crystalline polymers (LCPs) containing the SPBMs cross-linked via visible light, own a photoswitchable glass transition temperature (Tg) and retain the switchable property; however, the SPBMs cross-linked via UV light will be locked at the MC state, because the molecular movement was frozen at the room temperature lower than the given Tg of the LCP. Thus, programmable chromism and photoluminescence based on the tunable Tg can be endowed to the functional materials prepared from the SPBMs.
- Hu, Wei,Qin, Shengyu,Ren, Yunxiao,Shao, Yu,Sun, Chang,Wang, Qian,Wu, Yu,Yang, Dengke,Yang, Huai,Zhang, Lanying
-
supporting information
p. 19406 - 19412
(2021/08/06)
-
- Fast, reversible mechanochromism of regioisomeric oxazine mechanophores: Developing in situ responsive force probes for polymeric materials
-
To address hysteretic or irreversible mechanochromism found in most bond-scission-based mechanophores, we developed a new family of mechanophores based on the oxazine (OX) structural motif. Three OX regioisomers differing in their point of attachment to the indole ring show variable mechanochromic mechanoresponsiveness in a polydimethylsiloxane (PDMS) matrix. Constrained DFT simulations correlate the experimental findings to molecular scale events; two of the three regioisomers exhibit a force-activated rearrangement, while the third one is mechanochemically inactive. Most significantly, when compared with the spiropyran (SP) and the naphthopyran (NP), the OX mechanophores exhibit faster and reversible mechanochromism without any sign of fatigue. Such a rapid response to mechanical loads is rationalized by the difference between SP and OX scaffolds, given that the SP ring opening is accompanied by a trans-cis isomerization step. These fast-responsive mechanophores are anticipated to bring deeper understanding to a broad range of soft materials by in situ monitoring the local mechanics.
- Qian, Hai,Purwanto, Nathan S.,Ivanoff, Douglas G.,Halmes, Abigail J.,Sottos, Nancy R.,Moore, Jeffrey S.
-
supporting information
p. 1080 - 1091
(2021/04/19)
-
- Large, Tunable, and Reversible pH Changes by Merocyanine Photoacids
-
Molecular photoswitches capable of generating precise pH changes will allow pH-dependent processes to be controlled remotely and noninvasively with light. We introduce a series of new merocyanine photoswitches, which deliver reversible bulk pH changes up to 3.2 pH units (pH 6.5 to pH 3.3) upon irradiation with 450 nm light, displaying tunable and predictable timescales for thermal recovery. We present models to show that the key parameters for optimizing the bulk pH changes are measurable: the solubility of the photoswitch, the acidity of the merocyanine form, the thermal equilibrium position between the spiropyran and the merocyanine isomers, and the increased acidity under visible light irradiation. Using ultrafast transient absorption spectroscopy, we determined the quantum yields for the ring-closing reaction and found that the lifetimes of the transient cis-merocyanine isomers ranged from 30 to 550 ns. Quantum yields did not appear to be a limitation for bulk pH switching. The models we present use experimentally determined parameters and are, in principle, able to predict the change in pH obtained for any related merocyanine photoacid.
- Andreásson, Joakim,Beves, Jonathon E.,Peeks, Martin D.,Prasad, Shyamal K. K.,Schmidt, Timothy W.,Wimberger, Laura
-
supporting information
p. 20758 - 20768
(2021/12/14)
-
- Light-Switchable Buffers
-
A visible light-switchable buffer system based on a merocyanine photoacid is presented. Para-substitution of the indolium side with a methoxy group affords a compound suitable for making hydrolytically stable aqueous buffers whose pH can be tuned between 7 and 4 using 500 nm light.
- Berton, Cesare,Busiello, Daniel Maria,Fadaei-Tirani, Farzaneh,Pezzato, Cristian,Scopelliti, Rosario,Severin, Kay,Zamuner, Stefano
-
supporting information
p. 21737 - 21740
(2021/08/26)
-
- Bioinspired Synergistic Photochromic Luminescence and Programmable Liquid Crystal Actuators
-
Bioinspired smart materials with synergistic allochroic luminescence and complex deformation are expected to play an important role in many areas of science and technology. However, it is still challenging to fabricate such soft actuators with high programmability that can be manipulated in situ with high spatial resolution. Herein, we have incorporated terminally functionalized aggregation-induced emission active tetraphenylethene derivative and photochromic spiropyran moieties into the networks of liquid crystal elastomers through covalent bonding to obtain the synergistic photochromic luminescence and programmable soft actuators. Bio-mimic functions and light-induced auxetic metamaterial-like devices were shown to be feasible based on the combination of assembly and origami-programming strategy. These bioinspired devices with synergistic photochromic luminescence and complex photodeformation abilities provide an elegant strategy to design multi-functional liquid crystal actuators.
- Huang, Yinliang,Bisoyi, Hari Krishna,Huang, Shuai,Wang, Meng,Chen, Xu-Man,Liu, Zhiyang,Yang, Hong,Li, Quan
-
supporting information
p. 11247 - 11251
(2021/04/16)
-
- Force-Induced Near-Infrared Chromism of Mechanophore-Linked Polymers
-
A near-infrared (NIR) mechanophore was developed and incorporated into a poly(methyl acrylate) chain to showcase the first force-induced NIR chromism in polymeric materials. This mechanophore, based on benzo[1,3]oxazine (OX) fused with a heptamethine cyanine moiety, exhibited NIR mechanochromism in solution, thin-film, and bulk states. The mechanochemical activity was validated using UV-vis-NIR absorption/fluorescence spectroscopies, gel permeation chromatography (GPC), NMR, and DFT simulations. Our work demonstrates that NIR mechanochromic polymers have considerable potential in mechanical force sensing, damage detection, bioimaging, and biomechanics.
- Chandradat, Richard,Darie, Costel C.,Jayathirtha, Madhuri,Joy, Monu,Liu, Xiaogang,Lu, Xiaocun,Ofodum, Nnamdi M.,Qi, Qingkai,Scrimgeour, Jan,Sekhon, Gaganjot,Shen, Tianruo,Shipp, Devon A.,Wriedt, Mario
-
supporting information
p. 17337 - 17343
(2021/10/20)
-
- Near-Infrared Heptamethine Cyanine Dyes for Nanoparticle-Based Photoacoustic Imaging and Photothermal Therapy
-
We have synthesized and characterized a library of near-infrared (NIR) heptamethine cyanine dyes for biomedical application as photoacoustic imaging and photothermal agents. These hydrophobic dyes were incorporated into a polymer-based nanoparticle system to provide aqueous solubility and protection of the photophysical properties of each dye scaffold. Among those heptamethine cyanine dyes analyzed, 13 compounds within the nontoxic polymeric nanoparticles have been selected to exemplify structural relationships in terms of photostability, photoacoustic imaging, and photothermal behavior within the NIR (～650-850 nm) spectral region. The most contributing structural features observed in our dye design include hydrophobicity, rotatable bonds, heavy atom effects, and stability of the central cyclohexene ring within the dye core. The NIR agents developed within this project serve to elicit a structure-function relationship with emphasis on their photoacoustic and photothermal characteristics aiming at producing customizable NIR photoacoustic and photothermal tools for clinical use.
- St. Lorenz, Anna,Buabeng, Emmanuel Ramsey,Taratula, Oleh,Taratula, Olena,Henary, Maged
-
p. 8798 - 8805
(2021/06/28)
-
- Design, synthesis and biological evaluation of novel heptamethine cyanine dye-erlotinib conjugates as antitumor agents
-
Epidermal growth factor receptor tyrosine kinase (EGFR-TK) has been proved as a target for the treatment of non-small cell lung cancer (NSCLC) with specific gene mutations. However, EGFR-TK inhibitors (EGFR-TKIs) need to enter cancer cells and then competitively interact with the active site of tyrosine kinase receptors to suppress the downstream signaling pathway to inhibit tumor proliferation. In this study, in order to improve the tumor cell targeting ability of EGFR-TKI, EGFR-TKI erlotinib was conjugated with the cancer cell-targeting heptamethine cyanine dyes to form seventeen novel erlotinib-dye conjugates. The efficiency of tumor targeting properties of conjugates against cancer cell growth and EGFR-TK inhibition was evaluated in vitro. The result revealed that most erlotinib-dye conjugates exhibited stronger inhibitory effect on A549, H460, H1299 and MDA-MB-231 cell lines than the parent drug erlotinib. Meanwhile, representative compounds exhibited weak cytotoxicity on human normal mammary epithelial MCF-10A cells. Moreover, the conjugate CE17 also showed ~14-fold higher EGFR-TK inhibition activity (IC50 = 0.124 μM) than erlotinib (IC50 = 5.182 μM) in A549 cell line. Finally, molecular docking analysis verified that the erlotinib moiety of compound CE17 could form hydrogen bond with Met-769 and occupy active cavity of EGFR-TK. Therefore, we believed the integration strategy between heptamethine cyanine dyes and EGFR-TKI will contribute to enhancing the therapeutic effect of EGFR-TKI for NSCLC treatment.
- Guo, Chun,Hou, Zhuang,Mou, Yanhua,Wang, Dun,Yang, Xiaoguang
-
supporting information
(2020/10/02)
-
- A highly sensitive fluorescent probe that quantifies transthyretin in human plasma as an early diagnostic tool of Alzheimer's disease
-
The development of sensitive and reliable fluorescent probes for the early diagnosis of Alzheimer's disease (AD) is highly challenging and plays an important role in achieving effective treatments. Herein, we designed and synthesized an indole-based fluorophore for TTR in human plasma, an important hallmark of AD pathogenesis. This robust and simple fluorescent method allows quantification of TTR in the complex biological matrix.
- Lim, Hye Rim,Kim, Seo Yun,Jeon, Eun Hee,Kim, Yun Lan,Shin, Yu Mi,Koo, Tae-Sung,Park, Sung Jean,Hong, Ki Bum,Choi, Sungwook
-
supporting information
p. 10424 - 10427
(2019/09/07)
-
- Iodine-Promoted Domino Oxidative Cyclization for the One-Pot Synthesis of Novel Fused Four-Ring Quinoxaline Fluorophores by sp3 C?H Functionalization
-
A method for the synthesis of novel fused four-ring quinoxaline skeleton has been described by an I2 promoted sp3 C?H functionalization between 1,2,3,3-tetramethyl-3H-indolium iodides and 1,2-diamines. This transformation proceeds smoothly under metal- and peroxide-free conditions through a sequential iodination, oxidation, annulation and rearrangement. Moreover, 8,9-dichloro-5,12,12-trimethyl-2-(trifluoromethyl)-5,12-dihydroquinolino[2,3-b]quinoxaline showed good photophysical properties and was used in live cell imaging, indicating the potential value of this skeleton as a fluorophore in probes.
- Zhang, Yong,Yang, Min,Jia, Chengli,Ji, Min
-
supporting information
p. 13709 - 13713
(2019/11/05)
-
- Effects of Substituents on Metastable-State Photoacids: Design, Synthesis, and Evaluation of their Photochemical Properties
-
Recently, metastable-state photoacids have been widely used to control proton transfer in numerous chemical and biological processes as well as applications with visible light. Generally, substituents have a great influence on the photochemical properties of molecules, which will further affect their applications. Yet, the effects of substituents on metastable-state photoacids have not been studied systematically. In this work, 16 metastable-state photoacid derivatives were designed and synthesized on the basis of substituents having a large range of σ–π electron–donor–acceptor capabilities. The effects of substituents on the color display [or maximum absorption band(s)], solubility, pKa values, dark/photoacidity, photosensitivity, and relaxation kinetic(s) were investigated in detail. This study will be helpful for the targeted design and synthesis of promising photoacids and the application of their photocontrolled proton-release processes in functional materials/devices.
- Liu, Junning,Tang, Wenqi,Sheng, Lan,Du, Zhen,Zhang, Ting,Su, Xing,Zhang, Sean Xiao-An
-
supporting information
p. 438 - 445
(2019/01/08)
-
- Micellar-incorporated hydrogels with highly tough, mechanoresponsive, and self-recovery properties for strain-induced color sensors
-
Tough, mechanoresponsive hydrogels have broad and significant impacts on fundamental research and practical applications, but have proved to be extremely challenging to develop. The poor solubility of mechanophores makes them difficult to be integrated into a highly hydrophilic network of hydrogels. In this work, we synthesized dimethylacrylate-functionalized spiropyran (SP) mechanophores and used them as crosslinkers to copolymerize with hydrophobic methyl acrylate (MA) monomers and hydrophilic acrylamide (AM) monomers in the presence of surfactant polysorbate 80 (TWEEN 80) micelles, forming poly(AM-co-MA/SP) hydrogels. The mechanical properties of the as-prepared and swollen poly(AM-co-MA/SP) hydrogels strongly depend on network components (AM, MA, and SP concentrations). Thus, the optimal hydrogels can achieve excellent mechanical properties (tensile stress of 1.1 MPa, tensile strain of 6 mm mm-1, elastic modulus of 1.1 MPa, and tearing energy of 3200 J m-2). Due to multi-stimuli responses of SP crosslinkers, the hydrogels exhibited the reversible changes in color and mechanical properties between the force-, heat-, and UV light-induced deformation state and the white light-induced recovery state. Based on their fast, reversible, force-induced color change behavior, we further designed a conceptual hydrogel strain sensor to monitor color change under the stretching and relaxing processes in multiple cycles. This work demonstrates that the presence of dynamically reversible SP crosslinkers and micellar structures is the key to greatly enhance both mechanical and color recoverable properties of poly(AM-co-MA/SP) hydrogels, which could serve as promising smart materials for a variety of applications such as soft robots, electronic skins, and strain/motion/damage sensors.
- Zhang, Yanxian,Ren, Baiping,Yang, Fengyu,Cai, Yongqing,Chen, Hong,Wang, Ting,Feng, Zhangqi,Tang, Jianxin,Xu, Jianxiong,Zheng, Jie
-
p. 11536 - 11551
(2018/11/23)
-
- Synthesis and optical properties of near-infrared meso-phenyl-substituted symmetric heptamethine cyanine dyes
-
Heptamethine cyanine dyes are a class of near infrared fluorescence (NIRF) probes of great interest in bioanalytical and imaging applications due to their modifiability, allowing them to be tailored for particular applications. Generally, modifications at the meso-position of these dyes are achieved through Suzuki-Miyaura C-C coupling and SRN1 nucleophilic substitution of the chlorine atom at the meso-position of the dye. Herein, a series of 15 meso phenyl-substituted heptamethine cyanines was synthesized utilizing a modified dianil linker. Their optical properties, including molar absorptivity, fluorescence, Stokes shift, and quantum yield were measured. The HSA binding affinities of two representative compounds were measured and compared to that of a series of trimethine cyanines previously synthesized by our lab. The results indicate that the binding of these compounds to HSA is not only dependent on hydrophobicity, but may also be dependent on steric interferences in the binding site and structural dynamics of the NIRF compounds.
- Levitz, Andrew,Marmarchi, Fahad,Henary, Maged
-
-
- Photooxidation of oxazolidine molecular switches: Uncovering an intramolecular ionization facilitated cyclization process
-
Photooxidation of oxazoline (OXA) molecular switches through media-induced intramolecular ionization is reported. The formation of the photooxidation product occurs by attack of the flexible donor group (-CH2CH2OH) to the adjacent CC with 1O2 as the oxidant. The novel seven-membered ring sub-structure of the photooxidation product was inferred by HRMS, IR and 1H NMR spectroscopy. Additionally, acid released from solvent photolysis was found to affect the product formation and efficiency of the photooxidation.
- Chen, Qiaonan,Sheng, Lan,Du, Jiahui,Xi, Guan,Zhang, Sean Xiao-An
-
supporting information
p. 5094 - 5097
(2018/05/26)
-
- Diversely halogenated spiropyrans - Useful synthetic building blocks for a versatile class of molecular switches
-
Spiropyrans are dyes that can be reversibly switched to a highly colored merocyanine form by a number of stimuli such as light, mechanical force or temperature. To make use of these molecules, there is a requirement to functionalize them appropriately. Herein we report a library of spiropyrans bearing two (pseudo) halide functional groups on either half of the molecule. Such halide substituents are valuable, because they themselves may be used as reactive sites in cross-coupling reactions, for example. Different combinations of halides, for which different reactivities in cross-coupling reactions may be expected, will facilitate selective consecutive cross-coupling reactions and condensations. Data concerning the UV/vis characteristics, the photostationary equilibria of the materials as well as the half-life of the merocyanine forms in solution are presented.
- Schulz-Senft, Mathias,Gates, Paul J.,S?nnichsen, Frank D.,Staubitz, Anne
-
p. 292 - 301
(2016/09/09)
-
- Photophysical characterization and BSA interaction of the direct ring carboxy functionalized unsymmetrical NIR cyanine dyes
-
Novel near infrared (NIR) sensitive unsymmetrical cyanine dyes bearing direct –COOH functionalized indole ring were synthesized, characterized and subjected to photophysical investigations. These unsymmetrical cyanine dyes were then subjected to investigate their interaction with bovine serum albumin (BSA) as a model protein in Phosphate buffer solutions. Apart from NIR absorption and emission with high molar extinction coefficients they exhibit a blue shift in PBS solution owing to their enhanced dye aggregation. Interaction of these dyes with BSA leads to not only enhanced emission intensity but also bathochromically shifted absorption maximum due to formation of dye-BSA conjugate. These dyes bind strongly with BSA having about an order of magnitude higher binding constant as compared to the typical cyanine dyes. Amongst the unsymmetrical cyanine dyes investigated in this work one bearing substituents like Iodo and carboxylic acid in the terminal Indole rings (UCD-3) exhibited highest association with the BSA having very high binding constant of 1.01?×?107?M?1.
- Saikiran, Maryala,Sato, Daisuke,Pandey, Shyam S.,Ohta, Takeshi,Hayase, Shuzi,Kato, Tamaki
-
-
- Comparative Evaluation of Substituent Effect on the Photochromic Properties of Spiropyrans and Spirooxazines
-
Spiropyrans and spirooxazines represent an important class of photochromic compounds with a wide variety of applications. In order to effectively utilize and design these photoswitches it is desirable to understand how the substituents affect photochromic properties, and how the different structural motifs compare under identical conditions. In this work a small library of photoswitches was synthesized in order to comparatively evaluate the effect of substituent modifications and structure on photochromism. The library was designed to modify positions that were believed to have the greatest effect on C-O bond lability and therefore the photochromic properties. Herein we report a comparative analysis of the UV and visible light responses of 30 spiropyrans, spiroindolinonaphthopyrans, and spirooxazines. The influence of gadolinium(III) binding was also investigated on the library of compounds to determine its effect on photoswitching. Both assays demonstrated different trends in substituent and structural requirements for optimal photochromism.
- Balmond, Edward I.,Tautges, Brandon K.,Faulkner, Andrea L.,Or, Victor W.,Hodur, Blanka M.,Shaw, Jared T.,Louie, Angelique Y.
-
p. 8744 - 8758
(2016/10/14)
-
- Benz[c,d]indolium-containing monomethine cyanine dyes: Synthesis and photophysical properties
-
Asymmetric monomethine cyanines have been extensively used as probes for nucleic acids among other biological systems. Herein we report the synthesis of seven monomethine cyanine dyes that have been successfully prepared with various heterocyclic moieties such as quinoline, benzoxazole, benzothiazole, dimethyl indole, and benz[e]indole adjoining benz[c,d]indol-1-ium, which was found to directly influence their optical and energy profiles. In this study the optical properties vs. structural changes were investigated using nuclear magnetic resonance and computational approaches. The twisted conformation unique to monomethine cyanines was exploited in DNA binding studies where the newly designed sensor displayed an increase in fluorescence when bound in the DNA grooves compared to the unbound form.
- Soriano, Eduardo,Holder, Cory,Levitz, Andrew,Henary, Maged
-
-
- Near-Infrared Illumination of Native Tissues for Image-Guided Surgery
-
Our initial efforts to prepare tissue-specific near-infrared (NIR) fluorescent compounds generated successful correlation between physicochemical properties and global uptake in major organs after systemic circulation and biodistribution. Herein, we focus on the effects on biodistribution based on modulating electronic influencing moieties from donating to withdrawing moieties at both the heterocyclic site and through meso-substitution of pentamethine cyanine fluorophores. These selected modifications harnessed innate biodistribution pathways through the structure-inherent targeting, resulting in effective imaging of the adrenal glands, pituitary gland, lymph nodes, pancreas, and thyroid and salivary glands. These native-tissue contrast agents will arm surgeons with a powerful and versatile arsenal for intraoperative NIR imaging in real time.
- Owens, Eric A.,Hyun, Hoon,Dost, Tyler L.,Lee, Jeong Heon,Park, Gwangli,Pham, Dang Huan,Park, Min Ho,Choi, Hak Soo,Henary, Maged
-
p. 5311 - 5323
(2016/07/06)
-
- Efficient Synthesis of Chiral Indolines using an Imine Reductase from Paenibacillus lactis
-
An enzymatic process for the efficient asymmetric reduction of 3H-indoles as well as 3H-indole iodides was developed for the first time. Using a new imine reductase identified from Paenibacillus lactis (PlSIR), various chiral indolines were facilely synthesized in good yields and excellent enantiopurities (up to >99% ee) under mild reaction conditions.
- Li, Hao,Luan, Zheng-Jiao,Zheng, Gao-Wei,Xu, Jian-He
-
supporting information
p. 1692 - 1696
(2015/06/02)
-
- Synthesis of asymmetric monomethine cyanine dyes with red-shifted optical properties
-
Six novel asymmetrical monomethine cyanine dyes were synthesized via the condensation reaction of 1-butyl-2-(methylthio)benzo[c,d]indol-1-ium iodide and various 1,5-substituted indolenine salts under basic conditions. The dyes were characterized using UV-vis spectroscopy, fluorescence, 1H NMR, 13C NMR, and mass spectrometry; furthermore, the purity of these compounds was observed using LC/ELSD/MS.
- Soriano, Eduardo,Outler, Loretta,Owens, Eric A.,Henary, Maged
-
p. 180 - 184
(2015/01/30)
-
- Synthesis of novel hemicyanine dyes for color compensating film in plasma display panels
-
Five novel cyanine dyes containing julolidine and indole moieties were synthesized. Several color compensating films for plasma display panels (PDP) were prepared using these dyes. The spectroscopic and physicochemical properties of the synthesized dyes in both solution and film state were evaluated. For each color compensating film, the optimum ratio of dye to binder was determined on the basis of transmittance, half band width, and photo-stability of the color compensating film. The five synthesized dyes showed sharp absorption peaks near 590 nm (orange light) and had molar extinction coefficients above 1 × 105 M-1cm-1. The melting point of the dyes was above 200 °C and photo-stability of the color compensating films was improved by introducing substituents at the 5th position on the indole derivatives.
- Kim, Bo Hyung,Park, Se Woong,Lee, Donghyun,Kwon, I. I. Keun,Kim, Jae Pil
-
p. 2453 - 2459
(2014/10/15)
-
- Synthesis and effect of heterocycle modification on the spectroscopic properties of a series of unsymmetrical trimethine cyanine dyes
-
Carbocyanine dyes are a class of organic compounds that contain two heterocycles that act as electron donors and acceptors connected by a conjugated methine bridge. Herein the synthesis of a series of 16 novel unsymmetrical trimethine cyanine dyes is reported. Their structures were characterized by various spectroscopic techniques, and their optical properties were measured. Absorption maxima of the dyes were calculated using the time-dependent density-functional theory method and the computational absorption maxima are consistent with the experimental data. The addition of electron withdrawing substituents such as halogens on the heterocycle gave more favorable optical properties such as higher quantum yield and molar absorptivity. The aggregation of these cyanine dyes was studied and compared to a similar series of symmetric cyanine dyes. It was determined that the heterocycle has more effect on aggregation than the side chain and a dye with two different heterocycles will aggregate less than a dye with the same heterocycle. The dyes were also investigated for Lipinski Rule violations as their use is becoming more prevalent for in vivo applications.
- Levitz, Andrew,Ladani, Safieh Tork,Hamelberg, Donald,Henary, Maged
-
p. 238 - 249
(2014/04/03)
-
- Oxidative palladium(II)-catalyzed dehydrogenative C-H/C-H cross-coupling of 2,3-substituted indolines with arenes at the C7 position
-
Directed directing group: The C7 position of the indoline nucleus is difficult to address in C-H activation. An oxidative palladium(II) catalysis that allows for cross-dehydrogenative coupling in that position with activation of the C-H bond of the arene component is disclosed here. This C-H/C-H cross-coupling is applicable to various indolines acetylated at the nitrogen atom. Substitution at C2 is crucial for the C-H activation to occur at C7 (see scheme).
- Jiao, Lin-Yu,Oestreich, Martin
-
supporting information
p. 10845 - 10848
(2013/09/02)
-
- Development and application of a near-infrared fluorescence probe for oxidative stress based on differential reactivity of linked cyanine dyes
-
Reactive oxygen species (ROS) operate as signaling molecules under various physiological conditions, and overproduction of ROS is involved in the pathogenesis of many diseases. Therefore, fluorescent probes for visualizing ROS are promising tools with which to uncover the molecular mechanisms of physiological and pathological processes and might also be useful for diagnosis. Here we describe a novel fluorescence probe, FOSCY-1, operating in the physiologically favorable near-infrared region. The probe consists of two differentially ROS-reactive cyanine dyes connected by a linker; reaction of the more susceptible dye with ROS releases intramolecular fluorescence quenching of the less susceptible dye. We successfully applied this probe to detect ROS produced by HL60 cells and porcine neutrophils and for imaging oxidative stress in a mouse model of peritonitis.
- Oushiki, Daihi,Kojima, Hirotatsu,Terai, Takuya,Arita, Makoto,Hanaoka, Kenjiro,Urano, Yasuteru,Nagano, Tetsuo
-
supporting information; experimental part
p. 2795 - 2801
(2010/05/19)
-
- New 3H-indole synthesis by fischer's method. Part I.
-
Methyl indolenines (4a-c) and (5a-c) were prepared in high yield by a Fischer indole synthesis reaction of o,m-tolylhydrazine hydrochlorides (1a-b) with isopropyl methyl ketone (2) and 2-methylcyclohexanone (3) in acetic acid at room temperature. o,pNitrophenylhydrazines (1c-d) were reacted with 2-methylcyclohexanone (3) in acetic acid at reflux to give nitroindolenines (5d-e), while the attempted reactions of o,pnitrohydrazines with isopropyl methyl ketone (2) in acetic acid were not successful. Compounds (1c-d) were reacted with isopropyl methyl ketone (2) in acetic acid/HCl to give 2,3,3-trimethyl-5-nitro-indolenine (4e) and 2,3,3-trimethyl-7-nitroindolenine (4d). Copyright
- Sajjadifar, Sami,Vahedi, Hooshang,Massoudi, Abdolhossien,Louie, Omid
-
scheme or table
p. 2491 - 2498
(2010/07/10)
-
- Photoswitchable fluorescent dyads incorporating bodipy and [1,3]oxazine components
-
We designed and synthesized three compounds incorporating a BODIPY fluorophore and an oxazine photochrome within the same molecular skeleton and differing in the nature of the linker bridging the two functional components. The [1,3]oxazine ring of the photochrome opens in less than 6 ns upon laser excitation in two of the three fluorophore-photochrome dyads. This process generates a 3H-indolium cation with a quantum yield of 0.02-0.05. The photogenerated isomer has a lifetime of 1-3 μs and reverts to the original species with first-order kinetics. Both photochromic systems tolerate hundreds of switching cycles with no sign of degradation. The visible excitation of the dyads is accompanied by the characteristic fluorescence of the BODIPY component. However, the cationic fragment of their photogenerated isomers can accept an electron or energy from the excited fluorophore. As a result, the photoinduced transformation of the photochromic component within each dyad results in the effective quenching of the BODIPY emission. Indeed, the fluorescence of these photoswitchable compounds can be modulated on a microsecond time scale with excellent fatigue resistance under optical control. Thus, our operating principles and choice of functional components can ultimately lead to the development of valuable photoswitchable fluorescent probes for the super-resolution imaging of biological samples.
- Deniz, Erhan,Ray, Shuvasree,Tomasulo, Massimiliano,Impellizzeri, Stefania,Sortino, Salvatore,Raymo, Francisco M.
-
scheme or table
p. 11567 - 11575
(2011/02/27)
-
- Synthesis and properties of benzophenone-spiropyran and naphthalene-spiropyran conjugates
-
We have designed and synthesized four compounds integrating luminescent and photochromic components in their molecular skeletons. Two of them combine a nitrospiropyran photochrome with either one or two naphthalene fluorophores and can be prepared in three synthetic steps. The other two consist of a nitrospiropyran photochrome and a benzophenone phosphore connected by either ether or ester linkages and can be prepared in six or five, respectively, synthetic steps. The luminescent components of these assemblies are expected to transfer energy intramolecularly to the photochromic species upon excitation and encourage their photoisomerization. Consistently, the phosphorescence of the benzophenone units and the fluorescence of the naphthalene components are effectively quenched when these species are connected covalently to a nitrospiropyran. Nonetheless, the photoisomerization of the photochrome becomes significantly less efficient after the covalent attachment to the luminescent partner. The fraction of incident radiations absorbed by either the benzophenone or the naphthalene fragment does not promote the isomerization of the photochromic appendage. Instead, irreversible transformations occur upon irradiation of the luminophore-photochrome assemblies. Thus, the covalent attachment of a benzophenone or a naphthalene to a nitrospiropyran is not a viable strategy to improve the photocoloration efficiency of the photochromic component. Even although the very same luminophores are known to sensitize intermolecularly the isomerization of nitrospiropyrans, the transition to covalent luminophore-photochrome assemblies tends to promote degradation, rather than sensitization, upon irradiation.
- Tomasulo, Massimiliano,Kaanumal, Sireesha L.,Sortino, Salvatore,Raymo, Francisco M.
-
p. 595 - 605
(2007/10/03)
-
- Mechanophore-linked addition polymers
-
The use of mechanical energy to increase reaction rates and alter the distribution of products has gained considerable interest of late. However, the discovery of new mechanophores (i.e., mechanochemically reactive units) is currently time-consuming, expensive, low-yielding, and a process that is not easily scaled to large quantities. Here we show that mechanophore-linked addition polymers are easily prepared using bifunctional initiators with a living radical polymerization method. The mechanophore is positioned close to the center of the polymer, where ultrasound-generated forces are the largest. Since these forces are strongly dependent on molecular weight, the use of controlled polymerization enables fine-tuning of the mechanical activity so that mechanophore reactions are initiated while minimizing chain scission. The approach is illustrated first with the synthesis and investigation of a 1,2-disubstituted benzocyclobutene mechanophore that is incorporated into the center of a polymethacrylate (PMA) chain. Selected molecular weights are probed using ultrasound to illustrate that the 4π electrocyclic ring opening of the benzocyclobutene link is stress-induced. To demonstrate the broad applicability of this method for mechanophore screening, we also report a new spiropyran-linked PMA that undergoes an ultrasound-induced 6π-electron electrocyclic ring opening. The straightforward synthesis of mechanophore-linked addition polymers presented here shows considerable promise for the investigation of new mechanophores and will lead to a greater understanding of mechanochemical reactivity within polymer systems. Copyright
- Potisek, Stephanie L.,Davis, Douglas A.,Sottos, Nancy R.,White, Scott R.,Moore, Jeffrey S.
-
p. 13808 - 13809
(2008/04/04)
-
- Synthesis and structure of indoline spiropyrans of the coumarin series
-
New indoline spiropyrans of the coumarin series were synthesized by the condensation of indoline and hydroxyformylcoumarin derivatives. Spiropyrans, viz., derivatives of 8-formyl-7-hydroxy-4-methylcoumarin and 5-formyl-6-hydroxy-4-methylcoumarin, under irradiation are transformed into open forms, which are recyclized in the dark. The compounds formed by the condensation of the indoline derivatives with 3-formyl-4-hydroxycoumarin have an open structure of the merocyanine dyes and are transformed into spiro forms neither in the dark nor under irradiation with the visible light.
- Traven,Miroshnikov,Chibisova,Barachevsky,Venidiktova,Strokach
-
p. 2417 - 2424
(2007/10/03)
-
- Agent for dyeing fibers comprising an indoline/indolium derivative
-
The object of the present invention is an agent for dyeing fibers obtained by mixing two components and characterized in that one component (component A2) contains at least one carbonyl compound and the other component (component A1) contains at least one indoline derivative of formula (I) or a 3H-indoline derivative of formula (Ia) as well as a multicomponent kit for dyeing and later decolorizing fibers, said kit containing both an agent according to the invention for producing a coloration on the fiber and an agent for the reductive removal of said coloration.
- -
-
-
- Ring transformations of heterocyclic compounds. XXII [1]. Pyrido[1,2-a]indolium salts from 2-methyl-3H-indoles by pyrylium mediated three carbon annelation
-
The synthesis of pyrido[1,2-a]indolium perchlorates 8,11 from 2,4,6-triarylpyrylium perchlorates 1 and 2-methyl-3H-indoles 6,9 in the presence of a basic condensing agent (anhydrous sodium acetate, piperidine acetate, triethylamine/acetic acid, triethylamine) in ethanol by a 2,4-[C3+C2N] pyrylium ring transformation is reported. Spectroscopic data of the transformation products and their mode of formation are discussed.
- Zimmermann, Thomas,Hennig, Lothar
-
p. 263 - 269
(2007/10/03)
-
- 1-N-alkyl-5'-[(N'-(un)substituted)amido]spiroindolinonaphthoxazines, their preparation, compositions and (co)polymer matrices containing them
-
The object of the present invention is novel spiroindolinonaphthoxazine compounds as well as the compositions and (co)polymer matrices containing them. Said compounds have interesting photochromic properties. Another object of the present invention is a method of preparing said novel compounds.
- -
-
-
- SYNTHESE DE QUELQUES SPIRO ET SPIRO PHOTOCHROMIQUES. APPLICATION DE LA METHODOLOGIE DE LA RECHERCHE EXPERIMENTALE
-
Some spiro I and spiro II substituted by different groups were synthesized in order to evaluate their photochromic properties and to optimize the preparation of spiroheterocyclic systems.In addition, some spiro III were also prepared as reference compounds.Their physical and spectroscopic characteristics (UV, 1H and 13C) were determined.A study using the experimental design methodology allowed to point out the most important factors for improving the reaction yields. KEYWORDS: Photochromism, spirooxazines, spiropyrans, synthesis, 1H NMR, experimental design methodology.
- Pottier, E.,Sergent, M.,Luu, R. Phan Tan,Guglielmetti, R.
-
p. 719 - 740
(2007/10/02)
-
- Structures of Lithium Salts of 2,3,3-Trimethylindolenine and Its 5-Methoxy Derivative in Solution and the Solid State
-
An X-ray crystal structure of lithium 2,3,3-trimethylindolenide etherate shows it to be a disolvated dimer having a η3-azaallyl-type structure.The structures of the salt in several solvents have been established by studies of 13C chemical shifts, 6Li, 15N spin-spin splitting, 7Li quadrupole splitting constants, and apparent degrees of aggregation determined by vapor pressure barometry.It is the η3-azaallyl dimer disolvate in diethyl ether, a tetrasolvated dimer in dioxolane, a mixture of monomer splitting constants of 230, 156, 180 - 190 (0.27 - 0.75 M), and 217 kHz, respectively.In diethyl ether with 4 equiv of hexamethylphosphoric triamide, the salt is a mixture of monomeric and triple ion species.Lithium 5-methoxy-2,3,3-trimethylindolenide forms similar species except that, in tetrahydrofuran, the tendency for dimer formation is enhanced, which leads to a higher proportion of C- to N-methylation in its reaction with methyl chloride in that solvent.
- Jackman, L. M.,Scarmoutzos, L. M.,Smith, B. D.,Williard, Paul G.
-
p. 6058 - 6063
(2007/10/02)
-
- PHOTOCHROMISM. SYNTHESIS AND PROPERTIES OF INDOLINOSPIROBENZOTHIOPYRANS
-
Novel photochromic compounds, indolinospirobenzothiopyrans, were prepared and their properties in polymer films were examined.The absorption bands of the colored form lie around 100 nm deeper in the long-wave region of the spectrum than are the case with the common spiropyrans.
- Arakawa, Sei'ichi,Kondo, Hirofumi,Seto, Jun'etsu
-
p. 1805 - 1808
(2007/10/02)
-
- Preparation of indolenines
-
A process for the preparation of an indolenine of the formula STR1 where R, X and Y are conventional substituents, by thermal rearrangement of a compound of the formula STR2 to give a compound of the formula STR3 and cyclization of this compound in the presence of an acid catalyst.
- -
-
-
