新型螺吡喃衍生物: 离子传感和分子水平的信息处理

为实现金属离子检测和分子水平的信息处理, 合成了一类新型的含有功能配位基团的螺吡喃衍生物(SP1-SP4). 研究发现: 在没有UV光照的条件下, 金属离子可以促进螺吡喃(SP2和SP4)开环并形成稳定可逆的络合物(MC-Mⁿ⁺). 紫外-可见吸收光谱研究表明, 在UV光照前加入不同的金属离子会引起SP2 和SP4 的光学性质的特征变化, 因此提供了一种简易的通过裸眼就能辨别金属离子的比色方法. 荧光光谱研究表明, 这类化合物能够高灵敏高选择性地检测锌离子. 此外, 基于吸收光谱和荧光光谱的变化, 这类螺吡喃衍生物可以用于构建组合的逻辑门, 执行分子水平的信息处理, 从而展现了其在化学或环境传感和未来的分子计算机领域的潜在应用前景.     

Reversible photorheological fluids based on spiropyran-doped reverse micelles

We describe a new class of photorheological (PR) fluids whose rheological properties can be reversibly tuned by light. The fluids were obtained by doping lecithin/sodium deoxycholate (SDC) reverse micelles with a photochromic spiropyran (SP) compound. Initially, the lecithin/SDC/SP mixtures formed highly viscoelastic fluids, reflecting the presence of long, wormlike reverse micelles. Under UV irradiation, the SP was isomerized to the open merocyanine (MC) form, causing the fluid viscosity to decrease 10-fold. When the UV irradiation was switched off, the MC reverted to the SP form, and the viscosity recovered its initial value. This cycle could be repeated several times without loss of response. The rheological transitions are believed to reflect changes in the lengths of the reverse worms. To our knowledge, this is the first example of a simple, reversible PR fluid that can be made entirely from commercially available components.     

Conductance Photoswitching of Metal–Organic Frameworks with Embedded Spiropyran

Conductive metal–organic frameworks (MOFs) as well as smart, stimuli‐responsive MOF materials have attracted considerable attention with respect to advanced applications in energy harvesting and storage as well as in signal processing. Here, the conductance of MOF films of type UiO‐67 with embedded photoswitchable nitro‐substituted spiropyrans was investigated. Under UV irradiation, the spiropyran (SP) reversibly isomerizes to the open merocyanine (MC) form, a zwitterionic molecule with an extended conjugated π‐system. The light‐induced SP–MC isomerization allows for remote control over the conductance of the SP@UiO‐67 MOF film, and the conductance can be increased by one order of magnitude. This research has the potential to contribute to the development of a new generation of photoelectronic devices based on smart hybrid materials.     

Wetting properties of flat and porous silicon surfaces coated with a spiropyran

We report the immobilization and characterization of a spiropyran (SP) derivative (1) on smooth Si(100) and porous H-terminated silicon surfaces through a thermal hydrosilylation protocol. Under visible light exposure the SP is in a closed, hydrophobic form, whereas under UV irradiation it converts to a polar, hydrophilic open form named merocyanine (MC). The SP-MC photoinduced isomerization gives a small contact angle (CA) change of 9 degrees for smooth Si(100) samples under sequential irradiation cycles with white and UV light. Irradiation of porous silicon (PS) surfaces, under the same conditions, gave a CA change of 11 degrees. Treatment of PS surfaces, bearing the MC form of chromophore 1, with cobalt(II) ions enhances the wettability switching of the PS surface to a much larger extent, giving rise to a CA variation as high as 32 degrees.     

Photoregulation of α‐Chymotrypsin Activity by Spiropyran‐Based Inhibitors in Solution and Attached to an Optical Fiber

Here the synthesis and characterization of a new class of spiropyran‐based protease inhibitor is reported that can be reversibly photoswitched between an active spiropyran (SP) isomer and a less active merocyanine (MC) isomer upon irradiation with UV and visible light, respectively, both in solution and on a surface of a microstructured optical fiber (MOF). The most potent inhibitor in the series ( SP ‐ 3 b ) has a C‐terminal phenylalanyl‐based α‐ketoester group and inhibits α‐chymotrypsin with a K_i of 115 nM . An analogue containing a C‐terminal Weinreb amide ( SP‐2 d ) demonstrated excellent stability and photoswitching in solution and was attached to the surface of a MOF. The SP isomer of Weinreb amide 2 d is a competitive reversible inhibitor in solution and also on fiber, while the corresponding MC isomer was significantly less active in both media. The ability of this new class of spiropyran‐based protease inhibitor to modulate enzyme activity on a MOF paves the way for sensing applications.     

Spiropyran‐Conjugated Pluronic as a Dual Responsive Colorimetric Detector

Novel spiropyran‐conjugated Pluronic [polyethylene oxide (PEO)‐b‐polypropylene oxide (PPO)‐b‐polyethylene oxide (PEO)] micelles are developed as a new colorimetric detector showing photo‐ or thermo‐switchable behavior. Facile conjugation of spiropyran to Pluronic was confirmed by ¹H NMR, UV–Vis, and Fluorescence spectroscopy. A switchable photoluminescence is found depending on the irradiation with either UV or visible light, and temperature resulting from structural isomerization of spiropyran between spiropyran (SP) and merocyanine (MC) form. Cytotoxicity of the spiropyran‐conjugated Pluronic (SP‐PL) was evaluated following an MTT assay, whereas photo responsiveness of spiropyran within the micelles was determined by confocal laser scanning microscopy.     

螺吡喃逆向变色光量子产率测定及其光致变色特性研究

研究了1'-十八烷基-3',3',-二甲基-6,8-二硝基螺[2H-1-苯并吡喃-2,2'-吲哚啉]的逆向光致变色特性,通过吸收光谱测定了其在不同溶剂中可见光照后无色体(SP)的开环生色速率常数及在甲醇中有色体(MC)光照关环的光量子产率,发现溶剂的极性对开环有色体(MC)的吸收光谱影响较大,但对无色体的开环速率常数的影响相对较小。利用¹HNMR分析了SP和MC的结构,证实了MC处于反式构型。     

Photo‐switchable spiropyran immobilized polystyrene beads using catechol chemistry

Catechol and spiropyran functional groups were conjugated to a polymer backbone, allowing immobilization on polystyrene beads (PS beads). The final product was capable of stably reproducing the optical properties of spiropyran. Through the outstanding surface adhesion properties of the catechol functional group, spiropyran was immobilized on PS beads. Switchable photoluminescence in the spiropyran coated PS bead surfaces was observed depending on irradiation with either UV or visible light. The surfaces of the PS beads were morphologically examined by field emission scanning electron microscopy and X‐ray photoelectron spectroscopy was used for characterization of the constituent atoms. Furthermore, UV–Vis and fluorescence spectroscopy were used to confirm conversion between the spiropyran (SP) and merocyanine (MC) forms through UV or visible light irradiation on SP, while fluorescent images for both SP and MC were studied using confocal laser scanning microscopy. The confocal images of the SP‐PS beads system onto MDAMB‐231 cells under UV and visible light indicate the cellular uptake by emerging color within the cytoplasm. Advancing study, the remaining catechol groups can confers adhesive properties, given by contact angle data of various coated surfaces film. These stimuli‐responsive coatings are compatible as drawing switchable photochromic material on versatile substrate shown in confocal images of propylene film. Overall, this great water solubility and biocompatibility PS beads system also showed potential as cell bio‐imaging light stimuli responsive material, and the benefits of this system can also possibly address coat able advanced material for a wide range of surface light sensor applications. Copyright © 2017 John Wiley & Sons, Ltd.     

Photo-isomerization of spiropyran-modified cationic surfactants

Photo-induced isomerization of a newly synthesized surfactant, 1'(6-trimethylammoniododecyl)-3('),3(')-dimethyl-6-nitrospiro-(2H-1-benzopyran-2,2'-indoline) bromide (SP-Me-12), has been characterized on the basis of the UV-vis absorption spectra and the surface tension data. Visible light (lambda>420 nm) incident on the aqueous solution of SP-Me-12 results in the isomerization from the merocyanine (MC) form to the spiropyran (SP) form; this structural change was confirmed by a complete disappearance of a characteristic absorption peak of the MC form. When the surfactant solution is stored in the dark, the isomerized SP form reverts to the original MC form, however, the reverse isomerization rate is observed to be considerably slower than that seen for visible light irradiation (from the MC form to the SP form). A reversible change in the surface tension of the aqueous surfactant solution is observed for the photo-induced isomerization: the surface tension measured below the critical aggregation concentration decreases as a result of the visible light irradiation and it is gradually reversed to the original level during the equilibration in the dark.     

Photo‐/Baso‐Chromisms and the Application of a Dual‐Addressable Molecular Switch

Two typical molecular switches of spiropyran (SP) and benzoxazine (OX) were fused by sharing an indole to achieve a new dual‐addressable molecular switch (SP‐OX‐NO₂). Through proper molecular modification with NO₂, the transformation from merocyanine (MC) to ring‐closed SP or ring‐closed OX can be controlled separately with visible light or base stimuli in solution, respectively, and these processes are verified by UV‐vis and NMR spectroscopy as well as control experiments. The cis‐merocyanine (cis‐MC) form is involved in the basochromic process in solution. DFT calculation suggests that the bidirectional switching property of the fused SP‐OX molecular switch can be controlled separately, when the OX isomer is more stable than the deprotonated SP isomer. Because of the significant color variations in solution, the simple dual‐addressable switch has been further successfully applied to construct a multicolor reversible display on paper.     

Synthesis, photophysical, photochemical, and redox properties of nitrospiropyrans substituted with Ru or Os tris(bipyridine) complexes

Photochromic nitrospiropyrans substituted with 2,2'-bipyridine (bpy), [Ru(bpy)3]2+, and [Os(bpy)3]2+ groups were synthesized, and their photophysical, photochemical, and redox properties investigated. Substitution of the spiropyran with the metal complex moiety results in strongly decreased efficiency of the ring-opening process as a result of energy transfer from the excited spiropyran to the metal center. The lowest excited triplet state of the spiropyran in its open merocyanine form is lower in energy than the excited triplet MLCT level of the [Ru(bpy)3]2+ moiety but higher in energy than for [Os(bpy)3]2+, resulting in energy transfer from the excited ruthenium center to the spiropyran but inversely in the osmium case. The open merocyanine form reduces and oxidizes electrochemically more easily than the closed nitrospiropyran. Like photoexcitation, electrochemical activation also causes opening of the spiropyran ring by first reducing the closed form and subsequently reoxidizing the corresponding radical anion in two well-resolved anodic steps. Interestingly, the substitution of the spiropyran with a Ru or Os metal center does not affect the efficiency of this electrochemically induced ring-opening process, different from the photochemical path.     

Probing Metal Ion Complexation of Ligands with Multiple Metal Binding Sites: The Case of Spiropyrans

Among known molecular switches, spiropyrans attract considerable interest because of their reversible responsiveness to external stimuli and the deep conformational and electronic changes that characterize the switching process between the two isomeric forms [spiropyran (SP) and merocyanine (MC)]. Metal coordination is one of the most interesting aspects of spiropyrans for its potential in sensing, catalysis, and medicinal chemistry, but little is known about the details surrounding spiropyran–metal ion binding. We investigated the interplay between an N‐modified 8‐methoxy‐6‐nitrospiropyran (SP‐E), designed to provide appropriate molecular flexibility and a range of competing/collaborative metal binding sites, with Mg²⁺, Cu²⁺ and Zn²⁺, which were chosen for their similar coordination geometry preferences while differing in their hard/soft character. The formed molecular complexes were studied by means of UV/Vis, fluorescence, and NMR spectroscopies and mass spectrometry, and the crystal structure of the SP‐E–Cu complex was also obtained. The results indicate that the Mg²⁺, Zn²⁺ and Cu²⁺ complexes have identical coordination stoichiometry. Furthermore, the Mg²⁺ and Zn²⁺ complexes display fluorescence properties in solution and visible‐light responsiveness. These results provide important spectroscopic and structural information that can serve as a foundation for rational design of spiropyran‐based smart materials for metal sensing and scavenging applications.     

A semiclassical molecular dynamics of the photochromic ring-opening reaction of spiropyran

The photochromic ring-opening reaction of spiropyran(SP) has been investigated by a realistic semiclassical dynamics simulation,accompanied by SA3-CASSCF(12 10)/MS-CASPT2 potential energy curves(PECs) of S0–S2.The main simulation results show the dominate pathway corresponds to the ringopening process of trans-SP to form the most stable merocyanine(MC) product.These findings provide more important complementarity for interpreting experimental observations.     

Detailed investigation on a negative photochromic spiropyran

The negative photochromic properties of a spiropyran are investigated in various solvents and in solutions of different acidity. The results indicate that the polarity of the solvent has a prominent effect on λ_max of the coloured merocyanine form (MC), whereas its effects on λ_max of the closed form (SP) and on the coloration rates after visible bleaching are very weak. From the effect of acid concentration on the coloration rates the pK_a of the cis intermediate Y in the coloration process is determined to be about 1.1 lower than that of the protonated merocyanine (MCH⁺). The structures and configurations of MC, SP, MCH⁺ and Y are assigned via their ¹H NMR spectra.     

Photo-, thermally, and pH-responsive microgels

Microgels with photo-, thermally, and pH-responsive properties in aqueous suspension have been synthesized and characterized using dynamic light scattering and UV-visible spectroscopy. The new route involved first preparing poly(N-isopropylacrylamide) (PNIPAM)-allylamine copolymer microgels and a spiropyran photochrome (SP) bearing a carboxylic acid group. Then the functionalized spiropyran was coupled to the microgel via an amide bond. The dark-equilibrated gel particles feature spiropyran molecules in the polar, merocyanine form. After irradiation of visible light, the particle size becomes smaller because spiropyran changes to the relatively nonpolar, closed spiro form. The PNIPAM-SP microgels undergo a volume phase transition in water from a swollen state to a collapsed state with increasing temperature under all light conditions. However, the transition temperature range of the PNIPAM-SP is much broader than that for the PNIPAM without SP. The PNIPAM-SP microgels are monodisperse and self-assemble into a crystalline lattice while in suspension. The UV-visible spectra of an aqueous suspension of PNIPAM-SP microgel in the dark-adapted, merocyanine form showed both an absorption peak around 512 nm due to the merocyanine (giving a reddish color to the suspension) and two sharp peaks from Bragg diffraction of colloidal crystallites. Upon visible irradiation, the 512-nm band bleached significantly due to spiropyran photoisomerization. The spiropyran photoisomerization and accompanying color changes of the suspension were reversible upon alternating dark, UV, and visible light irradiation. Due to the residues of amine groups, the swelling capability of PNIPAM-SP microgels reduces as the pH value is changed from 7 to 10.     

Stabilization of merocyanine by protonation, charge, and external electric fields and effects on the isomerization of spiropyran: a computational study

Protonation, charging, and field effects on the thermal isomerization of a nitrospiropyran (SP) modified by a thiolated etheroxide chain into merocyanine (MC) are computationally studied at the DFT level. The ring opening leads to cis-MC conformers that then isomerize to the more stable trans forms. While the closed neutral spiropyran is more stable than the conjugated open forms, the merocyanine conformers are significantly stabilized by protonation, electron attachment, and ionization. For protonation on the pyran oxygen atom and electron attachment, the MC conformers are more stable than SP, and unlike for the neutral species, the ring opening is spontaneous at room temperature. Moreover, for the pyran oxygen-protonated form, the ring opening to the cis-merocyanine becomes barrierless. On the other hand, barriers comparable to the neutral remain along the thermal pathway to the cis-merocyanine conformer for ionization or electron attachment, and the barrier for isomerization is significantly higher for the N-protonated SP form. External field effects on the neutral reaction path show that ring opening to the cis-merocyanine is favored when the field reduces the electron density on the pyran part, as also induced by the local field due to O protonation.     

含BOC保护基团的螺吡喃类化合物的合成及其光致变色性能的研究

合成了5-[N-(叔丁氧甲酰基)氨基]-1,3,3-三甲基-6′-硝基吲哚啉螺吡喃(BOCSPI)和5-[N-(叔丁氧甲酰基)氨基]-1,3,3-三甲基-6′-硝基-8′-甲氧基吲哚啉螺吡喃(BOCSPII)两种光致变色化合物,采用紫外-可见光谱法研究了其在溶液和以不同质量比掺杂在聚甲基丙烯酸甲酯(PMMA)膜中的光致变色性能.研究表明螺吡喃的高掺杂量不利于其开环和闭环态的转化,BOCSPII分子中的甲氧基有利于有色开环体的部花菁的稳定.     

Brewster angle microscopic observations of the Langmuir films of amphiphilic spiropyran during compression and under UV illumination

The structure of the Langmuir film of an amphiphilic spiropyran, 1',3'-dihydro-3',3'-dimethyl-6-nitro-l'-octadecyl-8-(docosanoyloxyme thyl)spiro[2H-1-benzopyran-2,2'-(2H)-indole] (SP), is investigated using Brewster angle microscopy (BAM). The BAM observations show that the Langmuir film of SP can be roughly categorized into three regimes: a low-temperature regime at 7-13 degrees C; a medium-temperature regime at 23-30 degrees C; a high-temperature regime at 40 degrees C. The low-temperature regime is characterized both by the domains that are formed just after the spreading and by the onset of the surface pressure when the domains are merged together to form continuous trilayers. In the medium-temperature regime, a continuous monolayer film is formed after the solvent evaporation, followed by the growth of "embryos" with compression. Around the phase transition point, the "embryos" serve as the "nucleation sites" of the circular trilayer domains. The characteristic features of the high-temperature regime are similar to the ones of the medium-temperature regime except for the absence of a steep rise in surface pressure after the plateau region and the absence of the circular trilayer domains. UV illumination of the Langmuir films leads to the isomerization of SP into merocyanine (MC). However, J-aggregates of MC are formed only when the circular trilayer domains are present. On the basis of the above results, we present a phase diagram of the Langmuir film of SP. The structure and photoreaction depend strongly on the phase of the Langmuir film, indicating that the area/molecule is not the only decisive parameter.     

Thermal hysteresis in the photoresponsivity of a langmuir film of amphiphilic spiropyran

We have found a thermal hysteresis in the photoresponsivity of a Langmuir film for the first time. The Langmuir film of an amphiphilic spiropyran, 1',3'-dihydro-3',3'-dimethyl-6-nitro-1'-octadecyl-8-(docosanoyloxymethyl)spiro[2H-1-benzopyran-2,2'-(2H)-indole] (SP) was fabricated at 13 degrees C at 10 mN m-1, followed by heating to a given temperature. UV irradiation of this film caused only the isomerization of SP to the corresponding merocyanine (MC) up to 29 degrees C. Light-induced J-aggregation of MC occurred at 30 degrees C. On the other hand, once the film was heated to 30 degrees C, light-induced J-aggregation was observed down to 27 degrees C. The hysteresis should be related with the phase transitions that occur in the bulk of SP at similar temperatures. No significant morphological change occurred by light-induced J-aggregation in the Langmuir-Blodgett (LB) film of SP by the present method, in contrast to the case of the LB films fabricated under isothermal conditions at 30 degrees C. This feature enabled us to pattern the LB film with J-aggregate of MC by UV irradiation through a photomask of lines with a width of 5 mum each.     

Kinetic study of the helix to coil dark reaction of poly(spiropyran-L-glutamate).

An investigation of kinetics of the helix to coil dark reaction of light adapted poly(spiropyran-L-glutamic acid) (PSLG) dissolved in hexafluoroisopropanol was performed. The reaction was associated with the spiropyran (SP) to merocyanine (MC) ring opening. The ring opening reaction monitored with UV/VIS spectroscopy showed first order kinetics. Chromophore and polypeptide backbone circular dichroism data fit to an expression consistent with a single intermediate series mechanism. By FTIR, we monitored the polypeptide alpha-helix amide I, the MC chromophore--C = C--stretch and the protonated unmodified carboxylate C = O stretch bands. During the first step of the series mechanism, changes in the hydrogen bonding of the unmodified carboxylate groups occurred, suggesting breakup of polypeptide aggregates. The second step of the proposed series mechanism was dominated by the helix to coil transition and the ring opening of SP to MC. The CD spectrum of MC in the dark adapted PSLG was red shifted and had a narrower bandwidth than the UV/VIS spectrum. The kinetic and spectroscopic data suggested that a fraction (population I) of the MC chromophores experienced optical activity induced by the chiral polypeptide environment, while the remainder of the MC chromophores (population II) were solvated and enantiomeric.