Fluorescent Molecular Logic Gates and Pourbaix Sensors in Polyacrylamide Hydrogels

Polyacrylamide hydrogels formed by free radical polymerisation were formed by entrapping anthracene and 4-amino-1,8-naphthalimide fluorescent logic gates based on photoinduced electron transfer (PET) and/or internal charge transfer (ICT). The non-covalent immobilisation of the molecules in the hydrogels resulted in semi-solid YES, NOT, and AND logic gates. Two molecular AND gates, examples of Pourbaix sensors, were tested in acidic aqueous methanol with ammonium persulfate, a strong oxidant, and displayed greater fluorescence quantum yields than previously reported. The logic hydrogels were exposed to aqueous solutions with chemical inputs, and the fluorescence output response was viewed under 365 nm UV light. All of the molecular logic gates diffuse out of the hydrogels to some extent when placed in solution, particularly those with secondary basic amines. The study exemplifies an effort of taking molecular logic gates from homogeneous solutions into the realm of solid-solution environments. We demonstrate the use of Pourbaix sensors as pE-pH indicators for monitoring oxidative and acidic conditions, notably for excess ammonium persulfate, a reagent used in the polymerisation of SDS-polyacrylamide gels.     

La2/3Ca1/3MnO3薄膜的光致电阻率变化特性

射频磁控溅射法制备了La_2/3Ca_1/3MnO₃纳米薄膜(LCMO).该薄膜发生FM-PM相变的转变点温度为T_c≈308K（近似为电阻峰值温度T_p）；在不同温度下的光电导性质实验表明所制备的LCMO薄膜在连续激光作用时低温段（Tc）表现为光致电阻率增大效应，即ΔR/R＞0，并在R-T曲线拐点附近取得极大值，（ΔR/R）_max=43.5%；当T>T关键词： 钙钛矿薄膜 光响应 电子自旋 小极化子     

Spectroscopic study of the interaction between porphyrin and chlorin molecules of opposite charge in solutions

Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, Minsk, 220072, 70, F. Skorina Ave., Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 2, pp. 152–163, March–April, 1995.     

Spatial Frequency Response and Transient Anisotropy in Bacteriorhodopsin Thin Films

In this paper, we present new results describing the spatial frequency response in bacteriorhodopsin (bR), immobilised in gelatin films. It is shown that the spatial frequency response is flat, as compared to bR contained in solution form. An experimental investigation into the photoinduced anisotropy of bR films is also presented. It is shown that the anisotropy can be induced using two wavelengths (632.8 nm and 454 nm) and is dependent on the pH of the gelatin matrix, the 454 nm laser polarisation and the 454 nm pump power. The mechanisms producing the anisotropy are briefly discussed.Presented at the International Commission of Optics Topical Meeting, Kyoto, 1994.     

曙红染料-碘鎓盐复合体系的光化学性质和引发丙烯酸酯光交联的效果

合成了曙红(EO)二苯基碘鎓盐(DPIO)复合光引发体系,其光响应范围可至可见光区,最大吸收527nm。曙红鎓盐体系无暗反应,但在可见光作用下,由于光诱导电子转移敏化反应使染料发生漂白作用和鎓盐裂解产生活性自由基,由此可引发环氧6101双丙烯酸酯和季戊四醇三丙烯酸酯的光固化。光固化速度与复合体系的结构组成有关,其中曙红双盐(EO(Ph_I)_2)比曙红单盐(EO(Ph_2I))具有更高的引发效率;在同样条件下双分子体系(EONa_2+Ph_2I+BF_4~-)不能引起交联反应。     

Novel Photoinduced Electron Transfer Reaction of N-methylphenothiazine in Carbon Tetrachloride

PhenothiazinederivativeshaveattractedmuchinterestforalongtimeduetotheirdiversechemicalandbioIogicalproperties,aswellasmedicalaPplicationsl.Theradicalcationofphenothiazinesisbelievedtobeinvolvedinthebiotransformationofphenothiazinedrugs2andnumerousstudieshavethusfocusedonthegenerationandreactionsofphenothiazineradicalcations3-6.WereporthereinanovelphotochemicalreactionofN-methylphenothiazineincarbontetrachloridewhichcoupIestwoparentmoleculeswitheliminationofonemethylgroup(Schemel).Resultsandd…     

Influence of photoinduced isomerization on the chiral separation of novel liquid crystalline materials with a diazene moiety

The influence of photoinduced isomerization on the enantiomeric separation of two newly synthesized liquid crystalline materials, liquid crystals 1 and 2, was studied by high‐performance liquid chromatography on a chiral stationary phase Chiralpack AD‐3. Both materials have one chiral center and one diazene moiety. The compounds were separated into their E and Z isomeric forms. The conditions and time scale of the ultraviolet‐induced E to Z transition were briefly evaluated. Under the optimized conditions, we were able to baseline separate the S and R enantiomers of both the studied materials in their E isomeric form. The chiral separation of liquid crystal 2 after ultraviolet irradiation was unsuccessful. In contrast, the chiral separation of liquid crystal 1 possessing a similar structure to liquid crystal 2 provided baseline separation in its Z isomeric form as well. Previously, we have shown the influence of photoinduced isomerization and its utilization in the enantioseparation on relatively simple molecules. Here, we demonstrate that (1) much more complex compounds can also be successfully separated despite the bulkiness of the achiral part of the structure and (2) photoinduced isomerization even for such complex molecules still strongly influences their chromatographic properties.     

Time dependence of the NMR line shape for systems with chemical exchange in a zero saturation limit

An expression has been derived for the time dependence of the NMR line shape for systems with many-site chemical exchange in the absence of spin-spin coupling, in a zero saturation limit. The dynamics of variation of the NMR line shape with time is considered in detail for the case of two-site chemical exchange. Mathematica programs have been designed for numerical simulation of the NMR spectra of chemical exchange systems. The analytical expressions obtained are useful for NMR line shape simulations for systems with photoinduced chemical exchange.     

Novel Roles of Metal Ions in Layered Self-assembled Films of Polynuclear Complexes on Their Photoinduced Electron Transfer Properties

Three metal ion bridged self-assembled(SA)films of cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium were fabricated and characterized by contact angle,UV spectra,cyclic voltammetry and XPS.Theirphotoinduced electron transfer properties(PETP)were examined.Among the titled systems,the highest steady an-odic photocurrent of 1773—1843 nA/cm~1 and the highest quantum yield of 3.2% were achieved.The effects of in-cident light intensity,bias voltage,and electron donor were also studied.The possible mechanism of electron trans-fer was proposed.The results reveal that different metal ion in SA films could affect significantly the photoinducedelectron transfer property.Our experimental results clearly show that bridging metal ions can play both functionaland structural roles in these self-assembled systems.This method of forming functional films can provide a new ap-proach to regulate the property of similar systems.     

Photoinduced Electron Transfer (PET) between C_(60) and Amines in Micelle Solution A Kinetic ESR Study

Fullerene chemistry has been one of the most exciting research subjects in the recent decade1,2. However, the predominant hydrophobic character and the spherical carbon allotrope of C60 hinder its solubility in an aqueous solution. In order to efficiently slow down charge recombination in the PET system containing C60, water was selected as optimal polar media to stabilize charge separation state. Accordingly, solubility of fullerene in water had to be achieved by incorporating it into th…