Light-driven OR and XOR programmable chemical logic gates

Photoelectrodes made of nanocrystalline titanium dioxide modified with various pentacyanoferrates exhibit unique photoelectrochemical properties; photocurrent direction can be switched from anodic to cathodic and vice versa upon changes in photoelectrode potential and incident light wavelength (PhotoElectrochemical Photocurrent Switching, PEPS effect). At certain potentials, anodic photocurrent generated upon UV irradiation has the same intensity as the cathodic photocurrent generated upon visible irradiation. Under these conditions, simultaneous irradiation with UV and visible light results in compensation of anodic and cathodic photocurrents, and zero net photocurrent is observed. This process can be used for construction of unique light-driven chemical logic gates.     

Photocurrent Response of Surface‐Functionalized Metal Oxides with Well‐Matched Energy Levels: From Nothing to Something

In recent years, an enormous amount of research has been devoted to the study of photosensitive materials from both fundamental and practical viewpoints, due to their wide applications in photocatalytic 1 – 3 and optoelectronic devices, 4 , 5 ultraviolet (UV) photodetectors, 6 – 9 photoswitch microdevices, 10 , 11 light‐emitting diodes, 12 , 13 photovoltaic devices, 14 – 16 and photoelectrochemical cells. 17 Metal oxides, such as ZnO, TiO₂, SnO₂, and NiO have been the most investigated photosensitive materials. 3 , 6 – 8 , 18 – 21 To enhance and take full advantage of their photosensitivity, functionalizing their surface with a polymer that has a high light absorption ability has become one of the widely used methods. 1 – 12 , 22 – 24 For example, Z. L. Wang et al. reported that the UV photocurrent of a ZnO nanobelt‐based sensor was enhanced by close to five orders of magnitude after functionalizing its surface with polystyrene sulfate which has a high UV absorption ability. 25 T. Sasaki et al. reported the assembly of a TiO₂ nanoparticle film with poly(3,4‐ethylenedioxythiophene) and poly(4‐styrene sulfonate) (PEDOT‐PSS) through layer‐by‐layer fabrication in the nanometer scale. The electric conductivity of the TiO₂ composite films could be tuned by UV and visible (Vis) light. 22 Thus, sunlight or photon energy can be used and transformed to electrical energy by UV‐photosensitive metal oxides after their surfaces have been functionalized with a dye that has a high Vis absorption ability. To date, most of the dye‐sensitized solar cells are based on the surface functionalization of UV‐photosensitive metal oxides by dyes. 26 – 28 However, to the best of our knowledge, all of the reports on surface functionalization enhanced only the UV photosensitivity of the metal oxide. In other words, this method has been used exclusively to enhance the UV photocurrent in metal oxides that already have UV‐photosensitive properties, but not to induce UV photocurrent in metal oxides that have no UV‐photosensitive properties. In fact, to the best of our knowledge, there are no surface‐functionalizing reports on inducing UV or Vis photocurrent in metal oxides that have no UV‐ or Vis‐photosensitive properties.     

对四-2,3-吡啶并紫菜嗪铬的薄膜电极的光电化学研究

Photocurrent spectra and photoluminescence measurements of the electrode covered by a thin film of chromium tetra-2,3-pyridinoporphyrazine by conventional 3-electrode system method have been performed. The cathodic photocurrent has been measured. The shape of the photocurrent spectrum is similar to that of photoluminescence spectrum. Their intensities change as a function of the applied potential. Two photoluminescence peaks are located at about 470 nm and 520 nm. The results indicate that the thin film behaves like a p-type semiconductor with a band gap width of about 2 eV.     

对四-2,3-吡啶并紫菜嗪铬的薄膜电极的光电化学研究

由于叶绿素具有较高的光能转换效率,使许多人对类似于叶绿素结构的酞菁染料产生了兴趣,本文所研究的对四-2,3-吡啶并紫菜嗪铬的薄膜(PcCrPy)就是酞菁类(CrPy)染料的苯环用吡啶环取代的衍生物,从而使染料容易电沉积到各种支持导体上。已有不少人对酞菁的薄膜进行过电化学和光电化学的研究,但几乎没有人对PcCrPy进行过光电化学的研究。我们已对PeCrPy进行了原位吸收光谱研究和原位拉曼光谱研究。本文将对     

Photoelectrochemical study of organic–inorganic hybrid thin films via electrostatic layer-by-layer assembly

The stepwise assembly of negatively charged organic molecules (poly(sodium 4-styrenesulfonate) (PSS) or tetrasodium-meso-tetra(4-sulfonatophenyl) porphine (TPPS)) and positively charged TiO₂ colloids on pretreated substrate surfaces utilizing the layer-by-layer (LbL) approach was investigated. The step-by-step formation of these films was studied by UV–vis spectrophotometry and electrochemistry. Photocurrent was generated upon light irradiation of the hybrid thin films assembled on fluorine-doped tin oxide (FTO) conducting glass, which increased linearly as the deposited bilayers increased. In addition, compared to PSS/TiO₂ hybrid thin films, the enhancement of the generated photocurrent and the photocurrent response within the wavelength range from 400 to 450 nm were observed in the TPPS/TiO₂ hybrid thin films. This was attributed to the dye-sensitized effect of the layered TPPS molecules. It was demonstrated that electrostatic LbL films were attractive systems for the photoelectrochemical investigation, and the control of the generated photocurrent could be achieved by the structure of the multilayered films.     

Application of carbon fibers to biomaterials: a new era of nano-level control of carbon fibers after 30-years of development

Carbon fibers are state-of-the-art materials with properties that include being light weight, high strength, and chemically stable, and are applied in various fields including aeronautical science and space science. Investigation of applications of carbon fibers to biomaterials was started 30 or more years ago, and various products have been developed. Because the latest technological progress has realized nano-level control of carbon fibers, applications to biomaterials have also progressed to the age of nano-size. Carbon fibers with diameters in the nano-scale (carbon nanofibers) dramatically improve the functions of conventional biomaterials and make the development of new composite materials possible. Carbon nanofibers also open possibilities for new applications in regenerative medicine and cancer treatment. The first three-dimensional constructions with carbon nanofibers have been realized, and it has been found that the materials could be used as excellent scaffolding for bone tissue regeneration. In this critical review, we summarize the history of carbon fiber application to the biomaterials and describe future perspectives in the new age of nano-level control of carbon fibers (122 references).     

Optical Sensing by Silica/Titania Thin Films Doped with Oxacarbocyanine Dye

Photocurrent responses of sol-gel films of silica/titania doped with oxacarbocyanine dye were investigated with a sandwich-type photocell constructed with polymer electrolyte membrane and indium-tin-oxide glass electrodes. At an equilibrium and positive bias voltages, a typical photocell exhibited negative and positive current peaks when the visible light illumination was on and off, respectively. The wavelength dependence of the photocurrent responses well matched to the absorption band of the doped dye. This differential photocurrent response was attributed to trapping of carriers photoexcited in the dye molecules at the defect states in the matrix film. At negative bias voltages, on the other hand, the cell exhibited constant, negative photoelectrochemical currents under illumination. These differential and linear photocurrent responses were affected by the SiO₂/TiO₂ matrix structures depending on the Si : Ti ratio.     

Quantitative Photoelectrochemical Detection of Biotin Conjugated CdSe/ZnS Quantum Dots on the Avidin Immobilized ITO Electrodes

Photocurrent generation from CdSe/ZnS (core/shell) quantum dots (QDs) in a photoelectrochemical cell was proposed to perform a bioaffinity biosensor in this study. The photocurrent of QDs is reversible and methylene blue as an electron transfer mediator causes a four‐fold increase in the photocurrent. We further present quantitative photoelectrochemical detection of biotin conjugated QDs on the avidin immobilized ITO electrodes. A linear calibration graph was obtained in the range of 4 and 18 nM of biotin conjugated QDs with a coefficient of determination of 0.997. Results imply that QDs can be successfully used as photoelectroactive labels for the photoelectrochemical biosensor systems.     

Reactivity of monolayer-protected gold nanoclusters at dye-sensitized liquid/liquid interfaces

Hexanethiolate monolayer-protected gold nanoclusters (MPCs) were used as redox quenchers at the polarizable water/1,2-dichloroethane (DCE) interface. Photocurrent responses originating from the heterogeneous quenching of photoexcited water soluble porphyrin complexes by MPCs dissolved in the DCE phase were observed. As MPCs can function as both electron acceptors and donors, the photocurrent results from the superposition of two simultaneous processes, which correspond to the oxidation and reduction of MPCs. The magnitude of the net photocurrent is essentially determined by the balance of the kinetics of these two processes, which can be controlled by tuning the Galvani potential difference between the two phases. We show that, within the available potential window, the apparent electron-transfer rate constants follow classical Butler-Volmer dependence on the applied potential difference.     

Surface-modified anodic TiO2 films for visible light photocurrent response

N-doped titania thin films were prepared by anodic oxidation of titanium sheets and subsequent heat treatment in the presence of urea pyrolysis products at 400 °C. The resulting films are modified predominantly at the surface. They exhibited a significant photocurrent response upon visible light irradiation inducing an incident photon-to-current efficiency of 1.5% at 400 nm. The flatband potential was anodically shifted by 0.2 V as compared to the unmodified film. Photocurrent transients revealed that nitrogen-centered intra-bandgap states, responsible for visible light response, induce also enhanced recombination as indicated by a cathodic “overshoot” after turning off the light. This recombination can be inhibited by the presence of iodide.     

The photoelectrochemistry of platinum phthalocyanine films in aqueous media

Platinum phthalocyanine (PtPc) films applied to glassy carbon (GC) and platinum surfaces have been shown to exhibit complex photoelectrochemistry in aqueous media, acting as an n-type semi-conducting material. Using chopped polychromatic radiation and a lock-in amplifier to detect the modulated photocurrent, photo-responses were measured for PtPc films on GC in a variety of background electrolytes. In all instances the photo-responses were anodic over the voltage ranges used. Two peaks were seen in each sweep direction for the experiments performed in sulfuric acid and sodium hydroxide solutions. The origin of the photocurrent has been ascribed to the photo-oxidation of water in the electrolyte by positive holes produced under illumination, which accumulate at the PtPc/electrolyte interface. Photocurrent transients were also recorded and indicated some recombination of excitons within the system.     

Enhancement of photocurrent generation by honeycomb structures in organic thin films.

A light-emitting poly (distyryldimethylbenzene-co-triethylene glycol) rod-coil block copolymer was used to fabricate films with three-dimensionally ordered honeycomb structures by the breath-figure method. Photocurrent generation and photovoltaic performance are studied, and the dependence of photocurrent on applied electric field is investigated. Introducing the ordered porous structure significantly improves the photoelectric conversion behavior, because porous structures not only enhance the light-harvesting efficiency but also benefit charge separation and charge transfer. This phenomenon may have great prospects for enhancing the photovoltaic behavior of organic thin-film devices.     

Hydrochlorothiazide Enhances UVA‐Induced DNA Damage

The UVA is currently thought to be carcinogenic because, similar to UVB, it induces the formation of cyclobutane pyrimidine dimers (CPDs). Various drugs have been reported to cause photosensitive drug eruptions as an adverse effect. Although the precise mechanism of photosensitive drug eruption remains to be elucidated, it is generally accepted that free radicals and other reactive molecules generated via UV‐irradiated drugs play important roles in the pathogenesis of photosensitive drug eruptions. The waveband of concern for photo‐reactive drugs is UVA‐visible light, but some extend into the UVB region. We tested whether photosensitive drugs could enhance CPD formation after UVA exposure by using isolated DNA in the presence of several reported photosensitive drugs using high‐performance liquid chromatography. We found that the diuretic agent hydrochlorothiazide (HCT) significantly enhanced the production of TT dimers over a wide range of UVA. Furthermore, we investigated whether UVA plus HCT could enhance CPD production in xeroderma pigmentosum model mice defective in nucleotide excision repair. Immunofluorescence studies showed that CPD formation in the skin significantly increased after 365 nm narrow‐band UVA irradiation in the presence of HCT, compared with that in wild‐type mice. HCT could be used with caution because of its enhancement of UVA‐induced DNA damage.     

Molecular assembly of artificial photosynthetic antenna core complex on an amino-terminated ITO electrode

Bacterial photosynthetic membrane proteins, light-harvesting antenna complex (LH1), reaction center (RC), and their combined ‘core’ complex (LH1–RC) are functional elements in the primary photosynthetic events, i.e., capturing and transferring light energy and subsequent charge separation. These photosynthetic units (PSUs) isolated from Rhodospirillum rubrum (Rs. rubrum) were assembled onto an ITO electrode modified with 3-aminopropyltriethoxysilane (APS–ITO). The near IR absorption spectra of PSUs on the assembled electrodes were identical to those of solutions, indicating that the LH1 and LH1–RC core complexes were native on the electrode. Photocurrent response of PSUs on the electrode was examined upon illumination of the LH1 complex at 880 nm. The LH1–RC and a mixed assembly of LH1 and RC exhibited photocurrent response, but not LH1 only, consistent with the function of these PSUs, capturing light energy and transferring electron. This result provides useful methodology for building an artificial fabrication of PSUs on the electrode.     

Photosensitive and Biomimetic Core–Shell Nanofibrous Scaffolds as Wound Dressing

Tissue engineered skin grafts that mimic the native extracellular matrix of skin has gained huge popularity among clinicians since they increase the survival rate of the patients. Phototherapy shows promising results with respect to acute and chronic pain relief, treatment of inflammatory conditions and promotion of wound healing. Here, we encapsulated a photosensitive polymer poly (3‐hexylthiophene) (P3HT) and epidermal growth factor in the core–shell‐structured Gelatin/poly(L‐lactic acid)‐co‐poly‐(ε‐caprolactone) nanofibers [Gel/PLLCL/P3GF(cs)] by coaxial spinning and studied the potential application of the Gel/PLLCL/P3GF(cs) nanofibrous scaffold as a novel skin graft. The proliferation of fibroblasts was significantly improved on Gel/PLLCL/P3GF(cs) under light stimulation compared to fibroblasts on the same scaffold under dark condition. Studies on the in vitro wound healing ability of Gel/PLLCL/P3GF(cs) showed complete closure of wound after 9 days under “light stimulation” too. Furthermore, the potential of adipose‐derived stem cells (ASCs) to differentiate to epidermal cells on Gel/PLLCL/P3GF(cs) was evaluated. The differentiated ASCs with keratinocytes morphology were only found on the light stimulated Gel/PLLCL/P3GF(cs). Our results suggest that the photosensitive core–shell Gel/PLLCL/P3GF(cs) nanofibers could be a novel substrate to aid in the reestablishment of skin architecture.     

Characterizations of iron-rich clay modified electrodes and their applications in optical recognition

Optical recognition was studied with modified electrodes based on iron-rich clays. According to energy-dispersive X-ray spectroscopy (EDX), several clay minerals including montmorillonite K10 (mont. K10) contain a lot of iron. Cyclic voltammetry suggested that electrochemically active iron species exist in most iron-rich clays and are likely to reside at different sites. The associated electrochemical activity is strongly pH-dependent and photosensitive. Under UV irradiation (λ ≤ 420 nm), these iron species were activated, and a pronounced photocurrent resulted. When these electrodes were flow-injected with 2-pyridylcarboxylic acids (λ_ab,max = 260 nm), the originally monotonic photocurrent could be modulated into a more recognizable a.c. pattern and the 260 nm optical signal became distinguishable. The photoresponse was highly reproducible, and the response time (t₉₀) was less than 10s.     

Photochemical and photoelectrochemical behaviour of chlorophyll a-smectite conjugate

Chlorophyll a was adsorbed onto smectite to form chlorophyll-smectite conjugate, which became photostable against light illumination. The chlorophyll-smectite conjugate caused the photoreduction of nitro blue tetrazolium, NBT, through the formation of superoxide anion, and the conjugate retained the photosensitive activity even after 20 hour illumination. Furthermore, the conjugate deposited on SnO₂ electrode caused electron transfer under light illumination. The anodic photocurrent rose at ?200 mV versus Ag/AgCl electrode (KCl saturated) and reached a maximum level at approximately +100 mV. The photocurrent spectrum was in good agreement with the absorption spectrum of chlorophyll-smectite conjugate in an aqueous solution and the quantum efficiency was approximately 1% at 670 nm.     

Effect of Chemical Treatment on TiO2 Particles by IMPS

The photodegradation reaction rate of CHCl3 in TiO2 particulate suspension was imperoved significantly by HCl-treatment.The effect of HCl-treatment on the photocatalytic activity of TiO2 was strdied in a PEC cell by using Intensity-Modulated Photocurrent Spectroscopy(IMPS).The magntude of photocurrent response and the characteristic frequencies of the upper and lower semicircles in the complex plane of IMPS response were analyzed,and the ccathodic and anodic reaction processes of photogenerated holes and electrons were discussed.The increases in the cathodic and anodic photocurrent response and in the time constants of both cathodic and anodic reaction processes of photogenerated holes and electrons were discussed.The increases in the cathodic and anodic photocurrent response and in the time constants of both cathodic and anodic reaction processes indicate that HCl-treatment leads to the improvement of the photocatalytic activity of TiO2 and a change of the photocatalytic kinetic mechanism.     

Phototesting in lupus erythematosus tumidus--review of 60 patients

Photosensitivity is an important characteristic feature of several forms of lupus erythematosus (LE), and induction of skin lesions by UV-A and UV-B irradiation has been proved to be an optimal model for evaluating light sensitivity in patients with this disease. Because lupus erythematosus tumidus (LET) has rarely been documented in the literature and is often difficult to differentiate from other photodermatoses such as polymorphous light eruption, we performed photoprovocation tests in 60 patients with LET according to a standardized protocol. Areas of uninvolved skin on the upper back were irradiated with single doses of UV-A (100 J/cm2) and/or UV-B (1.5 minimal erythema dose) daily for three consecutive days. Interestingly, patients with LET are more photosensitive than those with subacute cutaneous lupus erythematosus, and in our study experimental phototesting revealed characteristic skin lesions in 43 patients (72%). Because of the latency period in developing positive phototest reactions, it might be difficult for these patients to link sun exposure with their skin lesions. Furthermore, our data revealed a positive correlation of antinuclear antibodies and positive provocative phototest reactions in these patients as seen for other forms of LE. In conclusion, the high incidence of positive phototest reactions in correlation with the clinical findings, history of photosensitivity and antinuclear antibodies enable the classification of LET as the most photosensitive type of LE.     

基于聚硫堇/过氧化氢光电化学敏感界面的胆碱传感器

将胆碱氧化酶固定在具有光电活性的聚硫堇光透电极的表面,利用壳聚糖和戊二醛键合胆碱氧化酶制备了光致电化学胆碱传感器.此传感器基于同时具有光敏和电子受体功能的聚硫堇光电界面,能与胆碱氧化酶催化胆碱反应产生的电子供体(H2O2)发生光致电化学反应的原理,实现了对胆碱的检测.探讨了传感器的光致电化学响应机理、偏压、光强及电解质...