Vanadium-doped metal-organic framework@Znln2S4 core-shell heterojunction-attenuated photoelectrochemical immunoassay.

Considering that cancer has become the second leading cause of death in humans, it is essential to develop an analytical approach that can sensitively detect tumor markers for early detection. We report an attenuated photoelectrochemical (PEC) immunoassay based on the organic-inorganic heterojunction 10MIL-88B(FeV)/ZnIn2S4 (10M88B(FeV)/ZIS) as a photoactive material for monitoring carcinoembryonic antigen (CEA). The 10M88B(FeV)/ZIS heterojunctions have excellent light-harvesting properties and high electrical conductivity, which are attributed to the advantages of both organic and inorganic semiconductors, namely, remarkable photogenerated carrier separation efficiency and long photogenerated carrier lifetime. Horseradish peroxidase (HRP) in the presence of H2O2 can catalyze 3,3'-diaminofenamide (DAB) producing brown precipitates (oxDAB), which is then loaded onto the 10M88B(FeV)/ZIS heterojunction to reduce the photocurrent and enable the quantitative detection of CEA. Under optimal conditions, the photocurrent values of the PEC biosensor are linearly related to the logarithm of the CEA concentrations, ranging from 0.01 ng mL-1 to 100 ng mL-1 with a detection limit (LOD) of 4.0 pg mL-1. Notably, the accuracy of the PEC biosensor is in agreement with that of the human CEA enzyme-linked immunosorbent assay (ELISA) kit.

Light-Induced Bipolar Photoresponse with Amplified Photocurrents in an Electrolyte-Assisted Bipolar p-n Junction.

The p-n junction with bipolar characteristics sets the fundamental unit to build electronics while its unique rectification behavior constrains the degree of carrier tunability for expanded functionalities. Herein, a bipolar-junction photoelectrode employed with a gallium nitride (GaN) p-n homojunction nanowire array that operates in electrolyte is reported, demonstrating bipolar photoresponse controlled by different wavelengths of light. Significantly, with rational decoration of a ruthenium oxides (RuOx ) layer on nanowires guided by theoretical modeling, the resulting RuOx /p-n GaN photoelectrode exhibits unambiguously boosted bipolar photoresponse by an enhancement of 775% and 3000% for positive and negative photocurrents, respectively, compared to the pristine nanowires. The loading of the RuOx layer on nanowire surface optimizes surface band bending, which facilitates charge transfer across the GaN/electrolyte interface, meanwhile promoting the efficiency of redox reaction for both hydrogen evolution reaction and oxygen evolution reaction which corresponds to the negative and positive photocurrents, respectively. Finally, a dual-channel optical communication system incorporated with such photoelectrode is constructed with using only one photoelectrode to decode dual-band signals with encrypted property. The proposed bipolar device architecture presents a viable route to manipulate the carrier dynamics for the development of a plethora of multifunctional optoelectronic devices for future sensing, communication, and imaging systems.

ZnO Materials as Effective Anodes for the Photoelectrochemical Regeneration of Enzymatically Active NAD.

This work reports the study of ZnO-based anodes for the photoelectrochemical regeneration of the oxidized form of nicotinamide adenine dinucleotide (NAD+). The latter is the most important coenzyme for dehydrogenases. However, the high costs of NAD+ limit the use of such enzymes at the industrial level. The influence of the ZnO morphologies (flower-like, porous film, and nanowires), showing different surface area and crystallinity, was studied. The detection of diluted solutions (0.1 mM) of the reduced form of the coenzyme (NADH) was accomplished by the flower-like and the porous films, whereas concentrations greater than 20 mM were needed for the detection of NADH with nanowire-shaped ZnO-based electrodes. The photocatalytic activity of ZnO was reduced at increasing concentrations of NAD+ because part of the ultraviolet irradiation was absorbed by the coenzyme, reducing the photons available for the ZnO material. The higher electrochemical surface area of the flower-like film makes it suitable for the regeneration reaction. The illumination of the electrodes led to a significant increase on the NAD+ regeneration with respect to both the electrochemical oxidation in dark and the only photochemical reaction. The tests with formate dehydrogenase demonstrated that 94% of the regenerated NAD+ was enzymatically active.

Peptide-Based Photocathodic Biosensors: Integrating a Recognition Peptide with an Antifouling Peptide.

Accurate and sensitive detection of targets in practical biological matrixes such as blood, plasma, serum, or tissue fluid is a frontier issue for most biosensors since the coexistence of both potential reducing agents and protein molecules has the possibility of causing signal interference. Herein, aiming at detection in a complex environment, an advanced and robust peptide-based photocathodic biosensor, which integrated a recognition peptide with an antifouling peptide in one probe electrode, was first proposed. Selecting human chorionic gonadotropin (hCG) as a model target, the recognition peptide with the sequence PPLRINRHILTR was first anchored on the CuBi2O4/Au (CBO/Au) photocathode and then the antifouling peptide with the sequence EKEKEKEPPPPC was further anchored to generate an antifouling biointerface. The peptide-based photocathodic biosensor demonstrated excellent anti-interference to both nonspecific proteins and reducing agents because of the capability of the antifouling peptide. It also exhibited good sensitivity owing to the utilization of the recognition peptide rather than an antibody probe. This peptide-integrated method offers a new perspective for practical applications of photocathodic biosensors.

Absolute quantum yield measurements of fluorescent proteins using a plasmonic nanocavity.

One of the key photophysical properties of fluorescent proteins that is most difficult to measure is the quantum yield. It describes how efficiently a fluorophore converts absorbed light into fluorescence. Its measurement using conventional methods become particularly problematic when it is unknown how many of the proposedly fluorescent molecules of a sample are indeed fluorescent (for example due to incomplete maturation, or the presence of photophysical dark states). Here, we use a plasmonic nanocavity-based method to measure absolute quantum yield values of commonly used fluorescent proteins. The method is calibration-free, does not require knowledge about maturation or potential dark states, and works on minute amounts of sample. The insensitivity of the nanocavity-based method to the presence of non-luminescent species allowed us to measure precisely the quantum yield of photo-switchable proteins in their on-state and to analyze the origin of the residual fluorescence of protein ensembles switched to the dark state.

Supramolecular and suprabiomolecular photochemistry: a perspective overview.

In this perspective review article, we have attempted to bring out the important current trends of research in the areas of supramolecular and suprabiomolecular photochemistry. Since the spans of the subject areas are very vast, it is impossible to cover all the aspects within the limited space of this review article. Nevertheless, efforts have been made to assimilate the basic understanding of how supramolecular interactions can significantly change the photophysical and other related physiochemical properties of chromophoric dyes and drugs, which have enormous academic and practical implications. We have discussed with reference to relevant chemical systems where supramolecularly assisted modulations in the properties of chromophoric dyes and drugs can be used or have already been used in different areas like sensing, dye/drug stabilization, drug delivery, functional materials, and aqueous dye laser systems. In supramolecular assemblies, along with their conventional photophysical properties, the acid-base properties of prototropic dyes, as well as the excited state prototautomerization and related proton transfer behavior of proton donor/acceptor dye molecules, are also largely modulated due to supramolecular interactions, which are often reflected very explicitly through changes in their absorption and fluorescence characteristics, providing us many useful insights into these chemical systems and bringing out intriguing applications of such changes in different applied areas. Another interesting research area in supramolecular photochemistry is the excitation energy transfer from the donor to acceptor moieties in self-assembled systems which have immense importance in light harvesting applications, mimicking natural photosynthetic systems. In this review article, we have discussed varieties of these aspects, highlighting their academic and applied implications. We have tried to emphasize the progress made so far and thus to bring out future research perspectives in the subject areas concerned, which are anticipated to find many useful applications in areas like sensors, catalysis, electronic devices, pharmaceuticals, drug formulations, nanomedicine, light harvesting, and smart materials.

Smart pH-Regulated Switchable Nanoprobes for Photoelectrochemical Multiplex Detection of Antibiotic Resistance Genes.

Antibiotic resistance, encoded via particular genes, has become a major global health threat and substantial burden on healthcare. Hence, the facile, low-cost, and precise detection of antibiotic resistance genes (ARGs) is crucial in the realm of human health and safety, especially multiplex sensing assays. Here, a smart pH-regulated switchable photoelectrochemical (PEC) bioassay has been created for ultrasensitive detection of two typical subtypes of penicillin resistance genes bla-CTX-M-1 (target 1, labeled as TDNA1) and bla-TEM (target 2, labeled as TDNA2), whereby pH-responsive antimony tartrate (SbT) complex-grafted silica nanospheres are ingeniously adopted as signal DNA1 tags (labeled as SDNA1-SbT@SiO2NSs). The operations of the PEC bioassay depend on the switchable dissociation of the pH-responsive SDNA1-SbT@SiO2NSs complex under the external pH stimuli, thus initiating the pH-regulated release of ions pre-embedded in sandwich-type DNA nanoassemblies. At acidic conditions, the dissociation of SDNA1 tags (ON state) triggers the release of the embedded SbO+. Under alkaline conditions, the dissociation of SDNA1 tags is inhibited (OFF state). The detection of TDNA2 was achieved via DNA hybridization-triggered metal ion release. The unwinding of the introduced hairpin T-Hg2+-T fragment, hybridized with the second anchored signal DNA (SDNA2), ignites the release of Hg2+. The released SbO+ or Hg2+ ions would trigger the formation of Sb2S3/ZnS or HgS/ZnS heterostructure through ion-exchange with the photosensitive ZnS layer, giving rise to the amplified photocurrents and eventually realizing the ultrasensitive detection of penicillin resistance genes subtypes, bla-CTX-M-1 and bla-TEM. The as-fabricated pH-regulated PEC bioassay, smartly integrating the pH-responsive intelligent unit as SDNA tags, pH-regulated release of embedded ions, and the subsequent ion-exchange-based signal amplification strategy, exhibits high sensitivity, specificity, low-cost, and ease of use for multiplex detection of ARGs. It can be successfully used for measuring bla-CTX-M-1 and bla-TEM in real E. coli plasmids, demonstrating great promise for developing a new class of genetic point-of-care devices.

Continuous Flow Photochemistry for the Preparation of Bioactive Molecules.

The last decade has witnessed a remarkable development towards improved and new photochemical transformations in response to greener and more sustainable chemical synthesis needs. Additionally, the availability of modern continuous flow reactors has enabled widespread applications in view of more streamlined and custom designed flow processes. In this focused review article, we wish to evaluate the standing of the field of continuous flow photochemistry with a specific emphasis on the generation of bioactive entities, including natural products, drugs and their precursors. To this end we highlight key developments in this field that have contributed to the progress achieved to date. Dedicated sections present the variety of suitable reactor designs and set-ups available; a short discussion on the relevance of greener and more sustainable approaches; and selected key applications in the area of bioactive structures. A final section outlines remaining challenges and areas that will benefit from further developments in this fast-moving area. It is hoped that this report provides a valuable update on this important field of synthetic chemistry which may fuel developments in the future.

Efficient removal of toxic organic dyes and photoelectrochemical properties of iron-doped zirconia nanoparticles.

Iron (Fe)-doped ZrO2 tetragonal nanoparticles were synthesized by a facile and inexpensive hydrothermal technique, that were doped with Fe3+ ions (0.1, 0.3, and 0.5 mol%) into the host lattice without altering the morphology and crystal structure of the nanoparticles. SEM and TEM investigations indicated that the morphology of ZrO2 nanoparticles did not change even after incorporation of Fe, while the band gap of semiconducting ZrO2 nanoparticles was reduced from 4.97 to 1.77 eV. Such a in band gap was responsible to harvest more photons to stimulate the generation of more electrons in the valence band, thereby enhancing the photoelectrochemical (PEC) water splitting as well as photocatalytic and photoelectrocatalytic activities in the photodegradation of Rhodamine B. The 0.3 mol%-doped ZrO2 electrode showed enhanced photocurrent density (0.07 × 10-3 A/cm2), that was 45-times greater than the pure sample. The electrochemical impedance spectroscopy (EIS) confirmed that 0.3 mol%-doped ZrO2 exhibited the best charge transfer characteristics, which increased with PEC water splitting activity. The maximum photocurrent density and long-term photo-stability were achieved in the light on-off states.

A sensitive photochemical reaction-capacitively coupled contactless conductivity detection system for HPLC and its application in determination of Cyclosporin A.

High performance liquid chromatography (HPLC) post-column photochemical reaction (PR) coupled capacitively coupled contactless conductivity detector (C4D) was used for the first time in analysis of weak ultraviolet (UV)-absorbing, non-fluorescence and nonpolar compound. A series of conditions including the radiation power of light source, the length of the reaction tube and the thickness of detection tube were investigated. HPLC-PR-C4D system was successfully applied to the determination of Cyclosporin A (CsA). Consequently, under optimal conditions, the detection system exhibited a detection limit of 0.04 µg/mL and wide linear range from 0.5 µg/mL to 100 µg/mL for CsA detection. Application of the HPLC-PR- C4D system to pharmaceutical formulation and biological samples revealed the system developed maybe reliably applied to clinical studies.

Designing Microflowreactors for Photocatalysis Using Sonochemistry: A Systematic Review Article.

Use of sonication for designing and fabricating reactors, especially the deposition of catalysts inside a microreactor, is a modern approach. There are many reports that prove that a microreactor is a better setup compared with batch reactors for carrying out catalytic reactions. Microreactors have better energy efficiency, reaction rate, safety, a much finer degree of process control, better molecular diffusion, and heat-transfer properties compared with the conventional batch reactor. The use of microreactors for photocatalytic reactions is also being considered to be the appropriate reactor configuration because of its improved irradiation profile, better light penetration through the entire reactor depth, and higher spatial illumination homogeneity. Ultrasound has been used efficiently for the synthesis of materials, degradation of organic compounds, and fuel production, among other applications. The recent increase in energy demands, as well as the stringent environmental stress due to pollution, have resulted in the need to develop green chemistry-based processes to generate and remove contaminants in a more environmentally friendly and cost-effective manner. It is possible to carry out the synthesis and deposition of catalysts inside the reactor using the ultrasound-promoted method in the microfluidic system. In addition, the synergistic effect generated by photocatalysis and sonochemistry in a microreactor can be used for the production of different chemicals, which have high value in the pharmaceutical and chemical industries. The current review highlights the use of both photocatalysis and sonochemistry for developing microreactors and their applications.

Scientific instrument Femtosecond X-ray Experiments (FXE): instrumentation and baseline experimental capabilities.

The European X-ray Free-Electron Laser (EuXFEL) delivers extremely intense (>1012 photons pulse-1 and up to 27000 pulses s-1), ultrashort (<100 fs) and transversely coherent X-ray radiation, at a repetition rate of up to 4.5 MHz. Its unique X-ray beam parameters enable novel and groundbreaking experiments in ultrafast photochemistry and material sciences at the Femtosecond X-ray Experiments (FXE) scientific instrument. This paper provides an overview of the currently implemented experimental baseline instrumentation and its performance during the commissioning phase, and a preview of planned improvements. FXE's versatile instrumentation combines the simultaneous application of forward X-ray scattering and X-ray spectroscopy techniques with femtosecond time resolution. These methods will eventually permit exploitation of wide-angle X-ray scattering studies and X-ray emission spectroscopy, along with X-ray absorption spectroscopy, including resonant inelastic X-ray scattering and X-ray Raman scattering. A suite of ultrafast optical lasers throughout the UV-visible and near-IR ranges (extending up to mid-IR in the near future) with pulse length down to 15 fs, synchronized to the X-ray source, serve to initiate dynamic changes in the sample. Time-delayed hard X-ray pulses in the 5-20 keV range are used to probe the ensuing dynamic processes using the suite of X-ray probe tools. FXE is equipped with a primary monochromator, a primary and secondary single-shot spectrometer, and a timing tool to correct the residual timing jitter between laser and X-ray pulses.

An ultrasensitive photoelectrochemical platform for quantifying photoinduced electron-transfer properties of a single entity.

Understanding the photoinduced electron-transfer process is of paramount importance for realizing efficient solar energy conversion. It is rather difficult to clarify the link between the specific properties and the photoelectrochemical performance of an individual component in an ensemble system because data are usually presented as averages because of interplay of the heterogeneity of the bulk system. Here, we report a step-by-step protocol to fabricate an ultrasensitive photoelectrochemical platform for real-time detection of the intrinsic photoelectrochemical behaviors of a single entity with picoampere and sub-millisecond sensitivity. Using a micron-thickness nanoparticulate TiO2-filmed Au ultramicroelectrode (UME) as the electron-transport electrode, photocurrent transients can be observed for each individual dye-tagged oxide semiconductor nanoparticle collision associated with a single-entity photoelectrochemical reaction. This protocol allows researchers to obtain high-resolution photocurrent signals to quantify the photoinduced electron-transfer properties of an individual entity, as well as to precisely process the data obtained. We also include procedures for dynamic light scattering (DLS) analysis, transmission electron microscopy (TEM) imaging and collision frequency-concentration correlation to confirm that the photoelectrochemical collision events occur at an unambiguously single-entity level. The time required for the entire protocol is ~36 h, with a single-entity photoelectrochemical measurement taking <1 h to complete for each independent experiment. This protocol requires basic nanoelectrochemistry and nanotechnology skills, as well as an intermediate-level understanding of photoelectrochemistry.

Sonophotocatalytic degradation of bisphenol A and its intermediates with graphitic carbon nitride.

Since bisphenol A (BPA) exhibits endocrine disrupting action and high toxicity in aqueous system, there are high demands to remove it completely. In this study, the BPA removal by sonophotocatalysis coupled with nano-structured graphitic carbon nitride (g-C3N4, GCN) was conducted with various batch tests using energy-based advanced oxidation process (AOP) based on ultrasound (US) and visible light (Vis-L). Results of batch tests indicated that GCN-based sonophotocatalysis (Vis-L/US) had higher rate constants than other AOPs and especially two times higher degradation rate than TiO2-based Vis-L/US. This result infers that GCN is effective in the catalytic activity in Vis-L/US since its surface can be activated by Vis-L to transport electrons from valence band (VB) for utilizing holes (h+VB) in the removal of BPA. In addition, US irradiation exfoliated the GCN effectively. The formation of BPA intermediates was investigated in detail by using high-performance liquid chromatography-mass spectrometry (HPLC/MS). The possible degradation pathway of BPA was proposed.

Antituberculosis drug isoniazid degraded by electro-Fenton and photoelectro-Fenton processes using a boron-doped diamond anode and a carbon-PTFE air-diffusion cathode.

Solutions with 0.65 mM of the antituberculosis drug isoniazid (INH) in 0.050 M Na2SO4 at pH 3.0 were treated by electro-Fenton (EF) and UVA photoelectro-Fenton (PEF) processes using a cell with a BDD anode and a carbon-PTFE air-diffusion cathode. The influence of current density on degradation, mineralization rate, and current efficiency has been thoroughly evaluated in EF. The effect of the metallic catalyst (Fe2+ or Fe3+) and the formation of products like short-chain linear aliphatic carboxylic acids were assessed in PEF. Two consecutive pseudo-first-order kinetic regions were found using Fe2+ as catalyst. In the first region, at short time, the drug was rapidly oxidized by ●OH, whereas in the second region, at longer time, a resulting Fe(III)-INH complex was much more slowly removed by oxidants. INH disappeared completely at 300 min by EF, attaining 88 and 94% mineralization at 66.6 and 100 mA cm-2, respectively. Isonicotinamide and its hydroxylated derivative were identified as aromatic products of INH by GC-MS and oxalic, oxamic, and formic acids were quantified by ion-exclusion HPLC. The PEF treatment of a real wastewater polluted with the drug led to slower INH and TOC abatements because of the parallel destruction of its natural organic matter content.

DNA nanostructures doped with lanthanide ions for highly sensitive UV photodetectors.

Deoxyribonucleic acid (DNA) and lanthanide ions (Ln3+) exhibit exceptional optical properties that are applicable to the development of nanoscale devices and sensors. Although DNA nanostructures and Ln3+ ions have been investigated for use in the current state of technology for more than a few decades, researchers have yet to develop DNA and Ln3+ based ultra-violet (UV) photodetectors. Here, we fabricate Ln3+ (such as holmium (Ho3+), praseodymium (Pr3+), and ytterbium (Yb3+))‒doped double crossover (DX)‒DNA lattices through substrate-assisted growth and salmon DNA (SDNA) thin films via a simple drop-casting method on oxygen (O2) plasma-treated substrates for high performance UV photodetectors. Topological (AFM), optical (UV-vis absorption and FTIR), spectroscopic (XPS), and electrical (I‒V and photovoltage) measurements of the DX‒DNA and SDNA thin films doped with various concentrations of Ln3+ ([Ln3+]) are explored. From the AFM analysis, the optimum concentrations of various Ln3+ ([Ln3+]O) are estimated (where the phase transition of Ln3+‒doped DX‒DNA lattices takes place from crystalline to amorphous) as 1.2 mM for Ho3+, 1.5 mM for Pr3+, and 1.5 mM for Yb3+. The binding modes and chemical states are evaluated through optical and spectroscopic analysis. From UV-vis absorption studies, we found that as the [Ln3+] was increased, the absorption intensity decreased up to [Ln3+]O, and increased above [Ln3+]O. The variation in FTIR peak intensities in the nucleobase and phosphate regions, and the changes in XPS peak intensities and peak positions detected in the N 1 s and P 2p core spectra of Ln3+‒doped SDNA thin films clearly indicate that the Ln3+ ions are properly bound between the bases (through chemical intercalation) and to the phosphate backbone (through electrostatic interactions) of the DNA molecules. Finally, the I‒V characteristics and time-dependent photovoltage of Ln3+‒doped SDNA thin films are measured both in the dark and under UV LED illuminations (λLED = 382 nm) at various illumination powers. The photocurrent and photovoltage of Ln3+‒doped SDNA thin films are enhanced up to the [Ln3+]O compared to pristine SDNA due to the charge carriers generated from both SDNA and Ln3+ ions upon the absorption of light. From our observations, the photovoltages as function of illumination power suggest higher responsivities, and the photovoltages as function of time are almost constant which indicates the stability and retention characteristics of the Ln3+‒doped SDNA thin films. Hence, our method which provides an efficient doping of Ln3+ into the SDNA with a simple fabrication process might be useful in the development of high-performance optoelectronic devices and sensors.

A Sunlight Powered Portable Photoelectrochemical Biosensor Based on a Potentiometric Resolve Ratiometric Principle.

As a new analysis tool, photoelectrochemical (PEC) biosensors have been widely studied in recent years. However, common PEC biosensors usually require a highly stable light source to excite the electrical signal and an electrochemical workstation to collect and process the signal data, which limited the development of portable PEC devices. Herein, we propose the design of a sunlight powered portable PEC biosensor that uses sunlight as the light source. The sunlight intensity changes over time and weather and results in varied background PEC currents. To eliminate the interference caused by unstable excitation light, the potentiometric resolve ratiometric principle was introduced. Coupled with a miniature electrochemical workstation and a laptop, a sensitive and portable PEC sensing platform was successfully developed. The detection may be achieved under the irradiation of sunlight and will no longer need an extra light source. In a proof of concept experiment, this platform was successfully applied in aflatoxin B1 analysis, which was promising in the development of portable biosensors.

A photoelectrochemical immunosensor based on gold nanoparticles/ZnAgInS quaternary quantum dots for the high-performance determination of hepatitis B virus surface antigen.

ZnAgInS quaternary quantum dots were prepared using glutathione as the capped reagent. Gold nanoparticles (GNPs) were integrated with ZnAgInS QDs to provide a GNPs/ZnAgInS QDs nanocomposite. The morphological image, component and crystal structure of GNPs/ZnAgInS QDs were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A glassy carbon electrode surface was coated with GNPs/ZnAgInS QDs nanocomposites to construct an interface for immobilizing the antibody of hepatitis B virus surface antigen (anti-HBsAg). By employing GNPs/ZnAgInS QDs as a photoactive element, a photoelectrochemical immunosensor for hepatitis B virus surface antigen (HBsAg) was developed. The results indicate that gold nanoparticles can dramatically enhance the photocurrent response of ZnAgInS QDs and thus improving the sensing performances of the immunosensor. The experimental conditions including incubation time, incubation temperature, and ascorbic acid concentration were optimized. The relative photocurrent decline [Ri = ΔI/I0= (I0 - I)/I0] shows a linear relationship to the logarithm of HBsAg concentration [lg(c, ng mL-1)] in the range from 0.005 to 30 ng mL-1. A detection limit of 0.5 pg mL-1 was obtained. The immunosensor shows excellent sensitivity, selectivity, stability and reproducibility. The HBsAg concentrations in clinical serum samples were also accurately determined with this new photoelectrochemical immunosensor.

Modelling of the cathodic and anodic photocurrents from Rhodobacter sphaeroides reaction centres immobilized on titanium dioxide.

As one of a number of new technologies for the harnessing of solar energy, there is interest in the development of photoelectrochemical cells based on reaction centres (RCs) from photosynthetic organisms such as the bacterium Rhodobacter (Rba.) sphaeroides. The cell architecture explored in this report is similar to that of a dye-sensitized solar cell but with delivery of electrons to a mesoporous layer of TiO2 by natural pigment-protein complexes rather than an artificial dye. Rba. sphaeroides RCs were bound to the deposited TiO2 via an engineered extramembrane peptide tag. Using TMPD (N,N,N',N'-tetramethyl-p-phenylenediamine) as an electrolyte, these biohybrid photoactive electrodes produced an output that was the net product of cathodic and anodic photocurrents. To explain the observed photocurrents, a kinetic model is proposed that includes (1) an anodic current attributed to injection of electrons from the triplet state of the RC primary electron donor (PT) to the TiO2 conduction band, (2) a cathodic current attributed to reduction of the photooxidized RC primary electron donor (P+) by surface states of the TiO2 and (3) transient cathodic and anodic current spikes due to oxidation/reduction of TMPD/TMPD+ at the conductive glass (FTO) substrate. This model explains the origin of the photocurrent spikes that appear in this system after turning illumination on or off, the reason for the appearance of net positive or negative stable photocurrents depending on experimental conditions, and the overall efficiency of the constructed cell. The model may be a used as a guide for improvement of the photocurrent efficiency of the presented system as well as, after appropriate adjustments, other biohybrid photoelectrodes.

Fabrication of Biomolecule Microarrays Using Rapid Photochemical Surface Patterning in Thiol-Ene-Based Microfluidic Devices.

In many biochip applications, it is advantageous to be able to immobilize biomolecules at specific locations on the surface of solid supports. In this protocol, we describe a photochemical surface patterning procedure based on thiol-ene/yne photochemistry which allows for the simple and rapid selective patterning of biomolecules on thiol-ene solid supports. We describe the preparation of solid supports which are required for the immobilization, including porous monoliths, as well as two different immobilization schemes based on biotin-streptavidin interactions and covalent linkage via free amino groups respectively.