Redox Properties of Self-Assembled Gold Nanoclusters

The redox properties of a monolayer of alkanethiolate-protected gold nanoclusters (MPCs) constructed on a gold slide electrode was studied in 1,2-dichloroethane (DCE) electrolyte solutions. The influence of the electrostatic interaction between attached MPCs and the substrate electrode on the absolute standard redox potential of MPCs was theoretically considered and studied experimentally

Size Dependence of Investigations of Hot Electron Cooling Dynamincs in Metal/Adsorbates Nanoparticles

The size dependence of electron-phonon coupling rate has been investigated by femtosecond transient absorption spectroscopy for gold nanoparticles (NPs) wrapped in a shell of sulfate with diameter varying from 1.7 to 9.2 nm. Broad-band spectroscopy gives an overview of the complex dynamics of nonequilibrium electrons and permits the choice of an appropriate probe wavelength for studying the electron-phonon coupling dynamics. Ultrafast experiments were performed in the weak perturbation regime (less than one photon in average per nanoparticle), which allows the direct extraction of the hot electron cooling rates in order to compare different NPs sizes under the same conditions. Spectroscopic data reveals a decrease of hot electron energy loss rates with metal/adsorbates nanosystem sizes. Electron-phonon coupling time constants obtained for 9.2 nm NPs are similar to gold bulk materials (a. 1 ps) whereas an increase of hot electron cooling time up to 1.9 ps is observed for sizes of 1.7 nm. This is rationalized by the domination of surface effects over size (bulk) effects. The slow hot electron cooling is attributed to the adsorbates-induced long-lived nonthermal regime, which significantly reduces the electron-phonon coupling strength (average rate of phonon emission)

Voltammetry for surface-active ions at polarisable liquid|liquid interfaces

Adsorption of charged species at the interface between two immiscible electrolyte solutions (ITIES) is simulated taking into account both the mutual influence between the potential dependent surface excess charge and the potential distribution between the two phases and the partition equilibrium of the surface- active molecules. The electrical potential profiles are calculated assuming a single adsorption plane separating two electrical diffuse layers following the modified Verwey–Niessen model (MVN). The interfacial boundary potential is obtained from the electroneutrality condition. The interplay between adsorption and partition under steady-state conditions is addressed yielding voltammetric responses for the adsorption–desorption processes along with the faradaic response

Microfluidic enzymatic reactors for proteome research

The field of proteomics has emerged as a valuable analytical tool for elucidating cellular and biological systems at the molecular level. As there is an ever-growing demand for new highly automated, high-throughput, and sensitive analytical tools, a key challenge is the characterization of low abundance proteins that are crucial in modulating biological functions of cells and may also be associated with a number of diseases. If the detection modes are mainly dominated by fluorescence spectroscopy and mass spectrometry, the recent advances in microfluidic techniques have the potential to meet the requirements for sample treatment and processing. Microfluidic devices can address the future analytical needs of increased throughput, lower sample and reagent consumption, smaller size, and lower operating costs. It has been found that microfluidic-based enzymatic reactors can carry out protein digestion with high efficiency to facilitate subsequent reliable protein identification by peptide mass fingerprinting. Compared to conventional digestion approaches, microfluidic enzymatic reactors can not only accelerate digestion rate but also reduce enzyme autolysis and, ultimately, achieve the purpose of repetitive utilization

Porphyrin ‘‘Mille-Feuilles” photo-electrodes

A porphyrin ‘‘Mille-Feuilles” photo-electrode is fabricated layer-by-layer by deposition of anionic [zinc meso-tetrakis(p-sulfonato phenyl) porphyrin]4- (ZnTPPS4−) and positively charged polypeptides on a 11-mercaptoundecanoic acid-modified gold electrode to form a photoactive film. This work demonstrates that it is possible to form 3D structures having regularly spaced layers of redox molecules. UV–visible spectra of the multilayer films display the characteristic absorption bands of the porphyrins and the absorbance increases linearly with the number of bilayers. The cyclic voltammetric response of the films in contact with 1,2-dichloroethane (DCE) varies from that of a modified electrode to that of a supported liquid film. Under illumination, a large photocurrent response for oxygen reduction with a maximum for a 5-bilayer film is observed

Protoporphyrin IX sensitized titanium oxide gel electrode

Titanium oxide (Ti(O)) xerogel films functionalized by protoporphyrin IX (PPIX) and ferrocene carboxylic acid (FCA) were deposited on indium tin oxide (ITO) electrodes following a sol–gel synthesis. PPIX and FCA were first complexed to titanium oxide precursors, which were then subjected to hydrolysis to obtain a homogenous Ti(O) polymeric network gel doped with PPIX and FCA. The Ti(O) film cast on the ITO electrode has been characterized by UV–Vis absorption, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy and cyclic voltammetry. Illumination of the PPIX doped Ti(O) films on the ITO electrode immersed in aqueous electrolytes onsets photoinduced electron transfer reactions, and a cathodic photocurrent was observed in most cases. This photocurrent response was investigated in detail using a kinetic model. Preliminary investigations of oxygen reduction, lithium and proton insertion into the Ti(O) film have also been carried out

On-column conductivity detection in capillary-chip electrophoresis

On-column conductivity detection in capillary-chip electrophoresis was achieved by actively coupling the high electric field with two sensing electrodes connected to the main capillary channel through two side detection channels. The principle of this concept was demonstrated by using a glass ch p with a separation channel incorporating two double-Ts. One double-T was used for sample introduction, and the other for detection. The two electrophoresis electrodes apply the high voltage and provide the current, and the two sensing electrodes connected to the separation channel through the second double-T and probe a potential difference. This potential difference is directly related to the local resistance or the conductivity of the solution defined by the two side channels on the main separation channel. A detection limit of 15 mM (600 ppb or 900 fg) was achieved for potassium ion in a 2 mM Tris-HCl buffer (pH 8.7) with a linear range of 2 orders of magnitude without any stacking. The proposed detection method avoids integrating the sensing electrodes directly within the separation channel and prevents any direct contact of the electrodes with the sample. The baseline signal can also be used for online monitoring of the electric field strength and electroosmosis mobility characterization in the separation channel

Electrochemical evidence of catalysis of oxygen reduction at the polarized liquid–liquid interface by tetraphenylporphyrin monoacid and diacid

Cyclic voltammetry is used to study the role of 5,10,15,20-tetraphenyl-21H,23H-porphine (H2TPP) in the reduction of molecular oxygen by decamethylferrocene (DMFc) at the polarized water|1,2-dichloroethane (DCE) interface. It is shown that this rather slow reaction proceeds remarkably faster in the presence of tetraphenylporphyrin monoacid (H3TPP+) and diacid (H4TPP2+), which are formed in DCE by the successive transfer of two protons from the acidified aqueous phase. A mechanism is proposed, which includes the formation of adduct between H3TPP+ or H4TPP2+ and O2 that is followed by electron transfer from DMFc to the adduct leading to the observed production of DMFc+ and to the regeneration of H2TPP or H3TPP+, respectively

Adsorbed protein detection by scanning electrochemical microscopy

A scanning electrochemical microscopy (SECM) protein detection methodology has been developed based on the tagging of free cysteines and other nucleophiles in proteins and peptides by benzoquinone. The tagged proteins are detected by the mediated reduction of benzoquinone with a redox species produced electrochemically at the SECM tip. After careful optimization, a sensitivity in the low ng mm 2 range was reached for bovine serum albumin. One of the major advantages of the present technique is that the selectivity of the protein tagging can be tuned by changing the pH of the reaction media. Depending on the requirements, cysteine selective or general detection can therefore be achieved with a high sensitivity. As a proof of concept, this technique was applied to the detection of protein spots and to the imaging of human fingerprints and further compared to the actual SECM state-of-art approach

Rapid Noninvasive Skin Monitoring by Surface Mass Recording and Data Learning.

Skin problems are often overlooked due to a lack of robust and patient-friendly monitoring tools. Herein, we report a rapid, noninvasive, and high-throughput analytical chemical methodology, aiming at real-time monitoring of skin conditions and early detection of skin disorders. Within this methodology, adhesive sampling and laser desorption ionization mass spectrometry are coordinated to record skin surface molecular mass in minutes. Automated result interpretation is achieved by data learning, using similarity scoring and machine learning algorithms. Feasibility of the methodology has been demonstrated after testing a total of 117 healthy, benign-disordered, or malignant-disordered skins. Remarkably, skin malignancy, using melanoma as a proof of concept, was detected with 100% accuracy already at early stages when the lesions were submillimeter-sized, far beyond the detection limit of most existing noninvasive diagnosis tools. Moreover, the malignancy development over time has also been monitored successfully, showing the potential to predict skin disorder progression. Capable of detecting skin alterations at the molecular level in a nonsurgical and time-saving manner, this analytical chemistry platform is promising to build personalized skin care