Dual microband electrodes: current distributions and diffusion layer ‘titrations’. Implications for electroanalytical measurements

The simulation of transport to double microband electrodes in generator–collector mode is reported focusing especially on the ‘titration curve’ approach to electroanalysis in which a titrant is electrogenerated from a redox active precursor on the generator electrode and reacts homogeneously with the target analyte. The current on the detector electrode reflects the amount of titrant ‘surviving’ passage between the two electrodes. The form of the titration curve – plots of detector current as a function of generator current – is shown to be highly sensitive to the electrode kinetics of the redox couple driven at the generator electrode. Accordingly the naïve use of such methodology for analysis without accompanying simulation and kinetic analysis is fraught with danger. Use of the conformal mapping approach in combination with the ADI method for investigation of the ‘titration’ current distributions at the double band system gives fast and precise simulation of this and similar problems. Convergence analysis is described which allows for the automatic selection of the simulation grid size so as to obtain a chosen accuracy (for example 1%) of the current for all experimentally meaningful values of the geometrical and physico-chemical parameters of the system to be investigated.     

Scratch and Abrasion Resistant Coatings on Plastic Lenses—State of the Art,Current Developments and Perspectives

The manufacturing of ophthalmic lenses is one of the most important markets worldwide and, therefore, strong research efforts are undertaken to continuously improve the quality of the products, either silicate glasses or organic polymer lenses. Hybrid sol-gel based materials play a major role in this highly competitive field and have contributed significantly to the commercial success of the organic base materials. Recent developments concern fast curing and patternable coatings that might soon become part of this business. The compatibility of hybrid sol-gel materials either with organic dyes or with inorganic vacuum borne coatings offers further possibilities to develop highly sophisticated lenses meeting not only customer needs like perfect corrective function, high optical quality and protection, but also high durability as well as cosmetic and decorative aspects. An overview and a few recent developments are outlined below.     

Influence of Urbach Energy,Temperature, and Longitudinal Position in the Active Layer on Carrier Diffusion Length in Perovskite Solar Cells

The diffusion length of charge carriers in the active layer of a perovskite solar cell (PSC) of the structure Glass/PEDOT: PSS/CH₃NH₃PbI₃/PC60BM/Al is modelled. It is found that the diffusion length depends on the position x in the active layer measured from the PEDOT: PSS interface, Urbach energy and temperature. By varying the voltage in the range from zero to , it is shown that the dependence of diffusion length on the position x in the active layer reduces at higher voltage. The combined influence of applied voltage and temperature on the diffusion length of charge carriers is investigated and it is found that in the low voltage range the diffusion length is temperature independent, but it becomes significantly temperature dependent at higher voltages. Also, it is found that the diffusion length decreases as the applied voltage increases and this reduction becomes much more significant at higher voltage and temperatures. The combined influence of applied voltage and Urbach energy on diffusion length of charge carriers reveals that the diffusion length decreases when both the applied voltage and Urbach energy increase. However, the reduction in the diffusion length due to the increase in Urbach energy becomes less significant at higher voltage.     

High temperature corrosion behaviour of M(Co,Ni)CrAIY-coatings on high temperature materials-microanalytical investigations

In our former investigations, the phenomenon high temperature corrosion (HTC) was described exemplarily on selected materialcoating combinations for blades of stationary gas turbines, mainly in the temperature region of up to 750° C. To answer the question, in which manner higher gas inlet and/or higher material surface temperature would influence the HTC behaviour, a special analytical technique—the integral layer profile analysis—was introduced to ameliorate concentration profile methods. By examining IN 738 LC specimens with CoCrAlY plasma spray coating, stressed by hot gas at 900° C, the limits of this system are shown by explaining the corrosion mechanism; the method is also used for other systems, e.g. U 520 with NiCrAlY coating at 750° C.     

Formal Mathematical Analysis of the Existence of the Common Intersection Point in Relation to Determining the Parameters Describing Ion Adsorption at the Oxide/Electrolyte Interface: Comparison of the Triple and Four-Layer Models

For most oxide/electrolyte systems potentiometric titration curves measured for different ionic strengths have a Common Intersection Point (CIP) which corresponds to the Point of Zero Charge (PZC). However, there are systems where a CIP exists but the surface charge at this point does not equal zero (PZC CIP). In this paper theoretical analysis of the systems in which the PZC and CIP do not coincide is presented. It is based on the well-known 2-pK surface charging approach and Triple Layer Model (TLM) as well as the Four Layer Model (FLM) of the electric double layer. The appropriate mathematical criterion for CIP existence was applied with detailed derivations, both for TLM and FLM. Having determined in this manner the parameter values, one can draw proper conclusions about the features of oxide/electrolyte adsorption systems, in which PZC and CIP do not coincide. The values of adsorption parameters are found by fitting simultaneously the obtained theoretical expressions to both of the experimental titration isotherms, and to the individual isotherms of electrolyte cation adsorption measured using radiometric methods.     

Application of self-assembly for replacing chromate in corrosion protection of zinc

Due to the toxic and carcinogenic properties of hexavalent chromium ion, the corrosion protection with chromating technique needs replacement. Several environmentally friendly alternative metal pretreatments have already been proposed. One of these methods is the application of self-assembling molecules to form mono- or multilayers on the metal surfaces. These layers can prevent metal dissolution due to their dense and stable structure. The objective of our studies was to protect zinc surface against corrosion, with a thin phosphonate layer. Aqueous solutions of diphosphonic acid with different alkyl chain lengths were applied with different treatment times. The layer formation, stability, and corrosion protection of these films were monitored by electrochemical impedance spectroscopy and the effect of 1,5-diphosphono-pentane (DPP) on zinc was studied by polarization curves. The wetting properties were determined by static contact angle measurement. 1,5-Diphosphono-pentane forms a thin layer, with a pronounced protective ability in neutral aqueous solutions. The application of self-assembling molecules can be a promising method to replace the chromating technique on zinc surface.     

Thin layer distillation for matrix isolation in flow analysis

Analyte transfer from the matrix in a thin layer distillation (TLD) cell and its subsequent measurement were investigated in a flow injection configuration. We designed the cell such that the donor and acceptor streams flowed in parallel channels separated by a thin dividing wall. The matrix transfer process involved room-temperature distillation of the analyte into the headspace of the TLD cell and its subsequent condensation/uptake by a concurrently flowing acceptor stream. There are no membranes; hence there are no membrane-related problems. The TLD system design was optimized with respect to its dimensions and operational parameters. Throughput and sensitivity were compared with a conventional pervaporation flow injection (PFI) system for ammonia and five different amines. For the higher molecular mass amines, the TLD approach provided comparable or superior performance. The TLD technique should be an attractive approach for online analysis of volatile chemical species in ‘dirty’ samples, especially for volatile analytes of higher molecular mass.     

Microgel-based engineered nanostructures and their applicability with template-directed layer-by-layer polyelectrolyte assembly in protein encapsulation

A novel strategy for the fabrication of microcapsules is elaborated by employing biomacromolecules and a dissolvable template. Calcium carbonate (CaCO(3)) microparticles were used as sacrificial templates for the two-step deposition of polyelectrolyte coatings by surface controlled precipitation (SCP) followed by the layer-by-layer (LbL) adsorption technique to form capsule shells. When sodium alginate was used for inner shell assembly, template decomposition with an acid resulted in simultaneous formation of microgel-like structures due to calcium ion-induced gelation. An extraction of the calcium after further LbL treatment resulted in microcapsules filled with the biopolymer. The hollow as well as the polymer-filled polyelectrolyte capsules were characterized using confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), and scanning force microscopy (SFM). The results demonstrated multiple functionalities of the CaCO(3) core - as supporting template, porous core for increased polymer accommodation/immobilization, and as a source of shell-hardening material. The LbL treatment of the core-inner shell assembly resulted in further surface stabilization of the capsule wall and supplementation of a nanostructured diffusion barrier for encapsulated material. The polymer forming the inner shell governs the chemistry of the capsule interior and could be engineered to obtain a matrix for protein/drug encapsulation or immobilization. The outer shell could be used to precisely tune the properties of the capsule wall and exterior. [Diagram: see text] Confocal laser scanning microscopy (CLSM) image of microcapsules (insert is after treating with rhodamine 6G to stain the capsule wall).     

LBL分子沉积法制备葡萄糖氧化酶电极

采用以静电力为主的逐层分子交替沉积技术制备葡萄糖氧化酶（GOD）电极.通过带有正电荷的聚二甲基二烯丙基铵盐酸盐（PDDA）和带有负电荷的GOD交替沉积在修饰有3-巯基-1-丙基磺酸钠（MPS）的金电极表面.以甲酸二茂铁为电子媒介体,用循环伏安法检测GOD电极对葡萄糖的响应.结果表明,当GOD电极组装层数小于4时,电流响应随着层数的增加而增大,超过4层时电流响应减小.其中4层GOD修饰电极的线性范围为0.55～6.63 mmol•L－1,当pH为7.0时,响应最大.同时电极的检测重现性能良好,相对标准偏差为2.4％.     

Spectroelectrochemical Measurements at Colloidal Au Multilayer Optically Transparent Electrodes

Application of thin colloidal Au multilayers on glass substrates as optically transparent electrodes is reported herein. Evaluation of the electrode by scanning electron microscopy and as an optically transparent thin layer electrode (OTTLE) illustrate its use for spectroelectrochemical applications. A spectroelectrochemical Nernst plot acquired for the oxidation of o‐tolidine yielded a value of E°=0.605 V (vs. Ag/AgCl) and n=1.88. Both of these values are in excellent agreement with previously published values obtained using a traditional Au minigrid OTTLE. The colloidal Au multilayer electrode is expected to offer many advantages over the minigrid OTTLE in specific applications. These advantages include direct control over microscopic surface topography, large electrochemical surface area, applicability to many different electrode geometries, and increased microscopic surface roughness for SERS and SPR applications.