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A model biological membrane was formed by fusion of mixed cholesterol and DMPC (dimyristoylphosphatidylcholine) phospholipid vesicles onto a gold-coated quartz support. The gold surface was charged and the influence of the charge at the solid support on the structure and integrity of the phospholipid bilayer was investigated using the specular reflection of neutrons and electrochemical measurements. When the surface charge density is close to zero, the lipid vesicles fuse directly on the surface to form a bilayer with a small number of defects and hence low water content. When the support's surface is negatively charged the film swells and incorporates water due to the field driven poration of the membrane. When the charge density is more negative then -8 microC cm(-2) the bilayer is detached from the metal surface. However, it remains in close proximity to the metal electrode, suspended on a thin cushion of water. The film thicknesses, calculated from neutron reflectivity, have allowed us to determine the tilt angle of the lipid molecules as a function of the support's charge density. The lipid molecules are tilted 55 degrees from the surface normal at zero charge density but become significantly more perpendicular (30 degrees tilt angle) at charge densities more negative than -8 microC cm(-2). The tilt angle measurements are in very good agreement with previous IR studies. This paper describes the highlights of a more in-depth study which is fully described in [1].

A mixed bilayer of cholesterol and dimyristoylphosphatidylcholine has been formed on a gold-coated block of quartz by fusion of small unilamellar vesicles. The formation of this bilayer lipid membrane on a conductive surface allowed us to study the influence of the support's surface charge on the structure and hydration of the bilayer lipid membrane. We have employed electrochemical measurements and the specular reflection of neutrons to measure the thickness and water content in the bilayer lipid membrane as a function of the charge on the support's surface. When the surface charge density is close to zero, the lipid vesicles fuse directly on the surface to form a bilayer with a small number of defects and hence small water content. When the support's surface is negatively charged the film swells and incorporates water. When the charge density is more negative than -8 micro C cm(-2), the bilayer starts to detach from the metal surface. However, it remains in a close proximity to the metal electrode, being suspended on a thin cushion of the electrolyte. The field-driven transformations of the bilayer lead to significant changes in the film thicknesses. At charge densities more negative than -20 micro C cm(-2), the bilayer is approximately 37 A thick and this number is comparable to the thickness determined for hydrated multilayers of dimyristoylphosphatidylcholine from x-ray diffraction experiments. The thickness of the bilayer decreases at smaller charge densities to become equal to approximately 26 A at zero charge. This result indicates that the tilt of the acyl chains with respect to the bilayer normal changes from approximately 35 degrees to 59 degrees by moving from high negative charges (and potentials) to zero charge on the metal.

Recently, there has been an upsurge in the extent to which electrochemiluminescence (ECL) working in synergy with bipolar electrochemistry (BPE) is being applied in simple biosensing devices, especially in a clinical setup. The key objective of this particular write-up is to present a consolidated review of ECL-BPE, providing a three-dimensional perspective incorporating its strengths, weaknesses, limitations, and potential applications as a biosensing technique. The review encapsulates critical insights into the latest and novel developments in the field of ECL-BPE, including innovative electrode designs and newly developed, novel luminophores and co-reactants employed in ECL-BPE systems, along with challenges, such as optimization of the interelectrode distance, electrode miniaturization and electrode surface modification for enhancing sensitivity and selectivity. Moreover, this consolidated review will provide an overview of the latest, novel applications and advances made in this field with a bias toward multiplex biosensing based on the past five years of research. The studies reviewed herein, indicate that the technology is rapidly advancing at an outstanding purse and has an immense potential to revolutionize the general field of biosensing. This perspective aims to stimulate innovative ideas and inspire researchers alike to incorporate some elements of ECL-BPE into their studies, thereby steering this field into previously unexplored domains that may lead to unexpected, interesting discoveries. For instance, the application of ECL-BPE in other challenging and complex sample matrices such as hair for bioanalytical purposes is currently an unexplored area. Of great significance, a substantial fraction of the content in this review article is based on content from research articles published between the years 2018 and 2023. [ABSTRACT FROM AUTHOR]

Many self-assembled monolayers of dithiols on gold feature terminal SH groups, the nucleophilic nature of which provides opportunities for covalent binding of electrophiles through sulfide linkages. This work describes an efficient coupling of dithiol derivative of 4,4'-dihydroxybiphenyl immobilized on Au surface with a mesylate ester present in the solution. The procedure did not require a glove box or any specialized equipment and provided a high surface concentration of the redox active product. The modified Au-SAM electrode was investigated electroanalytically. [ABSTRACT FROM AUTHOR]

The swelling behavior of polyelectrolyte multilayers (PEMs) of poly(sodium-4 styrene sulfonate) (PSS) and poly(diallyl dimethyl ammonium chloride) (PDADMAC) prepared from aqueous solution of 0.1 M and 0.5 M NaCl are investigated by ellipsometry and Atomic Force Microscopy (AFM). From 1 double-layer up to 4 double-layers of 0.1 M NaCl, the amount of swelling water in the PEMs decreases with increasing number of adsorbed double layers due to an increase in polyelectrolyte density as a result of the attraction between the positively charged outermost PDADMAC layer and the Si substrate. From 6 double layers to 30 double layers, the attraction is reduced due to a much larger distance between substrate and outermost layer leading to a much lower polyelectrolyte density and higher swelling water. In PEMs prepared from aqueous solution of 0.5 M NaCl, the amount of water constantly increases which is related to a monotonically decreasing polyelectrolyte density with increasing number of polyelectrolyte layers. Studies of the surface topology also indicate a transition from a more substrate affectedinterphasebehavior to acontinuumproperties of the polyelectrolyte multilayers. The threshold for the transition frominterphasetocontinuumbehavior depends on the preparation conditions of the PEM. [ABSTRACT FROM AUTHOR]

First papers on electroactivity of DNA and RNA were published more then 50 years ago. For about 8 years oscillographic polarography at controlled a.c. (OP, proposed by J. Heyrovský already in 1941) was the method of choice for DNA analysis. Since approximately 1954 Robert Kalvoda developed OP for wide application in various fields. It is shown that already before 1960 it was possible to detect damage to DNA in X-ray-irradiated rats by means of OP. DNA samples from irradiated animals produced significantly larger OP anodic guanine signal indicating changes in the DNA structure. At present, radiation-induced strand breaks and damage to bases in DNA can be electrochemically detected at high sensitivity. [ABSTRACT FROM AUTHOR]

The horizontal touch and Langmuir–Blodgett techniques have been used to transfer a monolayer of n-octadecanol from the gas–solution interface of a Langmuir trough onto the metal–solution interface of a Au(1 1 1) electrode. Chronocoulometry has been used to determine the charge density at the electrode surface covered by the film of n-octadecanol. The surface pressure of this film was calculated from the charge density data and was found to be controlled by the electrode potential. We have demonstrated that by dialing the potential applied to the electrode via a potentiostat the monolayer adsorbed on the surface can be compressed or decompressed. Two states of the monolayer were observed. The transition between these states took place at a film pressure ∼12 mN m-1. Neutron reflectometry and polarization modulation Fourier transform infrared reflection absorption spectroscopy have been employed to determine the nature of the two states. The results show that octadecanol molecules form a two-dimensional solid film at all film pressures. At film pressures larger than 12 mN m-1, the film has low compressibility and n-octadecanol molecules assume a small tilt angle with respect to the surface normal. At film pressures lower than 12 mN m-1 a compressive film is formed in which the tilt angle progressively increases with decreasing surface pressure. We have demonstrated that the properties of a monolayer of n-octadecanol at the metal–solution interface display many similarities to the properties of that film at the air–solution interface. [Copyright &y& Elsevier]

Over the past three decades, surface-enhanced Raman spectroscopy (SERS) has gone through a tortuous pathway to develop into a powerful surface diagnostic technique for in situ investigation of surface adsorption and reactions on electrodes. This review presents the recent progress achieved mainly in our laboratory on the improvement of detection sensitivities as well as spectral, temporal, and spatial resolutions. Various surface roughening procedures for electrodes of different metals coupled with maximum use of a high-sensitivity confocal Raman microscope enable us to obtain good-quality SER spectra on the electrode surfaces made from net Pt, Ni, Co, Fe, Pd, Rh, Ru, and their alloys that were traditionally considered to be non-SERS active. A novel technique called potential-averaged SERS (PASERS) has been developed for the quantitative study of electrochemical sorption. Applications are exemplified on extensively studied areas such as coadsorption, electrocatalysis, corrosion, and fuel cells, and several advantages of in situ electrochemical SERS are demonstrated. Finally, further developments in this field are briefly discussed with emphasis on the emerging methodology. [ABSTRACT FROM AUTHOR]

In the eye lens cell membrane, the lipid composition changes during the aging process: the proportion of sphingomyelins (SM) increases, that of phosphatidylcholines decreases. To investigate the protective role of the SMs in the lens cell membrane against oxidative damage, analytical techniques such as electrochemistry, high-resolution mass spectrometry (HR-MS), and atomic force microscopy (AFM) were applied. Supported lipid bilayers (SLB) were prepared to mimic the lens cell membrane with different fractions of PLPC/SM (PLPC: 1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphocholine). The SLBs were treated with cold physical plasma. A protective effect of 30% and 44% in the presence of 25%, and 75% SM in the bilayer was observed, respectively. PLPC and SM oxidation products were determined via HR-MS for SLBs after plasma treatment. The yield of fragments gradually decreased as the SM ratio increased. Topographic images obtained by AFM of PLPC-bilayers showed SLB degradation and pore formation after plasma treatment, no degradation was observed in PLPC/SM bilayers. The results of all techniques confirm the protective role of SM in the membrane against oxidative damage and support the idea that the SM content in lens cell membrane is increased during aging in the absence of effective antioxidant systems to protect the eye from oxidative damage and to prolong lens transparency. [ABSTRACT FROM AUTHOR]