scholarly journals Role of redox-active axial ligands of metal porphyrins adsorbed at solid–liquid interfaces in a liquid-STM setup

2020 ◽  
Vol 11 ◽  
pp. 1264-1271
Author(s):  
Thomas Habets ◽  
Sylvia Speller ◽  
Johannes A A W Elemans

In a liquid-STM setup environment, the redox behavior of manganese porphyrins was studied at various solid–liquid interfaces. In the presence of a solution of Mn(III)Cl porphyrins in 1-phenyloctane, which was placed at a conductive surface, large and constant additional currents relative to a set tunneling current were observed, which varied with the magnitude of the applied bias voltage. These currents occurred regardless of the type of surface (HOPG or Au(111)) or tip material (PtIr, Au or W). The additional currents were ascribed to the occurrence of redox reactions in which chloride is oxidized to chlorine and the Mn(III) center of the porphyrin moiety is reduced to Mn(II). The resulting Mn(II) porphyrin products were identified by UV–vis analysis of the liquid phase. For solutions of Mn(III) porphyrins with non-redox active acetate instead of chloride axial ligands, the currents remained absent.

2020 ◽  
Vol 16 (11) ◽  
pp. 7135-7147
Author(s):  
Jason Klebes ◽  
Sophie Finnigan ◽  
David J. Bray ◽  
Richard L. Anderson ◽  
William C. Swope ◽  
...  

Author(s):  
C. Julian Chen

This chapter presents the basic designs and working principles of STM and AFM, as well as an elementary theory of tunneling and the imaging mechanism of atomic resolution. Three elementary theories of tunneling are presented: the one-dimensional Schrödinger’s equation in vacuum, the semi-classical approximation, and the Landauer formalism. The relation between the decay constant and the work function, and a general expression of tunneling conductance versus tip-sample distance are derived. A brief summary of experimental facts on the mechanism of atomic resolution STM and AFM is presented, which leads to a picture of interplay between the atomic states of the tip and the sample, as well as the role of partial covalent bonds formed between those electronic states. Four illustrative applications are presented, including imaging self-assembed molecules on solid-liquid interfaces, electrochemical STM, catalysis research, and atom manipulation.


2018 ◽  
Vol 69 (8) ◽  
pp. 2278-2282
Author(s):  
Stelian Ioan Morariu ◽  
Letitia Doina Duceac ◽  
Alina Costina Luca ◽  
Florina Popescu ◽  
Liliana Pavel ◽  
...  

Maintaining the soil in optimal parameters is vital for mankind, given its essential role in providing the alimentary base, as well as its extremely slow formation and regeneration (hundreds or thousands of years). The direct and indirect pollution of the soil and especially its chemical pollution represent a corollary of other types of pollution, given that it is produced by solid, liquid and gaseous residues. It may be involved in a wide range of diseases (respiratory, cardiovascular, digestive, renal, haematological, osteoarticular, neurological) of allergic, infectious, degenerative or neoplastic nature, from infancy to the old age. Although there are natural causes of soil pollution (e.g. volcanic eruptions), most pollutants come from human activities, which are the most incriminated in its pollution, degradation and erosion at an accelerated pace. The growing concern of all nations for the adoption of measures to limit the chemical pollution of the soil is partially found so far in viable and effective solutions intended to combat soil contamination and degradation and ensure its restoration. Chemical industrialization leads to technical and scientific progress, but at the same time it can develop related pathologies, which means that the role of the occupational health physician is essential in ensuring prophylaxis and the early detection of occupational diseases. Besides that, the role of the pediatrician is equally precious for the detection of specific diseases caused by chemical pollutants to children, because they will develop into adults with pathological stigma.The chemical pollution of the soil is a major challenge for ecologists, given that it is an important risk factor for many types of afflictions. It requires maximum attention from civil society, health care professionals and government institutions. The specialist in occupational medicine, as well as the pediatrician bear an essential responsibility in both, prevention and treatment.


1995 ◽  
Vol 31 (1) ◽  
pp. 61-70 ◽  
Author(s):  
Graham F. White

Many organic pollutants, especially synthetic surfactants, adsorb onto solid surfaces in natural and engineered aquatic environments. Biofilm bacteria on such surfaces make major contributions to microbial heterotrophic activity and biodegradation of organic pollutants. This paper reviews evidence for multiple interactions between surfactants, biodegradative bacteria, and sediment-liquid interfaces. Biodegradable surfactants e.g. SDS, added to a river-water microcosm were rapidly adsorb to sediment surface and stimulated the indigenous bacteria to attach to the sediment particles. Recalcitrant surfactants and non-surfactant organic nutrients did not stimulate attachment Attachment of bacteria was maximal when biodegradation was fastest, and was reversed when biodegradation was complete. Dodecanol, the primary product of SDS-biodegradation, markedly stimulated attachment. When SDS was added to suspensions containing sediment and either known degraders or known non-degraders, only the degraders became attached, and attachment accelerated surfactant biodegradation to dodecanol. These cyclical cooperative interactions have implications for the design of biodegradability-tests, the impact of surfactant adjuvants on biodegradability of herbicides/pesticides formulated with surfactants, and the role of surfactants used to accelerate bioremediation of hydrocarbon-polluted soils.


1999 ◽  
Vol 39 (7) ◽  
pp. 91-98 ◽  
Author(s):  
Ryan N. Jordan ◽  
Eric P. Nichols ◽  
Alfred B. Cunningham

Bioavailability is herein defined as the accessibility of a substrate by a microorganism. Further, bioavailability is governed by (1) the substrate concentration that the cell membrane “sees,” (i.e., the “directly bioavailable” pool) as well as (2) the rate of mass transfer from potentially bioavailable (e.g., nonaqueous) phases to the directly bioavailable (e.g., aqueous) phase. Mechanisms by which sorbed (bio)surfactants influence these two processes are discussed. We propose the hypothesis that the sorption of (bio)surfactants at the solid-liquid interface is partially responsible for the increased bioavailability of surface-bound nutrients, and offer this as a basis for suggesting the development of engineered in-situ bioremediation technologies that take advantage of low (bio)surfactant concentrations. In addition, other industrial systems where bioavailability phenomena should be considered are addressed.


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