The chemistry and physics of zinc oxide surfaces

Metal oxides are virtually everywhere – only gold has the property not to form an oxide on its surface when exposed to the ambient. As a result, understanding the physics and chemistry of oxide surfaces is a topic of pronounced general interest and, of course, also a necessary prerequisite for many technical applications. The most important of these is certainly heterogeneous catalysis, but one has to realize that – under ambient conditions – virtually all phenomena occurring at liquid/metal and gas/metal interfaces are determined by the corresponding oxide. This applies in particular to friction phenomena, adhesion and corrosion. A necessary – but not necessarily sufficient – condition for unravelling the fundamentals governing this complex field is to analyze in some detail elementary chemical and physical processes at oxide surfaces. Although the Surface Science of metal surfaces has seen a major progress in the past decades, for oxides detailed experimental investigations for well-defined single crystal surfaces still represent a formidable challenge – mostly because of technical difficulties (charging), but to some extent also due to fundamental problems related to the stabilization of polar surfaces. As a result, the amount of information available for this class of materials is – compared to that at hand for metals – clearly not satisfactory. A particular disturbing lack of information is that about the presence of hydrogen at oxide surfaces – either as hydroxy-species or in form of metal hydrides.In the present review we will summarize recent experimental and theoretical information which has become available from single crystal studies on ZnO surfaces. While the number of papers dealing with another oxide, rutile TiO₂, is significantly larger (although titania does not exhibit a polar surface), also for zinc oxide a basis of experimental and theoretical knowledge as been accumulated, which – at least for the non-polar surfaces – allows to understand physico-chemical processes on an atomic level for an increasing number of cases. In particular with regards to the interaction with hydrogen a number of – often surprising – observations have been reported recently. Some of them carry implications for the behaviour of hydrogen on oxide surfaces in general. We will present the currently available information for both, experiment and theory, and demonstrate the rather large variety of this material’s surface properties.     

Mass spectrometry of 3-substituted 4-hydroxyisoquinolines and their derivatives

Under electron impact, 3-aryl-4-hydroxyisoquinolines form [M – H]⁺, [M – CO]⁺ and [M – H – CO]⁺ ions with a subsequent elimination of HCN or CH₃CN. A cyclic structure for the [M – H]⁺ ion is suggested. The primary act of fragmentation of the corresponding methyle ether derivatives is the loss of CH₃?, as well as H?; the further fragmentatio is similar to that described above. It has been established that the unusual [M – H]⁺, [M – OH]⁺ and [M – CH₅?]⁺ ions are formed when 8 fragments. Fragmentation schemes for all compounds are proposed based upon high resolution mass spectra and deuterated analogues.     

Efficient Synthesis of α‐Benzylidene‐γ‐methyl‐γ‐butyrolactones

A concise synthesis of α‐benzylidene‐γ‐methyl‐γ‐butyrolactones 5a – g from substituted benzaldehydes is described. Compounds 1a – g on reaction with phosphorane 2 , provide the pentenoates 3a – g , which can be hydrolyzed to the acids 4a – g . The latter are cyclized to the corresponding butyrolactones 5a – g in excellent yields. The pentenoates 3a – g , on acid catalyzed cyclization, also provide 5a – g in very high yields.     

Use of Cobalt Thiocyanate for Thin-Layer Chromatographic Detection of Neonicotinoid Insecticide Imidacloprid

JPC – Journal of Planar Chromatography – Modern TLC - Imidacloprid is a member of chloronicotinyl neonicotinoid compounds. It is the most important systemic insecticide and has a wide...     

Synthesis of Thiazole and Fused Thiazolo Derivatives

The syntheses of thiazole and fused thiazolo derivatives 2 – 4 , 6 – 8 , 10a – 11b , 13 – 16 from heterocylic isothiocyanates 1 , 5 , 9 , and 12 bearing an ortho ester group and bifunctional reagents, such as substituted propargylamines, is described. Different regioselectivity of intramolecular nucleophilic attack of the thiourea S-atom on the C ? C bond, resulting in the formation of both thiazolo and thiazino derivatives, as well as NMR structure elucidation are discussed.     

β-Cleavage of Bis(homoallylic) Potassium Alkoxides. Preparation of 3-Hydroxypropyl and 4-Hydroxybutyl Propenyl Ketones from γ- and δ-Lactones. Synthesis of (±)-Rose oxide

Starting from γ- and δ-lactones 1 – 3 , a two-step preparation of 3-hydroxypropyl and 4- hydroxybutyl propenyl ketones 10 – 18 is described, involving as the key step the β-cleavage of the bis(homoallylic) potassium alkoxides 4a – 9a . The novel methodology is illustrated by a short synthesis of (±)-rose oxide( 20 ).     

Modeling of Thin-Layer Chromatographic Separation of Androstane Isomers

JPC – Journal of Planar Chromatography – Modern TLC - Modeling of thin-layer chromatographic separation of androstane isomers to find the optimum mobile phase is described in this...     

Comparative Lipophilicity of Morphine Derivatives

JPC – Journal of Planar Chromatography – Modern TLC - Lipophilicity is an important physicochemical characteristic of compounds having potential use in the treatment of humans and...     

Use of HPTLC to Establish a Distinct Chemical Profile for Shankhpushpi and for Quantification of Scopoletin in Convolvulus pluricaulis Choisy and in Commercial Formulations of Shankhpushpi

JPC – Journal of Planar Chromatography – Modern TLC - Convolvulus pluricaulis is a highly valued rasayana drug of the Ayurvedic system of medicine. It is one of the four drugs...     

RP-HPLC Separation of Highly Charged Quaternary Ammonium Salts

Abstract

The reverse phase HPLC separation of polycationic viologenes 1 – 4 and macrotricyclic quaternary ammonium salts 5 – 8 using ion pair conditions is described. Whereas the compounds 1 – 4 could be analysed on any of 4 stationary RP-18 phases tested, the cage compounds 5 – 8 were much more sensitive to the source of the matrix material. Optimal separation conditions for the latter up to eightfold positively charged macrocycles employ sodium perchlorate in acidic aqueous methanol using Nucleosil RP-18 or Lichrospher CH-18 columns.     

Evaluation of High-Performance Thin-Layer Chromatography for the Quantification of Phenylpropanoids in Commercial Echinacea Products

JPC – Journal of Planar Chromatography – Modern TLC - There is a large chemical variability between commercially available Echinacea for both research and consumption impacts on the...     

Protection of carbon steel with superhydrophobic coating against corrosion in NaCl solution

Corrosion and kinetics of partial electrode reactions on carbon steel St3 with superhydrophobic coatings of three types were studied in 0.5 M NaCl and 50 g/L NaCl +400 mg/L H₂S solutions. The investigations were carried out on electrodes made of carbon steel St3 with a chemical composition, wt. %: C – 0.20; Mn – 0.50; Si – 0.15; P – 0.04; S – 0.05; Cr – 0.30; Ni – 0.20; Cu – 0.20, and Fe – 98.36. To obtain the type I coating, the metal surface was textured by an IR laser radiation of nanosecond duration followed by chemisorption of fluorobutylsilane out of a solution in n-decane. To obtain a coating of type II, a nanoscale composite layer consisting of aggregates of aerosil nanoparticles was applied additionally to the outcome of type I method. To obtain a coating of type III, the metal surface after being textured by the infrared (IR) laser radiation of nanosecond duration was followed by chemisorption of fluoroxy silane. The influence of duration τ of the medium corrosive impact on protective effect of the superhydrophobic coating is considered. It was shown that upon reaching a steady state (after 72 h), the corrosion rate of steel with a superhydrophobic coating of I and II types in a 0.5 M NaCl solution is reduced by 23 ± 3 times compared with unprotected samples. Approximately the same picture is characteristic of electrodes with a coating of type III in a solution of 50 g/L NaCl +400 mg/L H₂S.     

Development and Validation of TLC Method for Analysis of Stresroak Premix

JPC – Journal of Planar Chromatography – Modern TLC - With the realization of the growing popularity and demand for phytopharmaceuticals, standardization is becoming a mandatory part of...     

RPTLC Determination of log P of Structurally Diverse Neutral Compounds

JPC – Journal of Planar Chromatography – Modern TLC - A validated reversed-phase thin-layer chromatographic (RPTLC) method is proposed for parallel estimation of the lipophilicity of...     

Densitometric Quantification of Monogalactosyldiacylglycerol (MGDG) and Digalactosyldiacylglycerol (DGDG) in Extracts of Fresh Samples of Erigeron canadensis Collected at Different Stages of Growth

JPC – Journal of Planar Chromatography – Modern TLC - Erigeron canadensis is an annual plant of the Asteraceae family, widely distributed in rural and urban areas of Poland and other...     

Synthesis of Monosaccharide‐Derived Spirocyclic Cyclopropylamines and Their Evaluation as Glycosidase Inhibitors

The glucose‐, mannose‐, and galactose‐derived spirocyclic cyclopropylammonium chlorides 1a – 1d, 2a – 2d and 3a – 3d were prepared as potential glycosidase inhibitors. Cyclopropanation of the diazirine 5 with ethyl acrylate led in 71% yield to a 4 : 5 : 1 : 20 mixture of the ethyl cyclopropanecarboxylates 7a – 7d , while the Cu‐catalysed cycloaddition of ethyl diazoacetate to the exo‐glycal 6 afforded 7a – 7d (6 : 2 : 5 : 3) in 93–98% yield (Scheme 1). Saponification, Curtius degradation, and subsequent addition of BnOH or t‐BuOH led in 60–80% overall yield to the Z‐ or Boc‐carbamates 11a – 11d and 12a – 12d , respectively. Hydrogenolysis of 11a – 11d afforded 1a – 1d , while 12a – 12d was debenzylated to 13a – 13d prior to acidic cleavage of the N‐Boc group. The manno‐ and galacto‐isomers 2a – 2d and 3a – 3d , respectively, were similarly obtained in comparable yields (Schemes 2 and 4). Also prepared were the differentially protected manno‐configured esters 24a – 24d ; they are intermediates for the synthesis of analogous N‐acetylglucosamine‐derived cyclopropanes (Scheme 3). The cyclopropylammonium chlorides 1a – 1d, 2a – 2d and 3a – 3d are very weak inhibitors of several glycosidases (Tables 1 and 2). Traces of Pd compounds, however, generated upon catalytic debenzylation, proved to be strong inhibitors. PdCl is, indeed, a reversible, micromolar inhibitor for the β‐glucosidases from C. saccharolyticum and sweet almonds (non‐competitive), the β‐galactosidases from bovine liver and from E. coli (both non‐competitive), the α‐galactosidase from Aspergillus niger (competitive), and an irreversible inhibitor of the α‐glucosidase from yeast and the α‐galactosidase from coffee beans. The cyclopropylamines derived from 1a – 1d or 3a – 3d significantly enhance the inhibition of the β‐glucosidase from C. saccharolyticum by PdCl , lowering the K_i value from 40 μM (PdCl ) to 0.5 μM for a 1 : 1 mixture of PdCl and 1d . A similar effect is shown by cyclopropylamine, but not by several other amines.     

Application of HPTLC to the Analysis of Horminone in Sphacele chamaedryoides (Balbis) Briq.

JPC – Journal of Planar Chromatography – Modern TLC - Royleanones are diterpene quinones ubiquitous in plants belonging to the Lamiaceae family. Sphacele chamaedryoides is a plant used...     

Chromatographic Determination of Total Cholesterol in Human Lung Healthy and Cancer Tissues of the Same Patient

JPC – Journal of Planar Chromatography – Modern TLC - Cholesterol is an essential component of mammalian cells, but its role in cancer is unclear. We have determined the total...     

Development of HPTLC detection of synthetic pesticide carbosulfan in biological material

JPC – Journal of Planar Chromatography – Modern TLC - The field of agriculture is the key role in Indian society in which insecticides play a vital role in increasing the crop...