Hydrophobicity-induced drying transition in alkanethiol self-assembled monolayer—water interface

During the course of our investigation of the electron transfer properties of some redox species through highly hydrophobic long chain alkanethiol molecules on gold in aqueous and non-aqueous solvents, we obtained some intriguing results such as unusually low interfacial capacitance, very high values of impedance and film resistance, all of which pointed to the possible existence of a nanometer size interfacial gap between the hydrophobic monolayer and aqueous electrolyte. We explain this phenomenon by a model for the alkanethiol monolayer—aqueous electrolyte interface, in which the extremely hydrophobic alkanethiol film repels water molecules adjacent to it and in the process creates a shield between the monolayer film and water. This effectively increases the overall thickness of the dielectric layer that is manifested as an abnormally low value of interfacial capacitance. This behaviour is very much akin to the ‘drying transition’ proposed by Lum, Chandler and Weeks in their theory of length scale dependent hydrophobicity. For small hydrophobic units consisting of apolar solutes, the water molecules can reorganize around them without sacrificing their hydrogen bonds. Since for an extended hydrophobic unit, the existence of hydrogen bonded water structure close to it is geometrically unfavourable, there is a net depletion of water molecules in the vicinity leading to the possible creation of a hydrophobic interfacial gap.     

Multifunctional ToF-SIMS: combinatorial mapping of gradient energy substrates

We present a simple method for chemical modification of chlorosilane self-assembled monolayers (SAMs) on Si surfaces by exposure to a gradient of UV-ozone radiation to create stable substrates with a range of contact angles (θ_H2O≈5–95°) and surface energies on a single substrate. These gradient energy substrates are developed to potentially generate libraries for combinatorial studies of thin film phenomenology, where a systematic variation of interfacial surface energy represents one of the significant parameters along one axis. The graded oxidation process presents a systematic variation of surface chemical composition. We have utilized contact angle measurements and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to investigate this variation for a series of ions, among which are SiCH₃⁺, SiOH⁺ and COOH⁻. We show that the macroscopic measurements of surface free energy/contact angle correlate with the detailed analysis of surface chemistry (as assessed by ToF-SIMS) on these test substrates.     

Maskierung mit Kaliumjodid bei direkten Titrationen von Kupfer(II) mit Äthylendiamintetraessigsäure

Zusammenfassung Die Jodidoxydation durch Cu(II) wird in Anwesenheit von Ammoniak, Natriumtartrat, citrat oder -oxalat infolge Komplexbildung verhindert. Daher kann man z. B. Quecksüber(II) in Anwesenheit der genannten Komplexbildner mit Kaliumjodid maskieren und Kupfer(II) durch direkte Titration mit ÄDTA gegen Murexid, Brenzcatechinviolett, Chromazurol S, PAN oder PAR als Indikator bestimmen.

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Masking with potassium iodide in direct titrations of copper(II) with ethylenediamine tetraacetic acid

Summary The formation of a complex prevents the iodide oxidation by Cu(II) in the presence of ammonia, sodium tartrate, citrate, or oxalate. Hence mercury(II) for instance, can be masked against potassium iodide in the presence of these complex formers, and Cu(II) can be determined by direct titration with EDTA in the presence of murexide, pyrocatechol violet, chromazurol, PAN or PAR as indicator.

     

Oxidation of cyclohexane with molecular oxygen using a Schiff base cobalt complex bonded to carbamate-modified silica gel

The Schiff base [1,2-bis(salicylidene amino)phenylene]cobalt(II) complex, chemically bonded to a carbamate-modified silica gel catalyst, has been prepared by a four step procedure. The oxidation of cyclohexane was studied in the presence of this catalyst under relatively mild conditions (150–200 °C, 15–20 atm) using molecular oxygen. The catalyst was found to be very selective for the production of cyclohexanol, with cyclohexanone formed in only a small amount (45:1). This is in contrast to the commercially available processes in which cyclohexanol and cyclohexanone are both formed in appreciable amounts. The t.g.a. analysis shows the catalyst to be stable up to 211 °C and atomic absorption spectroscopy indicated negligible metal loss during 50 h use of the catalyst up to 180 °C.     

An efficient route to regioselective opening of N-tosylaziridines with zinc(II) halides

An efficient route for the regio- and stereoselective ring opening of N-tosylaziridines with zinc dihalides (ZnX₂, X = Cl, Br, I) is described. Depending on the solvent and Zn(II) halide, β-halo amines or imidazolines are obtained selectively in good to excellent yields.     

Cu-nanoparticles: a chemoselective catalyst for the aza-Michael reactions of N-alkyl- and N-arylpiperazines with acrylonitrile

A novel method for effecting the aza-Michael reactions of N-alkyl- and N-arylpiperazines with acrylonitrile using Cu-nanoparticles is described. The method features the use of 10 mol % Cu (14-17 nm) nanoparticles under mild reaction conditions to afford the addition products in good to excellent yields. The Cu-nanoparticles selectively catalysed the aza-Michael reaction of N-alkyl- and N-arylpiperazines in the presence of aromatic amino or aliphatic hydroxy groups.     

A new macrocyclic polystyrene-based sensor for chromium (III) ions

A new tetradentate dihydrogen perchlorate macrocyclic ligand (2,4,9,11-tetraphenyl-1,5,8,12-tetraazacyclotetradeca-1,4,8,11-tetraene dihydrogen perchlorate) was prepared and characterised. The macrocycle behaves as a selective chelating ion-exchanger for some metal ions. The polystyrene-based membrane electrode is found to exhibit quite promising selectivity for Cr3+ ions. It can be used to estimate chromium concentrations in the range 3.16x 10(-6)-1.00x10(-1) M with a near-Nernstian slope of 17.5 mV per decade of concentration between pH 3.0 to 6.5. The electrode is found to possess a fast response time of 15 s and was used over a period of three months with good reproducibility (s = +/- 0.3 mV). The selectivity coefficient values for mono-, di- and trivalent cations indicate excellent selectivity for Cr3+ ions over a large number of other cations. Anions such as Cl- and SO4(2-) do not interfere and the electrode also works satisfactorily in a mixed organic-water solution. The sensor has been used as an indicator electrode for the potentiometric titration of Cr3+ with EDTA. The practical utility of the membrane sensor has also been demonstrated in solutions contaminated with detergents (CTAB and SDS). Above all, the membrane sensor has been very successfully used to determine Cr3+ in some foods.