Acid/Base-treated activated carbons: characterization of functional groups and metal adsorptive properties

Surface modification of activated carbons by various physicochemical methods directs an attractive approach for improvement of heavy metal uptake from aqueous solutions. Activated carbons were modified with HCl and HNO3 optionally followed by NaOH. The effects of surface modifications on the properties of the carbons were studied by the specific surface area, carbon pH, and total acidity capacity as well as by scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The modifications bring about substantial variation in the chemical properties whereas the physical properties remain nearly unchanged. NaOH causes an increase in the content of hydroxyl groups, while the HCl treatment results in an increase in the amount of single-bonded oxygen functional groups such as phenols, ethers, and lactones. The HNO3 modification generates a large number of surface functional groups such as carbonyl, carboxyl, and nitrate groups. The HNO3 modification significantly increases the copper adsorption, while the HCl treatment slightly reduces the copper uptake. Most of the copper ions are adsorbed rapidly in the first 2 h; the adsorption equilibrium is established in around 8 h. An intraparticle diffusion model successfully describes the kinetics of copper adsorption onto the carbons.     

Restricted rotation about the boron---nitrogen bond in aminoboranes

The application of variable temperature ¹³C NMR to the study of a series of chlorodialkylaminophenylboranes has enabled G values for the rotational barrier, about the boron---nitrogen bond, to be determined.     

N-α-Benzyloxyacetyl derivatives of (S)-4-benzyl-5,5-dimethyloxazolidin-2-one for the asymmetric synthesis of differentially protected α,β-dihydroxyaldehydes

α-Dibenzylamino- and α-benzyloxy- derivatives of N-acetyl-(S)-4-benzyl-5,5-dimethyloxazolidin-2-one readily undergo highly stereoselective boron mediated syn-aldol reactions with a range of aromatic and aliphatic aldehydes, generating the syn-aldol products in good to excellent yields as single diastereoisomers after purification. In the α-dibenzylamino series, deprotection of the functionalised aldol fragments to the corresponding α-amino-β-hydroxy methyl ester or α-amino-β-hydroxyaldehyde proved problematic, with a range of N- and O-protecting groups giving mixtures of products arising from endocyclic and exocyclic cleavage pathways. However, in the α-benzyloxy series, O-silyl protection of the aldol products, and subsequent DIBAL reduction gives stereoselectively the corresponding N-1′-hydroxyalkyloxazolidin-2-ones, which undergo base promoted fragmentation to the desired highly functionalised and differentially protected α,β-dihydroxyaldehydes in good yields and without loss of stereochemical integrity.     

THE PRESENCE OF PHOTOREACTIVE β-CARBOLINE FLUOROPHORES IN WEATHERED WOOL KERATIN

Abstract Solvent-cleaned Merino wool, which was enzymatically digested with protease K, displayed a fluorescence maximum at 500 nm when excited at 430 nm. The yield of this emission was approximately 15 times greater for a fiber tips digest than for a digest of the mid-length region of the same fibers.
Separation of the components in the wool tip digest by silica gel thin-layer chromatography revealed the presence of several fluorescent species. The chromatographic mobility of these species was similar to the behavior observed in a preparation of authentic 1-methyltetrahydro-P-carboline, 1,3-dicarboxylic acid.
Mass spectroscopy of the fluorescent compounds in the wool tip digest displayed molecular ions, [M + H]⁺ with m/z = 273.0890 and 257.0560, and molecular weights that define the formulae C₁₄H₁₂N₂O₄ and C₁₁H₈O₄N₂, respectively, which correspond to β-carboline 1,3-dicarboxylic acids. Mass spectral evidence also indicates the presence of two other β-carbolines.     

Fe(CO)5 thin films adsorbed on Au(111) and on self-assembled organic monolayers: I. Structure

The adsorption of Fe(CO)(5) onto Au(111)/mica and C(4), C(8), C(12), and C(16) SAMs/Au(111)/mica surfaces has been studied using infrared spectroscopy to elucidate the coverage-dependent structures of these films and the intermolecular couplings that determine the form of the spectra. For all substrates, the first layer is composed of molecules physisorbed with one axial and two equatorial carbonyl groups directed toward the substrate; subsequent layers are preferentially oriented with the C(3) molecular axis aligned perpendicular to the substrate (i.e., one axial carbonyl group directed toward the substrate). The axial vibrational band systematically shifts to higher frequencies with increasing surface coverage because of the effects of intermolecular coupling of the quasiparallel transition dipole moments. The strong effects of dipolar coupling are also witnessed by the trends of the band positions when the distance to the image plane is systematically varied using highly organized self-assembled organic substrates; no band shifts are observed when dilute Fe(CO)(5) is embedded in Xe matrixes under identical experimental conditions. The as-deposited films are structurally stable below 125 K on Au(111)/mica surfaces and below 100 K on the organic self-assembled monolayers. The instability of the films above these temperatures demonstrates that the as-adsorbed films do not form thermodynamically well-defined phases but are structurally metastable. The results presented herein and in the companion paper provide a consistent framework to interpret the spectroscopy of these systems that resolves outstanding issues concerning these films and provides a structural model that explains the dynamic properties of these films during exposure to low-energy electron beams.     

Enolization of acetone in superheated water detected via radical formation

Muoniated free radicals have been detected in muon-irradiated aqueous solutions of acetone at high temperatures and pressures. At temperatures below 250 degrees C, the radical product is consistent with muonium addition to the keto form of acetone. However, at higher temperatures, a different radical was detected, which is attributed to muonium addition to the enol form. Muon hyperfine coupling constants have been determined for both radicals over a wide range of temperatures, significantly extending the range of conditions under which these radicals and the keto-enol equilibrium have been studied.