Comparison between adsorption isotherm determination techniques and overloaded band profiles on four batches of monolithic columns

The adsorption isotherms of 4-tert.-butyl phenol were measured on four different monolithic columns, using three different techniques, classical frontal analysis (FA), the perturbation on a plateau method (PP) and the recently introduced numerical procedure known as the inverse numerical method (IN). This last approach requires only the recording of a few overloaded profiles and has the potential advantage of affording a dramatic decrease of the amounts of compounds, solvent, and time needed to determine accurate estimates of the coefficients of the isotherm. The reproducibility of the adsorption data measured on the four columns is discussed with reference to the specific techniques used for obtaining these data and to the most suitable equation used for modeling them. The data obtained for the different columns were highly consistent. The inverse numerical approach was confirmed to provide a powerful, accurate, and economic method for measuring single component adsorption data.     

Reactions of hexamethylditin and trimethyltin sulfide withN-thio-derivatives of phthalimide

The initial formation of organotin derivatives with Sn-S-N bonds in heterolytic reactions of hexamethylditin or trimethyltin sulfide withN-(chlorothio)phthalimide is suggested. Subsequent interaction of these compounds with sulfenyl chloride affordsN, N-thioorN, N-dithiobisphthalimide. Homolytic reaction of hexamethylditin withN, N-dithiobisphthalimide also occursvia an organotin intermediate, which, in the absence of a nucleophilic reagent, eliminates sulfur and converts intoN-trimethylstannylphthalimide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2111–2114, December, 1993.     

How anomalous are the anomalous properties of fluorine? Ionization energy and electron affinity revisited

It is well established that atomic fluorine has a miserly high ionization energy and avariciously high electron affinity. Yet, as was shown some 30 years ago, the latter value is anomalously low-linear extrapolation shows the value to be some 110 kJ/mol less than expected by comparison to the heavier halogens. Related literature investigation extended this anomaly to nitrogen and oxygen and their (valence) isoelectronic congeners. We extend it to related cationic species and thereby the noble gases and alkali metals, and the aforementioned species are better understood. We thus ask if the ionization energy/electron affinity anomaly of fluorine remains an anomaly.     

Chemoselective synthesis of multiple epoxy-bridged tetrahydropyranone ring systems

Bis- as well as tris-tetrahydropyranone ring systems were obtained via multiple tandem cyclization-1,3-dipolar cycloaddition reactions of α-diazo ketones with ketone as well as aldehyde functional groups in a chemoselective manner.     

Enantioselectivity of 6-O-alkyldimethylsilyl-2,3-di-O-methyl-β-cyclodextrins as chiral stationary phases in capillary GC

Summary Clenbuterol has been determined in urine by solidphase extraction on a C₁₈ cartridge, diazotization of the eluate with nitrite, coupling of the diazonium ion with 1-(naphthyl)ethylenediamine, and separation of the azo dye formed by HPLC with a C₁₈ column and a micellar mobile phase containing 0.1 M sodium dodecyl sulphate, 12%n-butanol and 0.05 M citrate buffer, pH 3. Recoveries higher than 90% were obtained by mixing the samples with a 20% 0.2 M NaOH before extraction. Limits of detection of 51 and 6.7 ng L⁻¹ were obtained with spectrophotometric and thermal lens spectrometric detection, respectively; respective repeatabilities were 3.1% (5 μg mL⁻¹) and 5.6% (0.16 μg mL⁻¹).     

A simple method for the calculation of π-bond orders in alternant hydrocarbons

A new method for the calculation of bond orders in alternant hydrocarbons is presented. The method requires a summation over the contributions of various superposition diagrams. Quantitatively, the method is almost as reliable as PPP, and due to its simplicity it can be used for fast and relatively accurate calculation of bond orders. In addition some simple rules are derived, which in many cases can be used to predict the signs of bond orders between nonbonded atoms.Dedicated to Professor J. Koutecký on the occasion of his 65th birthdayResearch supported by the Robert A. Welch Foundation of Houston, Texas     

Reaction of 4,4′-dimethyldiphenyl ether with phosphorus trichloride in the presence of anhydrous aluminum chloride

The reaction of 4,4-dimethyldiphenyl ether with phosphorus trichloride in the presence of anhydrous aluminum chloride was studied. This reaction affords 2,8-dimethyl-10H-10⁵-phenoxaphosphine 10-oxide as virtually the only product. In air, the latter in an alkaline solution is quantitatively transformed into 10-hydroxy-2,8-dimethyl-10H-10⁵-phenoxaphosphine 10-oxide.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2762–2765, December, 2004.     

Stereoselective synthesis of (−)-microcarpalide

A highly convergent and efficient synthesis of (−)-microcarpalide, a 10-membered lactone displaying remarkable microfilament disrupting activity is described. Ring-closing metathesis and Sharpless asymmetric dihydroxylations are the key steps. Our strategy highlights the application of novel hydroxy lactone precursors for the stereoselective synthesis of (−)-microcarpalide.     

Effect of some additives on the reactions in fly ASH-Ca(OH)2 system

Differential thermal analysis and thermogravimetry were used to evaluate the effect of some additives, such as CaSO₄, CaCl₂ and silica fume amorphous silica from ferrosilicon synthesis on the mechanism and kinetics of reactions occurring in fly ash-Ca(OH)₂ system. The accelerating role of these additives was demonstrated from the data relating to Ca(OH)₂ consumption in hydrated pastes, determined by TG measurements. This revised version was published online in July 2006 with corrections to the Cover Date.