Problem of a wide variety of products in the Cu(hfac)2-nitroxide system

The stereochemically flexible Cu(hfac)(2) metal-ligand system when combined with polyfunctional nitroxides leads to a variety of solids with varying structure and composition. While investigating the products of Cu(hfac)(2) interaction with spin-labeled pyrazole 4,4,5,5-tetramethyl-2-(1-methyl-1H-pyrazol-4-yl)-imidazoline-3-oxide-1-oxyl, we have isolated a family of (12) heterospin compounds differing in structure and composition in the solid state. In synthetic systems, these compounds often cocrystallize and must be separated mechanically. It is also shown that minor variation of the structure of the solid heterospin complex can substantially change the magnetic properties of compounds.     

Synthesis of hcp-Co Nanodisks

hcp Co disk-shaped nanocrystals were obtained by rapid decomposition of cobalt carbonyl in the presence of linear amines. Other surfactants, in addition to the amines, like phosphine oxides and oleic acid were used to improve size dispersion, shape control, and nanocrystal stability. Co disks are ferromagnetic in character and they spontaneously self-assemble into long ribbons. X-ray and electron diffraction, electron microscopy, and SQUID magnetometry have been employed to characterize this material.     

Functional antibody immobilization on 3-dimensional polymeric surfaces generated by reactive ion etching

Reactive ion etching (RIE) was used to pattern antibodies onto the surfaces of polymer substrates. A low pressure, inductively coupled oxygen plasma was used to anisotropically etch 25-30 mum deep features into poly(methyl methacrylate) (PMMA), Zeonex, and polycarbonate (PC). Scanning electron microscopy and contact angle measurements show that the resulting surfaces exhibit significant microroughness and enhanced hydrophilicity. Fourier transform infrared spectroscopy suggests that, in addition to enhanced surface area, chemical modifications may contribute to antibody immobilization. Polyclonal antibodies preferentially bind to the etched areas in RIE-patterned PMMA and Zeonex substrates but localize in unetched regions of RIE-patterned PC surfaces. Simple immunoassays were performed to demonstrate a potential application for RIE-modified polymer surfaces. Antibodies specific for the capture of fluorescently labeled cholera toxin, S. aureus enterotoxin B, and B. anthracis protective antigen were immobilized onto etched PMMA surfaces and shown to specifically capture their labeled antigen from solution. This work demonstrates a potentially useful fabrication methodology for constructing antibody microarrays on plastic substrates.     

Reversed-phase affinity chromatography of ecdysteroids with boronic acid-containing eluents

Selective effects of boronic acid-containing eluents on the chromatographic behaviour of ecdysteroids are described. The use of such eluents provides a simple, rapid and sensitive means to assess the presence of certain diol groups in ecdysteroids by ordinary RP-HPLC. It is demonstrated that ecdysteroids with different sets of diols in their molecules have individual shapes of chromatographic peaks. A mechanism of the boronic acid effect is discussed.     

Die Reaktion zwischen Ozon und Wasserstoffperoxyd

Zusammenfassung Es wurde die Reaktion zwischen Ozon und Wasserstoffperoxyd in Lösungen von 0.01 normaler Schwefelsäure bei 0° untersucht. Sie verläuft unter diesen Umständen so langsam, daß die Geschwindigkeit gemessen werden kann.Die nach einer gewissen Zeit verschwundene Ozonmenge ist der verschwundenen Peroxydmenge nicht äquivalent, sondern erheblich größer, und zwar um so größer, je verdünnter das Peroxyd ist.Nur bei einem großen Überschuß an letzterem verläuft die Reaktion nach der Gleichung: H₂O₂+O₃=H₂O+2 O₂.Diese Ergebnisse lassen sich durch die Annahme erklären, daß neben der genannten Reaktion eine freiwillige Zersetzung des Ozons stattfindet, deren Geschwindigkeit durch die Anwesenheit von Wasserstoffperoxyd außerordentlich stark erhöht wird. Durch diese Annahme ist auch die Möglichkeit gegeben, die früher gefundenen Unregelmäßigkeiten im zeitlichen Verlauf der Zersetzungsgeschwindigkeit des gelösten Ozons zu verstehen.Über diese Untersuchung wurde auf dem Internationalen Kongreß für angewandte Chemie in New-York (1912) in der Sektion Xb berichtet. Or. Comm. 8. intern. Congreß of applied Chemistry, Vol. XXVI, S. 611.     

Isolation of the active constituents in natural materials by 'heart-cutting' isocratic reversed-phase two-dimensional liquid chromatography

A multidimensional heart-cutting reversed-phase HPLC separation approach, where two columns were operated independently via two six-port two-position switching valves, was employed in the isolation of a major bioactive found in the ethanol-water (80:20) crude extract of Clerodendrum floribundum. In this mode of operation, the specific productivity of the multidimensional approach under overload conditions was twice that of conventional gradient methods with the same loading factor. Isolated sample purities were greater than 99% with recoveries of 95%. The independent operation of each of the two columns employed in the multidimensional approach allowed the cycle time to be less than 7 min, compared to 23 min in the gradient elution single-dimension mode of operation.     

Characterization of chemically modified carbonaceous electrode materials by x-ray fluorescence and scanning electron microscopy

An attachment scheme which utilizes cyanuric chloride as a linking agent in the preparation of chemically modified electrodes was investigated by using simultaneous scanning electron microscopy and x-ray fluorescence. Certain contaminants were discovered on the surface of the material following various steps in the reaction scheme used for attachment. The iron storage protein, ferritin, was attached to the surface of spectroscopic-grade graphite rod. Attempts were made to establish the surface distribution of the ferritin and to correlate distribution with surface morphology.     

A family of novel DNA sequencing instruments based on single-photon detection

We have developed a family of high-performance capillary DNA sequencing instruments based on a novel multicolor fluorescent detection technology. This technology is based on two technical innovations: the multilaser excitation of fluorescence of labeled DNA fragments and the "color-blind" single-photon detection of modulated fluorescence. Our machines employ modern digital and broadband techniques that are essential for achieving superior instrument performance. We discuss the design and testing results for several versions of the automated single lane DNA sequencers, as well as our approach to scaling up to multilane instruments.     

Student Questionnaries

We have developed several alternative practical laboratory examinations for the beginning organic chemistry course and have field tested these laboratory exercises as a component of the final examination in the laboratory component of that course. Data correlating practicum scores with overall scores in the laboratory course show significant scatter, suggesting to us possible shortcomings in the traditional methods of evaluation of laboratory skills.