Field ionization mass spectrometry as a facile method for the study of the thermal formation of radicals

Electron impact spectra of thermolysis products of organic salts heated in the ion source of a mass spectrometer may give rise to organic ions corresponding to the cation of the salt. Field ionization mass spectrometry has been used as a facile method for detemining whether such an ion is due to ionization of the corresponding radical present in the gas phase, or to an electron impact induced fragmentation of a reaction product of higher mass. By comparison of the electron impact and field ionization spectra of a series of N-methyl pyridinium, tropylium and 1,2-dithiolylium salts it has been found possible to identify the radicals formed thermolytically, when present.     

Kinetics of heterogeneous cellulose reactions. I. Cyanoethylation of cotton cellulose

Sakurada's equation and fundamental kinetic laws were applied to the heterogeneous cyanoethylation of cellulose, performed by reacting fiber with liquid acrylonitrile, with sodium hydroxide as the catalyst. The data fit Sakurada's equation better at higher temperatures; deviation occurs at the initial stage, and the rate of reaction falls abruptly at a later stage. The degree of substitution at which the abrupt rate change occurred decreased as the temperature increased from 31 to 60°C. and also as the crystallinity of the fiber decreased. Diluting the reagent with different solvents decreased the rate of reaction and changed its transition points, but did not change the essential nature of the reaction, each segment of which fits Sakurada's equation very well. A uniform distribution of the catalyst (sodium hydroxide) throughout the fiber was attempted, and then the reaction was studied at 50°C. Diffractograms of the samples provided further evidence that the position of the rate change is associated with the change of cellulose (I) crystalline structure. Approximate energy of activation has been calculated, from the specific rate constants, between 31 and 40°C. as 10.6 kcal. and between 45 and 50°C. as 16.7 kcal. At other temperatures the determination was handicapped, due to temperature dependence of the order of reaction. An empirical relation between the constants of Sakurada's equation and the reaction temperature has been sought and correlated with the Arrhenius equation. Energies of activation, determined from this relationship, have been found to be very close to the above values. The change of order of reaction with temperature suggests that the reaction is affected by diffusion and the mechanism is interpreted as a diffusion-controlled reaction where hydrogen bonds play a significant role in diffusion.     

ELECTRON SPIN ECHO ENVELOPE MODULATION OF THE TRANSIENT EPR SIGNALS OBSERVED IN PHOTOSYNTHETIC ALGAE AND CHLOROPLASTS*

Phase memory decays were obtained from the transient signals sampled within 50 ns of laser excitation by time resolved electron spin echo (ese) spectroscopy in normal protonated, deuterated, deuterated ¹⁵N photosynthetic algae and broken chloroplasts. Previously, it has been shown that application of time resolved ese to study these systems, in particular, gives rise to two kinds of signals (standard and special ese). The standard ese signal at g = 2.0023 and the special ese signal exhibit similar electron spin echo envelope modulation (eseem). The modulation frequency and pattern can be identified with that obtained from stable oxidized P₇₀₀ in the same system. The two lower field resonances of the standard ese signal do not show eseem. The results support the proposed mechanism for formation of special ese and the notion that the standard ese is due to at least two radicals. It is also demonstrated that we can observe eseem of P⁺₇₀₀ under ambient temperature conditions.     

Macrocycle synthesis strategy based on step-wise “adding and reacting” three components enables screening of large combinatorial libraries

Macrocycles provide an attractive modality for drug development, but generating ligands for new targets is hampered by the limited availability of large macrocycle libraries. We have established a solution-phase macrocycle synthesis strategy in which three building blocks are coupled sequentially in efficient alkylation reactions that eliminate the need for product purification. We demonstrate the power of the approach by combinatorially reacting 15 bromoacetamide-activated tripeptides, 42 amines, and 6 bis-electrophile cyclization linkers to generate a 3780-compound library with minimal effort. Screening against thrombin yielded a potent and selective inhibitor (K_i = 4.2 ± 0.8 nM) that efficiently blocked blood coagulation in human plasma. Structure–activity relationship and X-ray crystallography analysis revealed that two of the three building blocks acted synergistically and underscored the importance of combinatorial screening in macrocycle development. The three-component library synthesis approach is general and offers a promising avenue to generate macrocycle ligands to other targets.

Combination of three efficient chemical reactions allows for solution-phase synthesis of 3780 macrocycles and identification of potent thrombin inhibitor.     

Derivation of class II force fields. VIII. Derivation of a general quantum mechanical force field for organic compounds

A class II valence force field covering a broad range of organic molecules has been derived employing ab initio quantum mechanical "observables." The procedure includes selecting representative molecules and molecular structures, and systematically sampling their energy surfaces as described by energies and energy first and second derivatives with respect to molecular deformations. In this article the procedure for fitting the force field parameters to these energies and energy derivatives is briefly reviewed. The application of the methodology to the derivation of a class II quantum mechanical force field (QMFF) for 32 organic functional groups is then described. A training set of 400 molecules spanning the 32 functional groups was used to parameterize the force field. The molecular families comprising the functional groups and, within each family, the torsional angles used to sample different conformers, are described. The number of stationary points (equilibria and transition states) for these molecules is given for each functional group. This set contains 1324 stationary structures, with 718 minimum energy structures and 606 transition states. The quality of the fit to the quantum data is gauged based on the deviations between the ab initio and force field energies and energy derivatives. The accuracy with which the QMFF reproduces the ab initio molecular bond lengths, bond angles, torsional angles, vibrational frequencies, and conformational energies is then given for each functional group. Consistently good accuracy is found for these computed properties for the various types of molecules. This demonstrates that the methodology is broadly applicable for the derivation of force field parameters across widely differing types of molecular structures. Copyright 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1782-1800, 2001     

Electrothermal stirring for heterogeneous immunoassays

A technique is proposed to enhance microfluidic immuno-sensors, for example, immunoassays, in which a ligand immobilized on a microchannel wall specifically binds analyte flowing through the channel. These sensors can be limited in both response time and sensitivity by the diffusion of analyte to the sensing surface. In certain applications, the sensitivity and response of these heterogeneous immunoassays may be improved by using AC electrokinetically-driven microscale fluid motion to enhance antigen motion towards immobilized ligands. Specifically, the electrothermal effect is used to micro-stir analyte near the binding surface. Numerical simulations of antigen in a microchannel flow subjected to the electrothermal effect show that 6 V(rms) applied to electrodes near a binding region can increase binding in the first few minutes by a factor of seven. The effectiveness of electrothermal stirring is a strong function of the Damk?hler number. The greatest binding enhancement is possible for high Damk?hler numbers, where the reaction is limited by diffusion. Based on these results, the utility of this technique for diffusion-limited microfluidic sensor applications is demonstrated.     

Mass spectrometry in structural and stereochemical problems–CXCV: The structure of the [C6H6O]+˙ ion in the spectrum of phenyl alkyl ethers

The [C₆H₆O]⁺˙ ion from C₆H₅OC₄H₉ is structurally similar to the molecular ion from phenol as demonstrated by ¹³C labeling.     

ESCA: Elektronen-Spektroskopie für chemische Analyse

Eine Substanzprobe, auf die Röntgen-Strahlung einwirkt, emittiert Photo- und Auger-Elektronen. Die Energiespektren der emittierten Elektronen geben Informationen über die Elektronen-struktur in der Probe — und zwar von den innersten atomaren Niveaus und ihrer Abhängigkeit von der chemischen Umgebung bis hin zu den Molekülorbitalen der Valenzelektronen sowie der Bandstruktur bei Festkörpern. Solche Elektronenspektren können jetzt mit hochauflösenden Instrumenten registriert werden; ihre Analyse ergibt neue Aspekte für die Untersuchung der chemischen Bindung. Die zu diesem Zweck entwickelte und inzwischen zu einem hohen Grad von Vollkommenheit ausgebaute Methode der Elektronenspektroskopie wird im folgenden als ESCA (Electron Spectroscopy for Chemical Analysis) bezeichnet.     

An inequality between thep- and (p, 1)-summing norm of finite rank operators fromC(K)-spaces

We show, for any operatorT from aC(K)-space into a Banach space with rank (T)≤n, the inequality , whereC≤4.671 is a numerical constant. The factor (1+logn)^1−1/p is asymptotically correct. This inequality extends a result of Jameson top ≠ 2. Several applications are given — one is a positive solution of a conjecture of Rosenthal and Szarek: For 1≤p<q<2,