Solid Phase Peptide Synthesis

The last two decades have been an era of rapid progress in peptide research. This era was begun by the work of Sanger on the amino acid sequence determination of insulin and by du Vigneaud on the structure determination and synthesis of oxytocin. This period has seen impressive progress in the structure elucidation and synthesis of many peptides of natural origin and of great biological significance, as well as in methods for sequence determination and chemical synthesis of peptides [1–4]. Perfection of techniques and instruments for automatic determination of the amino acid sequence of peptides and proteins has made possible a greatly broadened understanding of genetics and evolution as well as the more chemical areas of mechanism of action of enzymes and hormones, and physical chemistry of peptides and proteins. Effective methods of peptide synthesis are crucial to progress in this area, because only by synthesis can adequate amounts of important peptides be made available for chemical, biological, and physical studies, as well as for exploration of the structure-function aspects of biological molecules. In general, progress in peptide synthesis has lagged far behind that in amino acid sequence determination. This is not surprising since effective peptide synthesis requires a very sophisticated system of selectively removable protecting groups for functions of the amino acids involved, and the synthesis of a large heteropolytner of defined sequence requires near perfection of each one of the many steps of the assembly. The classical approach to peptide synthesis, using standard organic chemical methods of synthesis and purification of intermediates, has yielded impressive results during these two decades. However, the special problems associated with the assembly of large molecules make staggering investments in time and materials necessary for the synthesis of large peptides or proteins by classical methods.     

Examination of Template Structural Effects on CEC Chiral Separation Performance of Molecule Imprinted Polymers Made by a Generalized Preparation Protocol

Some acidic chiral templates were used to prepare open tubular (OT) molecule imprinted polymer (MIP) capillary columns to explore the effects of molecular structures of templates on chiral recognition capabilities and to verify the feasibility of the general MIP preparation protocol introduced in the previous study. The templates are phenyl carboxylic acids and their derivatives. Optimization was carried out for chiral separation of template enantiomers for each MIP column through varying pH and composition of eluent. It was found that the preparation protocol can be successfully applied for the appropriate templates with functional groups fulfilling the three-points interaction rule. The chiral separation performances were quite satisfactory for MIPs of such templates although they are yet inferior to the separation performances of the MIP columns fabricated with the templates of profen drugs (2-arylpropionic acids with a large substituent on the phenyl ring). Subtle variations of the template molecular structures have been found to be critical to enhance chiral recognition ability of the resultant MIP column.     

Measurement of trihalomethanes and methyl tertiary-butyl ether in tap water using solid-phase microextraction GC-MS

The prevalence of water disinfection byproducts in drinking water supplies has raised concerns about possible health effects from chronic exposure to these compounds. To support studies exploring the relation between exposure to trihalomethanes (THMs) and health effects, we have developed an automated analytical method using headspace solid-phase microextraction coupled with capillary gas chromatography and mass spectrometry. This method quantitates trace levels of THMs (chloroform, bromodichloromethane, dibromochloromethane, and bromoform) and methyl tertiary-butyl ether in tap water. Detection limits of less than 100 ng/L for all analytes and linear ranges of three orders of magnitude are adequate for measuring the THMs in tap water samples tested from across the United States. THMs are stable for extended periods in tap water samples after quenching of residual chlorine and buffering to pH 6.5, thus enabling larger epidemiologic field studies with simplified sample collection protocols.     

Europium(III) macrocyclic complexes with alcohol pendant groups as chemical exchange saturation transfer agents

Paramagnetic lanthanide(III) complexes that contain hyperfine-shifted exchangeable protons offer considerable advantages over diamagnetic molecules as chemical exchange saturation transfer (CEST) agents for MRI. As part of a program to investigate avenues to improve the sensitivity of such agents, the CEST characteristics of europium(III) macrocyclic complexes having appended hydroxyethyl groups were investigated. The CEST spectrum of the asymmetrical complex, EuCNPHC3+, shows five distinct peaks for each magnetically nonequivalent exchangeable proton in the molecule. The CEST spectra of this complex were fitted to NMR Bloch theory to yield exchange rates between each of six exchanging proton pools (five on the agent plus bulk water). Exchange between the Eu3+-bound hydroxyl protons and bulk water protons was slow in dry acetonitrile but accelerated incrementally upon stepwise addition of water. In pure water, exchange was too fast to observe a CEST effect. The utility of this class of europium(III) complex for CEST imaging applications is ultimately limited by the small chemical shifts induced by the hydroxyl-appended ligands of this type and the resulting small Deltaomega values for the exchangeable hydroxyl protons.     

Prediction of gas tungsten arc welding properties in mixtures ofargon and hydrogen

A theory of gas tungsten arc welding (GTAW) arcs that treats the tungsten electrode, the arc, and the workpiece as a unified system has been applied to make predictions in two dimensions of the temperature distributions in the arc, the tungsten cathode, and the workpiece, for any given arc current and gas mixture. Predictions of arc temperatures, radii, and voltages are compared for argon and mixtures of argon and hydrogen. It is found that arcs in gas mixtures containing hydrogen are more constricted and have a higher maximum temperature and arc voltage than arcs in pure argon. The addition of hydrogen also significantly increases the volume of molten material in the weld pool due to the higher thermal conductivity of argon-hydrogen mixtures at temperatures at which molecules of hydrogen dissociate. Predictions are also compared for workpieces of steel and aluminum. The volume of molten material is very much less for aluminum, despite its lower melting point, because of the higher thermal conductivity of aluminum. Predicted arc voltages as a function of current for a mixture of 10% hydrogen in argon are in good agreement with experimental results     

Simulation calculation of dielectric constants: Comparison of methods on an exactly solvable model

A mean spherical model of classical dipoles on a simple cubic lattice of sideM=2N+1 sites is considered. Exact results are obtained for finite systems using periodic boundary conditions with an external dielectric constant and using reaction field boundary conditions with a cutoff radiusR _c N and an external dielectric constant. The dielectric constant in the disordered phase is calculated using a variety of fluctuation formulas commonly implemented in Monte Carlo and molecular dynamics simulations of dipolar systems. The coupling in the system is measured by the parametery=4 ²/9kT, where ² is the fixed mean square value of the dipole moments on the lattice. The system undergoes a phase transition aty2.8, so that very high dielectric constants cannot be obtained in the disordered phase. The results show clearly the effects of system size, cutoff radius, external dielectric constant, and different measuring techniques on a dielectric constant estimate. It is concluded that with periodic boundary conditions, the rate of approach of the dielectric constant estimate to its thermodynamic limit is asN ^–2/3 and depends only weakly on. Methods of implementing reaction field boundary conditions to give rapid convergence to the thermodynamic limit are discussed.     

Photochemical Characteristics of the mode-locking dyes 1,1′-diethyl-4,4′ carbocyanine iodide (cryptocayanine,DCI) and 1,1′-diethyl-2,2′ dicarb

The fluorescence quantum efficiencies, lifetimes and triplet—triplet absorption spectra of the cyanine dyes DCI