Capillary electrochromatography of peptides and proteins

This review surveys the accomplishments in the separation of peptides and proteins by capillary electrochromatography (CEC) over the last decade. A significant number of research articles have been published on this topic since the last review. Peptide and proteins separations have been carried out in all three formats of CEC, i.e., packed bed, continuous bed and open-tubular (OT) format. In addition to electrophoresis, different chromatographic modes have been successfully exploited with the most prevalent being reversed-phase mode followed by ion-exchange. Although many researchers continue to use model proteins and peptides primarily to evaluate the performance of novel stationary phases some researchers have also applied CEC to the analysis of real-life samples. The potential of CEC to yield complementary information and sometimes a superior separation with respect to established techniques, i.e., microbore HPLC and capillary electrophoresis has been demonstrated. Instrumental modifications in order to facilitate coupling of CEC to mass spectrometry have further upgraded the value of CEC for proteomic analysis. Capillaries are still the separation vehicle of choice for most researchers yet the microfluidic platform is gaining momentum, propelled particularly by its potential for multitasking, e.g., performing different chromatographic modes in series.     

Transition from Mott insulator to superconductor in GaNb4Se8 and GaTa4Se8 under high pressure

Electronic conduction in GaM4Se8 (M=Nb,Ta) compounds with the fcc GaMo4S8-type structure originates from hopping of localized unpaired electrons (S=1 / 2) among widely separated tetrahedral M4 metal clusters. We show that under pressure these systems transform from Mott insulators to a metallic and superconducting state with T(C)=2.9 and 5.8 K at 13 and 11.5 GPa for GaNb4Se8 and GaTa4Se8, respectively. The occurrence of superconductivity is shown to be connected with a pressure-induced decrease of the MSe6 octahedral distortion and simultaneous softening of the phonon associated with M-Se bonds.     

Coherence of acoustic modes propagating through shallow water internal waves

The 1995 Shallow Water Acoustics in a Random Medium (SWARM) experiment [Apel et al., IEEE J. Ocean. Eng. 22, 445-464 (1997)] was conducted off the New Jersey coast. The experiment featured two well-populated vertical receiving arrays, which permitted the measured acoustic field to be decomposed into its normal modes. The decomposition was repeated for successive transmissions allowing the amplitude of each mode to be tracked. The modal amplitudes were observed to decorrelate with time scales on the order of 100 s [Headrick et al., J. Acoust. Soc. Am. 107(1), 201-220 (2000)]. In the present work, a theoretical model is proposed to explain the observed decorrelation. Packets of intense internal waves are modeled as coherent structures moving along the acoustic propagation path without changing shape. The packets cause mode coupling and their motion results in a changing acoustic interference pattern. The model is consistent with the rapid decorrelation observed in SWARM. The model also predicts the observed partial recorrelation of the field at longer time scales. The model is first tested in simple continuous-wave simulations using canonical representations for the internal waves. More detailed time-domain simulations are presented mimicking the situation in SWARM. Modeling results are compared to experimental data.     

Dynamics of the electric field-assisted charge carrier photogeneration in ladder-type poly(para-phenylene) at a low excitation intensity

Electric field-assisted charge carrier photogeneration in a ladder-type methyl-substituted poly(paraphenylene) was investigated by ultrafast absorption spectroscopy at low excitation intensity. The dissociation of excitons into electron-hole pairs occurs from the vibrationally relaxed excited state throughout its lifetime and is caused by the applied electric field, rather than by existence of special "dissociation sites." These findings are of importance for material choice in device applications.     

Charge-transfer states in strongly coupled phthalocyanine fullerene ensembles

Fluorescence and transient absorption measurements show that in strongly coupled ZnPc-C60 and H2Pc-C60 dyads charge-separated states are formed; large -delta GCR degree and small lambda assist in stabilising ZnPc(.+)-C60.-/H2Pc(.+)-C60.-.     

Evaluation of a two-stage screening procedure in the combinatorial search for serine protease-like activity

A series of peptidosteroid derivatives containing two independent peptide chains in which Ser and His are incorporated were synthesized by solid-phase peptide synthesis. The activity of the different compounds in the hydrolysis of the activated substrate NF31 was assessed in a stepwise fashion. First, the different resin-bound derivatives 6a-l and 6x-z were individually assayed for serine esterification in the absence of water. The use of a colored substrate allowed for a visual identification of the most active compounds. Through the inclusion of control substances, the involvement of histidine in the mechanism for serine acylation was shown. Second, the hydrolysis and methanolysis of the different acylated derivatives 8a-l and 8x were evaluated using UV spectroscopy, again indicating the involvement of histidine. The feasibility of applying the above procedures in a combinatorial context was proven via the screening of artificial libraries, created by mixing the different resin-bound peptidosteroid compounds. In this respect, the use of a photocleavable linker allowed for the unambiguous structural characterization of the selected members via application of single-bead electrospray tandem mass spectrometry.     

Multisensitive polymers based on 2‐vinylpyridine and N‐isopropylacrylamide *

Poly(2‐vinylpyridine) (P2VP) containing functionalized end groups was synthesized using nitroxyl‐mediated radical polymerization with a hydroxy‐functionalized stable free radical. It was shown that P2VP could be synthesized with variable molar masses and low polydispersities. The transformation of the hydroxy groups to an acrylic ester led to the formation of macromonomers. A free‐radical copolymerization of these macromonomers with N‐isopropylacrylamide gave a graft copolymer with a poly(N‐ispopropylacrylamide) backbone and P2VP side chains. Polymers containing different amounts of the monomers were synthesized. It was possible to vary both the amount of P2VP side chains at a constant chain length of the macromonomer and the chain length at a nearly constant chain number. The behavior of the multifunctional macromolecules at different temperatures and pH values was investigated using dynamic light scattering and DSC. The macromolecules were found to retain the specific properties of the homopolymers. The hydrodynamic radii of the synthesized graft copolymers were both dependent on the temperature and pH value. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3797–3804, 2001