Solid-phase ATRP synthesis of peptide-polymer hybrids

A versatile methodology to prepare hybrid biomaterials by atom transfer radical polymerization from resin-supported peptides has been established. As an example, we have synthesized a GRGDS-functionalized poly(2-hydroxyethyl methacrylate). The peptide-polymer was characterized by solid-state (13)C NMR and GPC and found to have a number average molecular weight of 4420 and a polydispersity of 1.47. These values are comparable to those obtained from solution-phase syntheses, suggesting the ATRP reaction is successful from a peptide-conjugated solid support. Solid-state (13)C NMR was used to characterize multiple steps in the reaction, and the synthesis was found to be near quantitative. We have performed cell adhesion experiments and observed the GRGDS sequence-promoted cell adhesion, whereas unfunctionalized poly(2-hydroxyethyl methacrylate) did not. By incorporating cell-signaling moieties in materials with defined molecular architecture, it will be possible to control the interactions between polymeric materials and biological systems.     

Fundamental amplitude noise limitations to supercontinuum spectra generated in a microstructured fiber

Broadband supercontinuum spectra are generated in a microstructured fiber using femtosecond laser pulses. Noise properties of these spectra are studied through experiments and numerical simulations based on a generalized stochastic nonlinear Schrödinger equation. In particular, the relative intensity noise as a function of wavelength across the supercontinuum is measured over a wide range of input pulse parameters, and experimental results and simulations are shown to be in good quantitative agreement. For certain input pulse parameters, amplitude fluctuations as large as 50% are observed. The simulations clarify that the intensity noise on the supercontinuum arises from the amplification of two noise inputs during propagation – quantum-limited shot noise on the input pulse, and spontaneous Raman scattering in the fiber. The amplification factor is a sensitive function of the input pulse parameters. Short input pulses are critical for the generation of very broad supercontinua with low noise. PACS 42.50.Lc; 42.65.Re; 42.81.Dp; 02.60.CbAn Erratum to this article can be found at     

Concise formal synthesis of (-)-peduncularine via ring-closing metathesis

[reaction: see text] A synthesis of the 6-aza[3.2.1]bicyclooctene (-)-2 has been completed by a short sequence of reactions that required only six operations from (S)-malic acid and featured a novel ring-closing metathesis to form the bridged bicyclic ring. Because 2 was previously converted into (-)-peduncularine (1), its preparation constitutes a formal enantioselective synthesis of 1.     

Parameter optimization and calibration of 19F magnetic resonance imaging at 1.5 Tesla

Fluorine-19 magnetic resonance imaging is limited by the fact that acquisition times are long and that high concentrations must be used in order to obtain good signal to noise. A significant improvement in signal to noise ratio may be brought about by the addition of Gd-DTPA, a paramagnetic agent which shortens T1. Images of phantoms containing trifluoroacetic acid (TFA) doped with Gd-DTPA were obtained using a standard spin echo sequence in a 1.5 T field. Interpulse times (TR and TE) and Gd-DTPA concentrations were optimized to yield maximum signal to noise ratios. The use of fast-field-echo scans to image fluorine is also demonstrated. Signal averaging successive FFE scans yields good signal to noise and resolution and may find clinical applicability in imaging areas subject to motion.     

Propagator resolved transverse relaxation exchange spectroscopy

We present in this communication a novel propagator-resolved transverse relaxation exchange experiment. This experiment enhances the previous technique of transverse relaxation exchange by enabling spatial resolution. Hence, we are able to obtain separate, and remarkably different, T2-T2 exchange plots, corresponding to different spatial displacement of the spin bearing water molecules in a porous sand matrix. This experiment is the first to combine two inverse Laplace dimensions with a Fourier dimension, opening the door to a host of new experiments combining Fourier and inverse Laplace spectroscopy.