Two speeches, by Frederick Douglass; : one on West India emancipation, delivered at Canandaigua, Aug. 4th, and the other on the Dred Scott decision, delivered in New York, on the occasion of the anniversary of the American Abolition Society, May, 1857.

"The Dred Scott decision: speech, delivered, in part, at the anniversary of the American Abolition Society, held in New York, May 14th, 1857" on pages [25]-46, with half title page.

An oration, delivered before the American Philosophical Society, held in Philadelphia on the 27th of February, 1786; containing an enquiry into the influence of physical causes upon the moral faculty ...

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Chemical and functional identification and characterization of novel sulfated alpha-conotoxins from the cone snail Conus anemone

An LC/MS analysis with diagnostic screening for the detection of peptides with posttranslational modifications revealed the presence of novel sulfated peptides within the -conotoxin molecular mass range in Conus anemone crude venom. A functional assay of the extract showed activity at several neuronal nicotinic acetylcholine receptors (nAChRs). Three sulfated alpha-conotoxins (AnIA, AnIB, and AnIC) were identified by LC/MS and assay-directed fractionation and sequenced after purification. The most active of these, alpha-AnIB, was further characterized and used to investigate the influence of posttranslational modifications on affinity. Synthetic AnIB exhibited subnanomolar potency at the rat alpha3/beta2 nAChR (IC50 0.3 nM) and was 200-fold less active on the rat alpha7 nAChR (IC50 76 nM). The unsulfated peptide [Tyr(16)]AnIB showed a 2-fold and 10-fold decrease in activities at alpha3beta2 (IC50 0.6 nM) and alpha7(IC50 836 nM) nAChR, respectively. Likewise, removal of the C-terminal amide had a greater influence on potency at the alpha7 (IC50 367 nM) than at the alpha3beta2 nAChR (IC50 0.5 nM). Stepwise removal of two N-terminal glycine residues revealed that these residues affect the binding kinetics of the peptide. Comparison with similar 4/7-alpha-conotoxin sequences suggests that residue 11 (alanine or glycine) and residue 14 (glutamine) constitute important determinants for alpha3beta2 selectivity, whereas the C-terminal amidation and sulfation at tyrosine-16 favor alpha7 affinity.

DOSY NMR studies of chemical exchange behavior of poly(2-hydroxyethyl methacrylate)

PFG-NMR was used to study the chemical exchange of linear PHEMA having a range of molecular weights with water in DMSO containing varying quantities of water. The aim was to investigate the use of PFG-NMR to study chemical exchange between a polymer with exchangeable protons and a small fast diffusing molecule to provide insight into the conformation adopted by a polymer in solution. The experimental data were simulated closely for the two-site exchange case using the Bloch equations modified for chemical exchange and diffusion. The exchange rate could be used to detect changes in polymer conformation resulting from changes in the solvent. PHEMA of MW 10 000 showed significant time-dependent changes in exchange rate, resulting from preferential solvation of the OH sites by water, and subsequent conformational changes which altered accessibility of the OH sites to water. This behavior was not observed for larger MW PHEMA, which adopted a stable conformation immediately. Large changes in the exchange rate were not reflected in changes to the hydrodynamic radius, suggesting that a minimal overall change in the chain dimensions occurred. DMSO was found to be a poor solvent for PHEMA, which adopts a compact conformation in DMSO. This work has demonstrated that PFG-NMR is a sensitive method for detecting subtle changes in polymer conformation in polymers with exchangeable protons.

True chemical shift correlation maps:a TOCSY experiment with pure shifts in both dimensions

Signal resolution in H NMR is limited primarily by multiplet structure. Recent advances in pure shift NMR, in which the effects of homonuclear couplings are suppressed, have allowed this limitation to be circumvented in 1D NMR, gaining almost an order of magnitude in spectral resolution. Here for the first time an experiment is demonstrated that suppresses multiplet structure in both domains of a homonuclear two-dimensional spectrum. The principle is demonstrated for the TOCSY experiment, generating a chemical shift correlation map in which a single peak is seen for each coupled relationship, but the principle is general and readily extensible to other homonuclear correlation experiments. Such spectra greatly simplify manual spectral analysis and should be well-suited to automated methods for structure elucidation. © 2010 American Chemical Society.

Magnetic resonance imaging of the manipulation of a chemical wave using an inhomogeneous magnetic field

The effects of applied magnetic fields on the traveling wave formed by the reaction of (ethylenediaminetetraacetato)cobalt(II) (Co(II)EDTA2-) and hydrogen peroxide have been studied using magnetic resonance imaging (MRI). It was found that the wave could be manipulated by applying pulsed magnetic field gradients to a sample contained in a vertical cylindrical tube in the 7.0 T magnetic field of the spectrometer. Transverse field gradients decelerated the propagation of the wave down the high-field side of the tube and accelerated it down the low-field side. This control of the wave propagation eventually promoted the formation of a finger on the low-field side of the tube and allowed the wave to be maneuvered within the sample tube. The origin of these effects is rationalized by considering the Maxwell stress arising from the combined homogeneous and inhomogeneous magnetic fields and the magnetic susceptibility gradient across the wave front.

Quantitative characterization of physico-chemical properties of the active layers of reverse osmosis and nanofiltration membranes, and their relation to membrane performance

The main objectives of this dissertation were: (i) to develop experimental and analytical procedures to quantify different physico-chemical properties of the ultra-thin (~ 100 nm) active layers of reverse osmosis (RO) and nanofiltration (NF) membranes and their interactions with contaminants; (ii) to use such procedures to evaluate the similarities and differences between the active layers of different RO/NF membranes; and (iii) to relate characterization results to membrane performance. Such objectives were motivated by the current limited understanding of the physico-chemical properties of active layers as a result of traditional characterization techniques having limitations associated with the nanometer-scale spatial resolution required to study these ultra-thin films. Functional groups were chosen as the main active layer property of interest. Specific accomplishments of this study include the development of procedures to quantify in active layers as a function of pH: (1) the concentration of both negatively and positively ionized functional groups; (2) the stoichiometry of association between ions (i.e., barium) and ionized functional groups (i.e., carboxylate and sulfonate); and (3) the steric effects experienced by ions (i.e., barium). Conceptual and mathematical models were developed to describe experimental results. The depth heterogeneity of the active layer physico-chemical properties and interactions with contaminants studied in this dissertation was also characterized. Additionally, measured concentrations of ionized functional groups in the polyamide active layers of several commercial RO/NF membranes were used as input in a simplified RO/NF transport model to predict the rejection of a strong electrolyte (i.e., potassium iodide) and a weak acid (i.e., arsenious acid) at different pH values based on rejection results at one pH condition. The good agreement between predicted and experimental results showed that the characterization procedures developed in this study serve as useful tools in the advancement of the understanding of the properties and structure of the active layers of RO/NF membranes, and the mechanisms of contaminant transport through them.