One simple modification of existing external fixation equipment has allowed a new halo-pelvic device to be constructed and used effectively to immobilize the spine.
Solution-phase ion-polymer interactions between polyethylene glycols) (PEG's) and alkali metal ions (in glycerol) were studied by electrohydrodynamic ionization mass spectrometry. Metal complexes of different oligomers (with degree of polymerization (n) as low as 4) were resolved. Mass spectral intensities of these complex ions supported the prediction of multiple-ion association by larger oligomers. The minimum n required for this multiple-ion association correlated positively with the size of the metal ion. In EH mass spectra of glycerol solutions containing PEG and more than one metal ion, preferential complexation by the PEG oligomers for one metal over another was observed. From the total spectral intensities of each metal complex, bulk selectivity of PEG for alkali metal ions was found to follow the order K+ > Cs+ > Rb+ > Na+ > Li+ (1:0.94:0.79:0.46:0.08). These findings generally agreed with studies by other methods, although detection of lithium-PEG adducts has apparently not been previously reported in protic solvents.
Electrohydrodynamic ionization mass spectrometry was applied to the analysis of poly(ethy1ene glycols) of number-average molecular weights 406,605, 1041, and 1396 (determined by end-group titration). Spectra were obtained from glycerol solutions of each polymer, using NaI as supporting electrolyte. Singly, doubly, and triply charged ion series were detected, corresponding to attachment of one, two, or three sodium ions to oligomer molecules. Ions of low intensity attributable to protonated oligomers were also detected in the lighter samples. No evidence of significant fragmentation was obtained. Molecular weight distributions calculated from mass spectra could be used to obtain estimates of number-average molecular weights in excellent agreement with end-group-titration determinations. In addition to molecular weight information, the spectra also provided estimates of the level of vinyl, methylene, and propylene impurities in the sample.Both average molecular weight and molecular weight distribution are among the physical properties which determine whether a given polymer is suitable for a certain application. Sensitivity of bulk behavior to these parameters, and also to the presence of low-level impurities, can be extreme. The resultant need for characterization of the degree of polymerization in many systems has promoted the development of a variety of analytical techniques for determining polymer molecular weights.End-group titration is probably the most reliable method for absolute determination of number-average molecular weight, MnIn eq 1 Ni is the number of moles of molecules of molecular weight M , contained in a polymer sample. Titrations give no information about molecular weight distributions. Furthermore, the measured average can be spuriously lowered for branched polymers with multiple end groups.The only common technique which routinely provides both weight-average and weight-distribution information is gel permeation chromatography (GPC). Recent developments in "high-performance'' GPC (see, for example, ref 1 and 2) have extended its applicability to relatively low-molecular-weight samples. However, resolution falls quickly with increasing molecular weight, requiring multiple-column, time-consuming experiments for characterization of a broadly distributed sample. In addition, molecular weight standards of near monodispersity are usually required for good quantitation. Even when such standards are available, morphological differences between samples and standards (e.g., different branching or conformation) may shift molecular weight calibration. The need for calibration standards can be relieved by use of low-angle laser light scattering (LALLS) detection of the GPC effluenta3 However, this technique measures instantaneous average effluent molecular weight and requires efficient chromatographic separation for accurate determination of molecular weight distributions. Furthermore, calculation of molecular weights from scattering data requires prior knowledge of sample virial coefficients and "refracti...
A stable isotope-labeled drug method was used to determine the absolute bioavailability and absorption kinetics of a transdermal nicotine-delivery system (TTS). TTSs are being developed as an adjunct to smoking-cessation therapy. Deuterium-labeled nicotine was infused for 24 hours simultaneously to TTS application in cigarette-abstinent smokers. In 11 subjects with good patch adhesion, an average systemic dose of 19 mg nicotine was delivered, with average absolute bioavailability of 82%. The rate of nicotine absorption was maximal between 6 and 12 hours after TTS application and declined thereafter, plateauing between 16 and 24 hours at 62% of the maximal rate. Ten percent of nicotine was absorbed after the TTS was removed, demonstrating a reservoir for nicotine in the skin. Our study demonstrates the applicability of stable isotope methods in understanding the clinical pharmacology of transdermal drugs.
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