Facile RAFT precipitation polymerization for the microwave-assisted synthesis of well-defined, double hydrophilic block copolymers and nanostructured hydrogels

Water-soluble macromolecular chain transfer agents (Macro-CTAs) were developed for the microwave-assisted precipitation polymerization of N-isopropylacrylamide. Two types of Macro-CTAs, amphiphilic (Macro-CTA1) and hydrophilic (Macro-CTA2), were investigated regarding their activity for the facile formation of nanoparticles and double hydrophilic block copolymers by RAFT processes. While both Macro-CTAs functioned as steric stabilization agents, the variation in their surface activity afforded different levels of control over the resulting nanoparticles in the presence of cross-linkers. The cross-linked nanoparticles produced using the amphiphilic Macro-CTA1 were less uniform than those produced using the fully hydrophilic Macro-CTA2. The nanoparticles spontaneously formed core-shell structures with surface functionalities derived from those of the Macro-CTAs. In the absence of cross-linkers, both types of Macro-CTAs showed excellent control over the RAFT precipitation polymerization process with well-defined, double hydrophilic block copolymers being obtained. The power of combining microwave irradiation with RAFT procedures was evident in the high efficiency and high solids content of the polymerization systems. In addition, the "living" nature of the nanoparticles allowed for further copolymerization leading to multiresponsive nanostructured hydrogels containing surface functional groups, which were used for surface bioconjugation.     

One-step synthesis of large-aspect-ratio single-crystalline gold nanorods by using CTPAB and CTBAB surfactants

Gold nanorods were prepared in high yields by using a one-step seed-mediated process in aqueous cetyltripropylammonium bromide (CTPAB) and cetyltributylammonium bromide (CTBAB) solutions in the presence of silver nitrate. The diameters of the nanorods range from 3 to 11 nm, their lengths are in the range of 15 to 350 nm, and their aspect ratios are in the range of 2 to 70. The diameters of the Au nanorods obtained from one growth batch in CTPAB solutions decrease as their lengths increase, and their volumes decrease as the aspect ratios increase. The diameters of the Au nanorods obtained from one growth batch in CTBAB solutions first decrease and then slightly increase as their lengths increase, and their volumes increase as the aspect ratios increase. These Au nanorods are single-crystalline and are seen to be oriented in either the [100] or [110] direction under transmission electron microscopy imaging, irrespective of their sizes. To the best of our knowledge, this is the first report of the preparation by using wet-chemistry methods of single-crystalline Au nanorods with aspect ratios larger than 15.     

Microwave spectra of O(2)-HF and O(2)-DF: hyperfine interactions and global fitting with infrared data

Spectra of the open shell complexes O(2)-HF and O(2)-DF were recorded using Fourier transform microwave spectroscopy. A complete analysis of the hyperfine structure and a global fit including microwave and infrared frequencies [W. M. Fawzy, C. M. Lovejoy, D. J. Nesbitt, and J. T. Hougen, J. Chem. Phys. 117, 693 (2002)] are reported. The Fermi contact interaction between the electron and nuclear spins, the electron spin-nuclear spin dipolar interaction, the nuclear spin-nuclear spin dipolar interaction, and the nuclear electric quadrupole interaction (for O(2)-DF) were considered in the analysis. The correspondence between the magnetic hyperfine constants and the two nuclei of the H(D)F is unambiguously established. In both O(2)-HF and O(2)-DF, the Fermi contact parameter is larger for the fluorine than for the hydrogen, while for the nuclear spin-electron spin dipolar hyperfine constants, the reverse is true. The effective angle between the HF bond and the a axis of the complex, determined from the nuclear spin-nuclear spin interaction constant, is 38(4) degrees. The same angle for the DF complex, derived from the deuterium nuclear quadrupole coupling constant, is 31(4) degrees.     

High throughput screening and measurements of proton conductivity of newly developed PEM materials based on proton transport visualization

An electrochemical method for proton transport visualization was developed and applied to the investigation of proton-conducting membrane materials. The method employs the change in the visual appearance of chemo-chromic tungsten oxide WO₃ in the presence of atomic hydrogen. An all-solid electrochemical cell arranged by substituting a fuel cell cathode with a thin film of WO₃-electrode was built and shown to generate both optical and electrical response to hydrogen gas exposure. The design of the cell was extended to a high throughput screening system that was utilized to characterize proton transport properties of samples, including a number of new compounds synthesized in-house by sol–gel wet chemistry. Non-destructive introduction of superacidic groups promoting proton hopping in the membrane materials was achieved by photodecomposition of a photoacid generator just after membrane casting. A model quantitatively describing current–voltage relation in the cell was developed and successfully applied to derive area-specific resistance of proton-conductive membranes from the experimental results. Area-specific resistances of membranes are derived from the slopes of optically reconstructed voltage–current curves. Sensitivity and dynamic range of the screening method are discussed.     

A general synthetic strategy for oxide-supported metal nanoparticle catalysts

Despite recent exciting progress in catalysis by supported gold nanoparticles, there remains the formidable challenge of preparing supported gold catalysts that collectively incorporate precise control over factors such as size and size-distribution of the gold nanoparticles, homogeneous dispersion of the particles on the support, and the ability to utilize a wide range of supports that profoundly affect catalytic performance. Here, we describe a synthetic methodology that achieves these goals. In this strategy, weak interface interactions evenly deposit presynthesized organic-capped metal nanoparticles on oxide supports. The homogeneous dispersion of nanoparticles on oxides is then locked in place, without aggregation, through careful calcination. The approach takes advantage of recent advances in the synthesis of metal and oxide nanomaterials and helps to bring together these two classes of materials for catalysis applications. An important feature is that the strategy allows metal nanoparticles to be well dispersed on a variety of oxides with few restrictions on their physical and chemical properties. Following this synthetic procedure, we have successfully developed efficient gold catalysts for green chemistry processes, such as the production of ethyl acetate from the selective oxidation of ethanol by oxygen at 100 degrees C.     

Performance of cryogenic probes as a function of ionic strength and sample tube geometry

The pursuit for more sensitive NMR probes culminated with development of the cryogenic cooled NMR probe. A key factor for the sensitivity is the overall resistance of RF circuitry and sample. Lowering the coil temperature to approximately 25 K and the use of superconducting coil material has greatly reduced the resistance contribution of the hardware. However, the resistance of a salty sample remains the same and evolves as the major factor determining the signal-to-noise ratio. Several approaches have been proposed to reduce the resistance contribution of the sample. These range from encapsulating proteins in a water cavity formed by reverse micelles in low viscosity fluids to the optimal selection of low mobility, low conductivity buffer ions. Here we demonstrate that changing the sample diameter has a pronounced effect on the sample resistance and this results in dramatic improvements of the signal-to-noise ratio and shorter pi/2 pulses. We determined these parameters for common 5 mm NMR tubes under different experimental conditions and compared them to the 2, 3 and 4 mm tubes, in addition, 5mm Shigemi tubes were included since these are widely used. We demonstrate benefits and applicability of studying NMR samples with up to 4M salt concentrations in cryogenic probes. Under high salt conditions, best results in terms of short pi/2 pulses and high signal-to-noise ratios are obtained using 2 or 3mm NMR tubes, especially when limited sample is available. The 4 mm tube is preferred when sample amounts are abundant at intermediate salt conditions.     

Directly detected Mn MRI: Application to phantoms for human hyperpolarized C MRI development

In this work we demonstrate for the first time directly detected manganese-55 (⁵⁵Mn) magnetic resonance imaging (MRI) using a clinical 3 T MRI scanner designed for human hyperpolarized ¹³C clinical studies with no additional hardware modifications. Due to the similar frequency of the ⁵⁵Mn and ¹³C resonances, the use of aqueous permanganate for large, signal-dense, and cost-effective “¹³C” MRI phantoms was investigated, addressing the clear need for new phantoms for these studies. Due to 100% natural abundance, higher intrinsic sensitivity, and favorable relaxation properties, ⁵⁵Mn MRI of aqueous permanganate demonstrates dramatically increased sensitivity over typical ¹³C phantom MRI, at greatly reduced cost as compared with large ¹³C-enriched phantoms. A large sensitivity advantage (22-fold) was demonstrated. A cylindrical phantom (d = 8 cm) containing concentrated aqueous sodium permanganate (2.7 M) was scanned rapidly by ⁵⁵Mn MRI in a human head coil tuned for ¹³C, using a balanced steady state free precession acquisition. The requisite penetration of radiofrequency magnetic fields into concentrated permanganate was investigated by experiments and high frequency electromagnetic simulations, and found to be sufficient for ⁵⁵Mn MRI with reasonably sized phantoms. A sub-second slice-selective acquisition yielded mean image signal-to-noise ratio of ~ 60 at 0.5 cm³ spatial resolution, distributed with minimum central signal ~ 40% of the maximum edge signal. We anticipate that permanganate phantoms will be very useful for testing HP ¹³C coils and methods designed for human studies.     

Planar Groups

In abstract algebra courses, teachers are often confronted with the task of drawing subgroup lattices. For purposes of instruction, it is usually desirable that these lattices be planar graphs (with no crossings). We present a characterization of abelian groups with this property. We also resolve the following problem in the abelian case: if the subgroup lattice is required to be drawn hierarchically (that is, in monotonic order of index within the group), when is it possible to draw the lattice without crossings?