Rigid Rod-like Viscoelastic Behaviors of Methyl Cellulose Samples with a Wide Range of Molar Masses Dissolved in Aqueous Solutions.

The viscoelastic behaviors of aqueous solutions of commercially available methyl cellulose (MC) samples with a degree of substitution of 1.8 and a wide range of weight average molar masses (Mw) were investigated over a wide concentration (c) range at some temperatures from -10 to 25 °C. The viscoelastic parameters useful to discuss the structure and dynamics of MC-forming particles in aqueous solutions were precisely determined, such as the zero-shear viscosity (η0), the steady-state compliance (Je), the average relaxation time (τw), and the activation energy (E*) of τw. Because previously obtained scattering and intrinsic viscosity ([η]) data revealed that the MC samples possess a rigid rod-like structure in dilute aqueous solutions over the entire Mw range examined, the viscoelastic data obtained in this study were discussed in detail based on the concept of rigid rod particle suspension rheology. The obtained Je-1 was proportional to the number density of sample molecules (ν = cNAMw-1, where NA means the Avogadro's constant) over the ν range examined irrespective of Mw. The reduced relaxation time (4NAτw(3νJe [η]ηmMw)-1), where ηm means the medium viscosity, was proportional to (νL3)2, L; the average particle length depending on Mw for each sample was determined in a previous study; and the reduced specific viscosity (ηspNAL3(Mw [η])-1), where ηsp means the specific viscosity, was proportional to (νL3)3 in a range of νL3 < 3 × 102. These findings were typical characteristics of the rigid rod suspension rheology. Therefore, the MC samples behave as entangling rigid rod particles in the νL3 range from rheological points of view. A stepwise increase in E* was clearly observed in a c range higher than the [η]-1 value irrespective of Mw. This observation proposes that contact or entanglement formation between particles formed by MC molecules results in an increase in E*.

Enabling Pd Catalytic Selectivity via Engineering Intermetallic Core@Shell Structure.

Core@shell nanoparticles (NPs) have been widely explored to enhance catalysis due to the synergistic effects introduced by their nanoscale interface and surface structures. However, creating a catalytically functional core@shell structure is often a synthetic challenge due to the need to control the shell thickness. Here, we report a one-step synthetic approach to core-shell CuPd@Pd NPs with an intermetallic B2-CuPd core and a thin (∼0.6 nm) Pd shell. This core@shell structure shows enhanced activity toward selective hydrogenation of Ar-NO2 and allows one-pot tandem hydrogenation of Ar-NO2 to Ar-NH2 and its condensation with Ar-CHO to form Ar-N═CH-Ar. DFT calculations indicate that the B2-CuPd core promotes the Pd shell binding to Ar-NO2 more strongly than to Ar-CHO, thereby selectively activating Ar-NO2. The chemoselective catalysis demonstrated by B2-CuPd@Pd can be extended to a broader scope of substrates, allowing green chemistry synthesis of a wide range of functional chemicals and materials.

Nanofibers Produced by Electrospinning of Ultrarigid Polymer Rods Made from Designed Peptide Bundlemers.

Mimicking the hierarchical assembly of natural fiber materials is an important design challenge in the manufacturing of nanostructured materials with biomolecules such as peptides. Here, we produce nanofibers with control of structure over multiple length scales, ranging from peptide molecule assembly into supramolecular building blocks called "bundlemers," to rigid-rod formation through a covalent connection of bundlemer building blocks, and, ultimately, to uniaxially oriented fibers made with the rigid-rod polymers. The peptides are designed to physically assemble into coiled-coil bundles, or bundlemers, and to covalently interact in an end-to-end fashion to produce the rigid-rod polymer. The resultant rodlike polymer exhibits a rigid, cylindrical nanostructure confirmed by transmission electron microscopy (TEM) and, correspondingly, exhibits shear-thinning behavior at low shear rates observed in many nanoscopic rod systems. The rigid-rod chains are further organized into final fiber materials via electrospinning processing, all the while preserving their unique rodlike structural characteristics. Morphological and structural investigations of the nanofibers through scanning electron microscopy, transmission electron microscopy, and X-ray scattering, as well as molecular characterization via Fourier transform infrared (FTIR) and Raman spectroscopy, show that continuous nanofibers are composed of oriented rigid-rod chains constituted by α-helical peptides within bundle building blocks. Mechanical properties of electrospun fibers are also presented. The ability to produce nanofibers from the oriented rigid-rod polymer reveals bundlemer chains as a viable tool for the development of new fiber materials with targeted structure and properties.

Multi-axis alignment of Rod-like cellulose nanocrystals in drying droplets.

HYPOTHESIS: Radial capillary flow in evaporating droplets carry suspended nanoparticles to its periphery where they are deposited and form a coffee-ring. Rod-like nanoparticles seeking to minimize their capillary energy will align with their long-axis parallel to the contact line. Particles exhibiting electrostatic repulsion, such as cellulose nanocrystals (CNCs), establish a competition between capillary flow-induced impingement against a growing coffee-ring and entropic minimization leading to enhanced particle mobility. Therefore, balancing these effects by manipulating the local particle concentration in drying droplets should result in deposition with a controlled orientation of CNCs. EXPERIMENTS: The dynamic local order in aqueous suspensions of CNCs in evaporating sessile droplets was investigated through time-resolved polarized light microscopy. The spatial distribution of alignment in deposited CNCs was explored as a function of nanoparticle concentration, droplet volume, initial degree of anisotropy, and substrate hydrophobicity. Computational analysis of the rotational Péclet number during evaporation was also investigated to evaluate any effects of shear-induced alignment. FINDINGS: Multiple modes of orientation were identified suggesting local control over CNC orientation and subsequent properties can be attained via droplet-based patterning methods. Specifically, high local particle concentrations led to tangential alignment and lower local particle concentrations resulted in new evidence for radial alignment near the center of dried droplets.

On the Cluster Formation of α-Synuclein Fibrils.

The dense accumulation of α-Synuclein fibrils in neurons is considered to be strongly associated with Parkinson's disease. These intracellular inclusions, called Lewy bodies, also contain significant amounts of lipids. To better understand such accumulations, it should be important to study α-Synuclein fibril formation under conditions where the fibrils lump together, mimicking what is observed in Lewy bodies. In the present study, we have therefore investigated the overall structural arrangements of α-synuclein fibrils, formed under mildly acidic conditions, pH = 5.5, in pure buffer or in the presence of various model membrane systems, by means of small-angle neutron scattering (SANS). At this pH, α-synuclein fibrils are colloidally unstable and aggregate further into dense clusters. SANS intensities show a power law dependence on the scattering vector, q, indicating that the clusters can be described as mass fractal aggregates. The experimentally observed fractal dimension was d = 2.6 ± 0.3. We further show that this fractal dimension can be reproduced using a simple model of rigid-rod clusters. The effect of dominatingly attractive fibril-fibril interactions is discussed within the context of fibril clustering in Lewy body formation.

Determination of the Orientation of Pendants on Rigid-Rod Polymers.

Bis-norbornene and bis-cyclobutene with different kinds of linkers have been extensively used for the synthesis of double stranded ladderphanes under ruthenium- or molybdenum-catalyzed ring opening metathesis polymerization (ROMP) conditions. The key to the success relies on the selective formation of comb-like polynorbornenes or polycycloubtenes, where pendants are all aligned towards similar direction. This minireview summarizes various methods (chemical methods, spectroscopic means, and nonlinear optical measurements) for determining the comb-like conformations of pendants on these rigid-rod polymers. The approach is based on the proximal relationship between adjacent pendants. Interactions between these adjacent pendants would enable a change in chemical reactivity.

Highly Conductive and Thermally Stable Ion Gels with Tunable Anisotropy and Modulus.

A new liquid-crystalline ion gel exhibits unprecedented properties: conductivity up to 8 mS cm(-1) , thermal stability to 300 °C, and electrochemical window to 6.1 V, as well as adjustable transport anisotropy (up to 3.5×) and elastic modulus (0.03-3 GPa). The combination of ionic liquid and magnetically oriented rigid-rod polyanion provides widely tunable properties for use in diverse electrochemical devices.

Rods in spinal surgery: a review of the literature.

BACKGROUND CONTEXT: Spinal instrumentation has been used for more than five decades. Since the introduction of the Harrington rod in 1962, new rod materials and concepts have been developed. Rigid rod fixation has achieved higher fusion rates than previous methods. Recently, semirigid rod fixation devices have been used for both dynamic stabilization and fusion fixation. Memory rods, which have an interesting ability to return to their pre-bent shape when the temperature increases, are expected to be used for scoliosis correction. PURPOSE: To review the previous literature regarding biofunctionality and biocompatibility of rods in spinal surgery. CONCLUSION: The properties of each type of rod need to be taken into consideration when performing spinal instrumentation surgery.