Ultrasonication In Solution Research Articles

A Thermally Stable SO2-Releasing Mechanophore: Facile Activation, Single-Event Spectroscopy, and Molecular Dynamic Simulations.

Polymers that release small molecules in response to mechanical force are promising candidates as next-generation on-demand delivery systems. Despite advancements in the development of mechanophores for releasing diverse payloads through careful molecular design, the availability of scaffolds capable of discharging biomedically significant cargos in substantial quantities remains scarce. In this report, we detail a nonscissile mechanophore built from an 8-thiabicyclo[3.2.1]octane 8,8-dioxide (TBO) motif that releases one equivalent of sulfur dioxide (SO2) from each repeat unit. The TBO mechanophore exhibits high thermal stability but is activated mechanochemically using solution ultrasonication in either organic solvent or aqueous media with up to 63% efficiency, equating to 206 molecules of SO2 released per 143.3 kDa chain. We quantified the mechanochemical reactivity of TBO by single-molecule force spectroscopy and resolved its single-event activation. The force-coupled rate constant for TBO opening reaches ∼9.0 s-1 at ∼1520 pN, and each reaction of a single TBO domain releases a stored length of ∼0.68 nm. We investigated the mechanism of TBO activation using ab initio steered molecular dynamic simulations and rationalized the observed stereoselectivity. These comprehensive studies of the TBO mechanophore provide a mechanically coupled mechanism of multi-SO2 release from one polymer chain, facilitating the translation of polymer mechanochemistry to potential biomedical applications.

Thermally conductive composites with hydroxylated boron nitrides for the efficient thermal management of superconducting coils

The thermal conductivity (κ) of polymer nanocomposites with boron nitride (BN) nanoplates is critically dependent on the distribution of BN in the polymer matrix. Here, we heavily functionalized BN nanoplates with hydroxyl groups by ultrasonication in solution with boric acid. Then, the hydroxylated BN nanoplates could be homogeneously distributed in an epoxy matrix, which improved the through-plane κ of 2.09 and 1.96 W/m·K at 25 and -90 °C, respectively. Processable composite resin with hydroxylated BN was utilized as an adhesive for a low-temperature superconducting (LTS) coil to enhance its normal zone propagation velocity (NZPV) and cooling rate performance. Consequently, fast heat dissipation through the adhesive between superconductors contributed to a 65.8% of increase in NZPV and a 13.1% improvement in the cooling rate of the device compared with a commercial adhesive.

Detection of <I>K</I>-Ras Oncogene from the Human Genomic DNA Using Ultrasonication and a Quantum Dots-Based Microfluidic Chip

In clinical diagnostics, single-stranded DNAs (ssDNA) have been prepared from the human genomic DNA for the detection of a specific gene. In this study, the human genomic DNA was degraded via ultrasonication in solution, and K-ras oncogene was detected from the DNA fragments via the fluorescence quenching of quantum dots (QDs) by intercalating dyes after hybridization of the target, to probe DNAs in a microfluidic chip. K-ras is one of the most activated common oncogenes, and many human tumors are known to be due to the mutation of this gene. QDs are nano-sized semiconductors with a wide selection of emission wavelengths and exceptional stability against photo bleaching. In this study, probe DNA-conjugated QDs were immobilized to polystyrene microbeads, and the DNA-microbead-QDs complexes were packed through a microchannel by pillars that trap the beads in the microfluidic chip. The fluorescence of the QDs could be quenched by intercalating dye (TOTO-3) after hybridization of K-ras oncogene to the probe DNA in the channel. The fluorescence intensity decrease of the QDs can be used as an indication of the K-ras oncogene. By introducing an alkaline buffer solution, the DNAs were denatured, and the fluorescence intensity of the QDs again increased, which shows the possibility of reuse of the microfluidic chip for the detection of the K-ras gene.

Polymer reinforcement using liquid-exfoliated boron nitride nanosheets

We have exfoliated hexagonal boron nitride by ultrasonication in solutions of polyvinylalcohol in water. The resultant nanosheets are sterically stabilised by adsorbed polymer chains. Centrifugation-based size-selection was used to give dispersions of nanosheets with aspect ratio (length/thickness) of ∼1400. Such dispersions can be used to produce polyvinylalcohol-BN composite films. Helium ion microscopy of fracture surfaces shows the nanosheets to be well dispersed and the composites to fail by pull-out. We find both modulus, Y, and strength, σ(B), of these composites to increase linearly with volume fraction, V(f), up to V(f)∼ 0.1 vol% BN before falling off. The rates of increase are extremely high; dY/dV(f) = 670 GPa and dσ(B)/dV(f) = 47 GPa. The former value matches theory based on continuum mechanics while the latter value is consistent with remarkably high polymer-filler interfacial strength. However, because the mechanical properties increase over such a narrow volume fraction range, the maximum values of both modulus and strength are only ∼40% higher than the pure polymer. This phenomenon has also been observed for graphene-filled composites and represents a serious hurdle to the production of high performance polymer-nanosheet composites.

Mechanical Activation of Catalysts for C−C Bond Forming and Anionic Polymerization Reactions from a Single Macromolecular Reagent

Coupling of pyridine-capped poly(methyl acrylate)s, PyP(M) (where M corresponds to the number average molecular weight in kDa), to the SCS-cyclometalated dipalladium complex [(1)(CH(3)CN)(2)] afforded organometallic polymers [(1)(PyP(M))(2)] with a concomitant doubling in molecular weight. Ultrasonication of solutions containing [(1)(PyP(M))(2)] effected the mechanical scission of a palladium-pyridine bond, where the liberated PyP(M) was trapped with excess HBF(4) as the corresponding pyridinium salt, harnessed to effect the stoichiometric deprotonation of a colorimetric indicator, or used to catalyze the anionic polymerization of α-trifluoromethyl-2,2,2-trifluoroethyl acrylate. The mechanically induced chain scission also unmasked a catalytically active palladium species which was used to facilitate carbon-carbon bond formation between benzyl cyanide and N-tosyl imines. Spectroscopic and macromolecular analyses as well as a series of control experiments demonstrated that the aforementioned structural changes were derived from mechanical forces that originated from ultrasound-induced dissociation of the polymer chains connected to the aforementioned Pd complexes.

Supergrowth of Aligned Carbon Nanotubes Directly on Carbon Papers and Their Properties as Supercapacitors

We demonstrate that vertically aligned carbon nanotubes can be synthesized directly on conductive carbon papers and used as excellent electrochemical capacitors. The carbon nanotubes were synthesized with use of an Al/Fe catalyst via water-assisted chemical vapor deposition. They grew as fast as ∼100 μm/min and approximately 70% of them had double walls with an average diameter of ∼6 nm. Interestingly, the carbon nanotube forest showed microscale patterns defined by the structure of underlying carbon papers. The nanotubes were attached well to the carbon papers and maintained their adhesion under mild ultrasonication in solution. Owing to the direct integration, naturally patterned structure, and good alignment, the carbon nanotubes showed excellent performance as supercapacitors. In aqueous 1 M H2SO4 solution, specific capacitance, energy, and power measured at the current density of 20 A/g were ca. 200 F/g, 20 Wh/kg, and 40 kW/kg, respectively. A specific energy of >100 Wh/kg was achieved when organic e...