Development of Dissolved Oxygen Sensor Based on Time-domain Lifetime Measurement with a Sensing Film Fabricated by Embedding PtOEP in Highly Stable and Highly Hydrophobic Fluorinated Matrix.

A dissolved oxygen sensor was developed based on time-domain lifetime measurement with an oxygen sensing film. The oxygen sensing film was fabricated by embedding PtOEP in a highly stable and highly hydrophobic fluorinated matrix synthesized from methacrylate, fluorinated methacrylate, and 3-(tris(trimethylsilyloxy)silyl)propyl methacrylate via free radical polymerization. The fluorinated methacrylate provided the high stability and the 3-(tris(trimethylsilyloxy)silyl)propyl methacrylate provided the extra hydrophobicity. The PtOEP was excited using pulsed signals from a green-light LED and the fluorescence lifetime was evaluated by time-domain lifetime measurement. The dynamical quenching of fluorescence response by dissolved oxygen was calibrated using the Stern-Volmer plot with a high τ 0 / τ 100 ratio of 5.68 and a Stern-Volmer constant of 0.112 mg-1 dm3 . It was demonstrated that the dissolved oxygen sensing film showed high stability under the varied excitation intensity and long-term stability in the accelerated aging experiment and the repeated freeze-thaw-cycling tests.

Synthesis and Characterization of Poly(5'-hexyloxy-1',4-biphenyl)-b-poly(2',4'-bispropoxysulfonate-1',4-biphenyl) with High Ion Exchange Capacity for Proton Exchange Membrane Fuel Cell Applications.

Proton exchange membrane (PEM) is pivotal for proton exchange membrane fuel cells (PEMFCs). In the present work, a block copolymer with hydrophilic alkyl sulfonated side groups and hydrophobic flexible alkyl ether side groups, poly(5'-hexyloxy-1',4-biphenyl)-b-poly(2',4'-bispropoxysulfonate-1',4-biphenyl) (HBP-b-xBPSBP), is designed and synthesized by copolymerization of the hydrophilic and hydrophobic oligomers. The oligomers are synthesized via a Pd-catalyzed Suzuki cross-coupling of 1,3-dibromo-5-hexyloxybenzene, and 3,3'-[(4,6-dibromo-1,3-phenylene)bis(oxy)]bis(propane-1-sulfonate) or 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene. The good solubility and film-forming characteristics are achieved via the introduction of flexible hexyloxy side groups, and high ion exchange capacity (IEC) is achieved via the introduction of high density of alkyl sulfonated side groups. The HBP-b-0.5BPSBP has the highest IEC of 3.17 mmol/g, the highest proton conductivity of 43.5 mS/cm at 95 °C and 90% relative humidity (RH) and low methanol permeability of 6.45×10-7  cm2 /s. Meanwhile, crosslinked HBP-b-xBPSBP exhibits promising water uptake, swelling ratio and low methanol permeability. These characteristics are attributed to the crosslinked structure and the hydrophilic/hydrophobic nanophase separation morphology promoted by the poly(m-phenylene) main chains, flexible alkyl ether groups, and alkyl sulfonated side groups.

Sulfonation Mechanism of Polysulfone in Concentrated Sulfuric Acid for Proton Exchange Membrane Fuel cell Applications.

The sulfonated polysulfone is a competitive proton-conducting material for proton exchange membrane fuel cells because of its relatively low cost and adequate performance compared with the perfluorinated sulfonic acid ionomers. This material can be economically synthesized by postsulfonation of commercial polysulfone; however, the inadequate sulfonation degree and the chain-scission degradation during sulfonation prevent the further optimization of its overall performance. In this work, the sulfonation mechanism of polysulfone is studied in terms of the transition state and activation energy based on density functional theory calculations, and the optimization of sulfonation processing parameters are discussed.

Hydrogen generation from glucose catalyzed by organoruthenium catalysts under mild conditions.

Concerns about the depletion of fossil fuel reserves and environmental pollution make hydrogen an attractive alternative energy source. Here, we first describe a catalytic reaction system that produces H2 from glucose using a homogeneous catalyst [(p-cymene)Ru(NH3)]Cl2 with the maximum TOF = 719 h-1 at 98 °C and an initial pH = 0.5.

Coiled Plant Tendril Bioinspired Fabrication of Helical Porous Microfibers for Crude Oil Cleanup.

Fabrication of the helical fibers with sheath/core structure comprising 3D interconnected porous polystyrene (PS) and ductile polyvinylidene fluoride is inspired by coiled plant tendril. The key innovation point applied in this study is to produce a helical porous system based on sheath/core structure that can come into being a huge storage space in the sorption process for crude oil. More importantly, the mechanical properties confirm to have a more excellent improvement than that of the initial PS fibers, which make it become a possible candidate for the large-area sorption and reuse of crude oil from the ocean or industry. The bioinspired fabricating strategy opens a significant avenue between the coaxial electrospinning and crude oil contamination cleanup. It is also expected that the unique structure can make it a promising candidate for applications in energy conversion, tissue engineering, and intelligent devices.

Solubility and Stability of Baclofen 3 mg/mL Intrathecal Formulation and Its Compatibility With Implantable Programmable Intrathecal Infusion Systems.

BACKGROUND: Commercial baclofen formulations used with infusion pumps are available at therapeutic concentrations of 0.5-2.0 mg/mL. However, patients who receive higher daily doses of baclofen may benefit from products with greater baclofen concentrations since their refill frequency would be reduced (up to a maximum of 180 days). We evaluated baclofen solubility, baclofen 3 mg/mL intrathecal (IT) formulation stability, and chemical and physical compatibility with Medtronic SynchroMed® II and Codman Medstream® programmable IT infusion pumps. METHODS: For solubility evaluations, baclofen powder was dissolved into isotonic saline and tested at 5°C, 25°C, and 40°C. To demonstrate drug product stability, both physical and chemical stability attributes of baclofen 3 mg/mL in prefilled syringes were evaluated over 36 months with storage at 25°C. For a simulated in-use stability (compatibility) study, a 3 mg/mL baclofen IT formulation was placed in SynchroMed II and Codman Medstream pumps at 37ºC for study durations, and evaluated at different flow rates. Pump effluent was collected at various times and analyzed by high-performance liquid chromatography for baclofen content. On completion of the in-use stability study, pumps exposed to baclofen 3 mg/mL were dissected and visually evaluated for signs of deterioration. RESULTS: Baclofen solubility was found to be 3.2 mg/mL at 5°C, 3.6 mg/mL at 25°C, and 3.9 mg/mL at 40°C. During the 36-month stability study of prefilled syringes stored at 25°C, baclofen content remained unchanged and no precipitation was observed. The simulated in-use pump study performed at 37ºC showed that a baclofen 3 mg/mL IT formulation was stable at different flow rates and throughout different expected residence times for both pump models. Components from both pumps exhibited no noticeable deterioration after exposure to the 3 mg/mL formulation. CONCLUSION: Baclofen 3 mg/mL IT formulation was stable during long-term storage at 25°C and remained stable under conditions matching those encountered in clinical practice (37°C).

Massively Screening the Temporal Spectra of Single Nanoparticles to Uncover the Mechanism of Nanosynthesis.

Nanosynthesis is the basis of nanotechnology and its applications. It is necessary to understand the growth mechanism of nanoparticles and the functions of growth factors. An effective way to study the synthesis is at the single nanoparticle level. This study reports a single nanoparticle spectrometer, which is based on a commercial dark-field microscopy and a group of narrowband filters. This spectrometer has many advantages, such as high light transparency (35%-75%), low cost (<$1500), massive screening (≈200 nanoplates at a time), and a high time resolution (<5 s). By using this spectrometer, the galvanic replacement reaction (GRR) is studied on single Ag nanoplates in situ and in real time. The research reveals that GRR on single Ag nanoplates has three different types according to the change of peak wavelength during reaction. Such diverse reaction types can be attributed to the different relative reaction rates of GRR on the faces and edges of Ag nanoplate with different facets. Further research shows that the relative reaction rates of different facets vary a lot under different concentrations of tri-sodium citrate. This research successfully demonstrates that the new single nanoparticle spectrometer can study the growth of single nanoparticles and the effect of growth factors.

Hydrogen transfer reaction in polycyclic aromatic hydrocarbon radicals.

Density functional theory calculations have been successfully applied to investigate the formation of hydrocarbon radicals and hydrogen transfer pathways related to the chemical vapor infiltration process based on model molecules of phenanthrene, anthra[2,1,9,8-opqra]tetracene, dibenzo[a,ghi]perylene, benzo[uv]naphtho[2,1,8,7-defg]pentaphene, and dibenzo[bc,ef]ovalene. The hydrogen transfer reaction rate constants are calculated within the framework of the Rice-Ramsperger-Kassel-Marcus theory and the transition state theory by use of the density functional theory calculation results as input. From these calculations, it is concluded that the hydrogen transfer reaction between two bay sites can happen almost spontaneously with energy barrier as low as about 4.0 kcal mol(-1), and the hydrogen transfer reactions between two armchair sites possess lower energy barrier than those between two zigzag sites.

Hydrogen bond and proton transport in acid-base complexes and amphoteric molecules by density functional theory calculations and 1H and 31P nuclear magnetic resonance spectroscopy.

Intermolecular and intramolecular hydrogen bond (H-bond) and proton transport in acid-base complexes and amphoteric molecules consisting of phosphonic acid groups and nitrogenous heterocyclic rings are investigated by density functional theory calculations and (1)H NMR and (31)P NMR spectroscopy. It is concluded that a phosphonic acid group can act both as H-bond donor and H-bond acceptor, while an imine nitrogen atom can only act as H-bond acceptor and an amine group as H-bond donor. And the intramolecular H-bond is weaker than the intermolecular H-bond attributing to configurational restriction. In addition, the strongest H-bond interaction is observed between a phosphonic acid and a 1H-indazole because of the formation of double H-bonds. The (1)H NMR and (31)P NMR chemical shifts for the acid-base complexes are consistent with the density functional theory calculations. From the (1)H NMR chemical shifts, fast proton exchange is observed between a phosphonic acid and 1H-benzimidazole or 1H-indazole. Finally, it is proposed that polymeric material tethered with 1H-benzimidazole or 1H-indazole rings is a favorable component for high-temperature proton exchange membranes based on acid-base complexes or acid-base amphoteric molecules.

Proton transport pathways in an acid-base complex consisting of a phosphonic acid group and a 1,2,3-triazolyl group.

The proton transport pathways in an acid-base complex consisting of a phosphonic acid group and a 1,2,3-triazolyl group were studied using density functional theory (DFT) calculations in terms of stable configurations and transition states of the molecular or ionic dimers and trimers and verified by proof-of-concept experiments including experimental measurements of overall conductivity and (1)H NMR and FTIR spectroscopy of the methylphosphonic acid (MPA) and 1,2,3-triazole (Tri) complex as well as overall proton conductivity of polymeric blend of poly(vinylphosphonic acid) (PVPA) and poly(4-vinyl-1H-1,2,3-triazole) (PVTri). From the DFT calculations of dimers and trimers composed of ethylphosphonic acid (EPA), Tri, and their deprotonated counterparts, it was concluded that the intermolecular hydrogen bonds of the transition states corresponding to proton transport are much shorter than those of stable configurations, but the O-H and N-H bonds are much longer than those of stable configurations. The tautomerization activation energy decreases from 0.927-1.176 eV in Tri-Tri dimers to 0.336-0.444 eV in the EPA-Tri dimers. From the proof-of-concept experiments, about a 50 fold increase in overall conductivity was observed in the MPA-Tri complex consisting of 10% (molar ratio) MPA compared to pure Tri, and the calculated activation energy is consistent with the experimental activation energy evaluated from temperature dependence of proton conductivity of pure Tri and the MPA-Tri complex. In addition, the fast proton exchange between MPA and Tri, consistent with the DFT calculations, was verified by (1)H NMR and FTIR spectroscopy. Finally, a polymeric blend of PVPA and PVTri was prepared, and its proton conductivity at about 2.1 mS·cm(-1) in anhydrous state at 100 °C was observed to be significantly higher than that of PVPA or of poly(VPA-co-1-vinyl-1,2,4-triazole). The proton conductivity of the polymeric PVPA and PVTri blend in humidity state is in the same range as that of NAFION 117.

Polymeric nanocomposites of functionalized carbon nanotubes synthesized in supercritical CO2.

A novel method to synthesize single-wall carbon nanotube (SWNT)/poly(methyl methacrylate) (PMMA) nanocomposite by in-situ polymerization in supercritical CO2 is presented. The surfaces of the SWNT bundles were first functionalized with amino ethyl methacrylate (AEMA) followed by co-polymerization with methyl methacrylate. Supercritical fluid enhanced the diffusivity of monomer and facilitated the growth of tethered PMMA chains near the entanglement area and the interstitial space of the SWNT bundles. Partial debundling and disentanglement of the SWNT bundles and an enhanced dispersion in the polymer matrix were observed under SEM and TEM. After the removal of the polymer matrix physically attached to the nanotubes, it is found that the nanotubes were covered by tethered PMMA chains, which were a few nanometers in thickness. This work creates a route for improving impregnation and dispersion in SWNT composites; the same process can be extended to other vinyl polymers.

Highly stable phospholipid unilamellar vesicles from spontaneous vesiculation: A DLS and SANS study.

Spontaneously formed unilamellar vesicles (ULV) composed of short- and long-chain phospholipids, dihexanoyl phosphorylcholine (DHPC) and dimyristoyl phosphorylcholine (DMPC), respectively, were doped with a negatively charged lipid, dimyristoyl phosphorylglycerol (DMPG), and studied with small-angle neutron scattering (SANS) and dynamic light scattering (DLS). Upon dilution, the spontaneous formation of vesicles was found to take place from bilayered micelles, or so-called "bicelles". SANS and DLS data show that ULV with narrow size distributions are highly stable at low lipid (C(lp) < 0.50 wt %) and NaCl salt (C(s)) concentrations. ULV size was found to be independent of both C(lp) and C(s) when they were below 0.33 and 0.5 wt %, respectively. Surface charge and salinity were found to be important factors in preparing ULV of a certain size. This observation is not in complete agreement with previous experimental results and cannot be completely explained with current theoretical predictions based on equilibrium calculations for catanionic surfactant mixtures. ULV size is found to be invariant over a wide range of temperatures, both below and above the phase-transition temperature, T(M), of DMPC, and was stable for periods of weeks and months, even after sonication.