Interaction of silane with 10-MDP on affecting surface chemistry and resin bonding of zirconia.

OBJECTIVE: To investigate the effect of silane contents on their chemical interaction with 10-methacryloyloxydecyl-dihydrogen phosphate (MDP), and affecting the bonding of MDP to zirconia by time-of-flight secondary ion mass spectrometry (TOF-SIMS) and solid-state nuclear magnetic resonance (SSNMR) spectroscopy. METHODS: Zirconia (Cercon ht, Dentsply) slabs were prepared and fully sintered. Experimental primers SE-5 and SE-10 were formulated by adding 5 wt% and 10 wt% γ-methacryloxypropyltrimethoxysilane to an MDP-based primer SE BOND (SE), respectively. SE, SE-5, and SE-10 were applied on the assigned zirconia slabs. The chemical compositions on the surface and adhesive interfaces were examined by TOF-SIMS in a depth-profiling mode. Hydrophilicity and resin affinity of treated zirconia were analyzed. The bond strengths to resin cylinder were examined either after 24-h storage or thermocycles. In addition, zirconia powders treated with three primers were assessed by SSNMR spectrometry for the adsorption of MDP. RESULTS: TOF-SIMS analysis showed that SE treatment generated the greatest amount of P-O-Zr related ions, which reduced in SE-5 and SE-10 groups. The 3D ion-images illustrated the generation of ZrO2(OH)- ions with silane contents. The SSNMR analysis revealed that the chemical bonding was mainly P-O-Zr ionic bonds in SE but shifted to P-OH-Zr hydrogen bonds in SE-5 and SE-10. SE-5 and SE-10 treated zirconia presented higher hydrophilicity and affinity to resin compared to Zr did. SE showed the highest initial bond strength which significantly decreased after thermocycling. SIGNIFICANCE: MDP adsorption onto zirconia via P-O-Zr ionic bond promotes bonding with resin. The silane enhances the hydroxylation of zirconia and impairs the adsorption of MDP, but does not adversely affect the bond durability.

Investigations of silane-MDP interaction in universal adhesives: A ToF-SIMS analysis.

OBJECTIVES: The purposes of this study were to investigate whether the presence of silane in universal adhesives affects the functions of 10-methacryloyloxydecyl dihydrogen phosphate (MDP) and adhesion to zirconia. METHODS: Two silane-containing universal adhesives (Scotchbond Universal (SBU) and Clearfil Universal-Bond (CUB)) and two silane-free adhesives (All-Bond Universal (ABU) and SE-Bond primer (SE)) were individually applied on zirconia disks. Time-of-flight secondary-ion-mass-spectrometry (ToF-SIMS) examined the distributions of MDP- and silane-related ions, as well as evidence of zirconium phosphate (ZrP) compounds, on the surface and interfacial regions using a depth profiling mode. The hydrophilicity and resin wettability of the treated zirconia were examined using a contact angle test. For the shear bond strength (SBS) test, the zirconia disks were air-blasted, treated with the assigned adhesives, and bonded with pre-cured composite cylinders using a resin cement. These resin-zirconia assemblies received a bond test after 24-h storage. RESULTS: Both SBU and CUB exhibited silane-related ions and ZrO2(OH)-, but fewer PO- ions in the interfacial regions. CUB had more siloxane-related ions. SE-treated zirconia had abundant PO- ions and particularly high PO3-- and ZrP- related ions in the interfacial regions. The silane-free adhesives exhibited a higher affinity to both water and adhesive liquids. SE showed significantly higher SBSs compared to ABU, while SBU and CUB were not statistically different. SIGNIFICANCE: The silane content may cause hydroxylation of zirconia and affect MDP adsorption. An acidic pH accelerated the condensation of silanol. The bond performance of the MDP-based adhesive could be influenced by the silane content and other components.

Microscopic Revelation of Charge-Trapping Sites in Polymeric Carbon Nitrides for Enhanced Photocatalytic Activity by Correlating with Chemical and Electronic Structures.

The influences of chemical and electronic structures on the photophysical properties of polymeric carbon nitrides (PCNs) photocatalysts, which govern the microscopic mechanisms of the superior photocatalytic activity under visible-light irradiation, have been resolved in this work. Time-resolved photoluminescence and in situ electron paramagnetic resonance measurements indicate that the photoexcited electrons in the fractured PCNs swiftly transfer to the C2p-localized states where the trapped photoelectrons exhibit longer lifetime compared to those in the ordinary PCNs. Moreover, the structure deviation at the carbon (Cb) atoms around the bridging sites of heptazine ring units, where trapped photoelectrons are localized, has been determined in the fractured PCNs based on the 13C solid-state nuclear magnetic resonance spectra and the density functional theory calculations. Accordingly, the formation of fractured PCNs by breaking the in-plane hydrogen bonds at a high temperature is a promising strategy for the enhancement of photocatalytic activity.

Minimization of Ion-Solvent Clusters in Gel Electrolytes Containing Graphene Oxide Quantum Dots for Lithium-Ion Batteries.

This study uses graphene oxide quantum dots (GOQDs) to enhance the Li+ -ion mobility of a gel polymer electrolyte (GPE) for lithium-ion batteries (LIBs). The GPE comprises a framework of poly(acrylonitrile-co-vinylacetate) blended with poly(methyl methacrylate) and a salt LiPF6 solvated in carbonate solvents. The GOQDs, which function as acceptors, are small (3-11 nm) and well dispersed in the polymer framework. The GOQDs suppress the formation of ion-solvent clusters and immobilize PF6- anions, affording the GPE a high ionic conductivity and a high Li+ -ion transference number (0.77). When assembled into Li|electrolyte|LiFePO4 batteries, the GPEs containing GOQDs preserve the battery capacity at high rates (up to 20 C) and exhibit 100% capacity retention after 500 charge-discharge cycles. Smaller GOQDs are more effective in GPE performance enhancement because of the higher dispersion of QDs. The minimization of both the ion-solvent clusters and degree of Li+ -ion solvation in the GPEs with GOQDs results in even plating and stripping of the Li-metal anode; therefore, Li dendrite formation is suppressed during battery operation. This study demonstrates a strategy of using small GOQDs with tunable properties to effectively modulate ion-solvent coordination in GPEs and thus improve the performance and lifespan of LIBs.

Structure and molecular dynamics of sodium dodecylsulfate micelles modified with hydrophilic short-chain imidazolium salts in aqueous solution.

This study uses pyrene solubilization and NMR experiments to investigate the effects of two hydrophilic short-chain ionic liquids (ILs), 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF4) and 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) on the micellization of sodium dodecylsulfate (SDS) in the aqueous phase. The results of the pyrene solubilization experiments indicate that the added short-chain ILs not only promote the micellization of SDS but also modify micelle properties. For NMR studies, the present study focuses on (1) the compositions and spatial arrangements of component molecules and (2) the molecular dynamics of DS(-) in the Rmim-modified SDS micelle. Using pulsed field gradient (PFG) NMR measurements, the composition of the Rmim-modified SDS micelle was calculated by the diffusion data and was found to be correlated with the [SDS]. Two-dimensional nuclear Overhauser effect spectroscopy (2D NOESY) experiments confirm that the 1-alkyl-3-methylimidazolium cation (Rmim(+)) is located inside the Rmim-modified SDS micelle. Corresponding to the microstructure of the Rmim-modified SDS micelle, in terms of (1)H T1 relaxation, the fast motion of SDS α-CH2 and ß-CH2 segments are markedly restricted by the attached Rmim(+) to the sulfate group of DS(-), whereas the central carbons and the terminal CH3 group of DS(-) are only slightly affected. The chemical shift analysis indicates that the surface of the Rmim-modified SDS micelle is dehydrated by the absorbed Rmim(+) and becomes more hydrophobic than that of the pure SDS micelle. Insertion of Rmim(+) into the Rmim-modified SDS micelle appears to be driven through the hydrophobic interaction, and it is shown to combine with SDS molecules to constitute the hydrophobic part of the Rmim-modified SDS micelle.

Alkyl-poly(l-threonine)/Cyclodextrin Supramolecular Hydrogels with Different Molecular Assemblies and Gel Properties.

We report alkyl-poly(l-threonine)/cyclodextrin (alkyl-PLT/CD) supramolecular hydrogels with different molecular assemblies. Their properties are determined by the interplay between host-guest chemistry and hydrogen-bonding interactions. The gelation process was mainly dictated by the formation of alkyl chain/CD inclusion complex and PLT chain conformation. The dodecyl-PLT20/α-CD hydrogel exhibited laminar packing due to the sheet-to-coil conformational change upon forming inclusion complex. The hexadecyl-PLT20/ß-CD hydrogel exhibited ribbon-like assemblies instead, because the peptide adopted mainly sheet conformation. The gel-to-sol transition occurred upon increasing temperature because of the decrease in hydrogen-bonding interactions and partly conformational change.

Interaction between hydrophobically modified 2-hydroxyethyl cellulose and sodium dodecyl sulfate studied by viscometry and two-dimensional NOE NMR spectroscopy.

Interaction between an anionic surfactant, sodium dodecyl sulfate (SDS), and a nonionic polymer, 2-hydroxyethyl cellulose (HEC) hydrophobically modified with benzoyl chloride (bmHEC), is studied by viscometry and two-dimensional nuclear Overhauser effect NMR spectroscopy (2D NOESY) in a semidilute regime of bmHEC. The hydrophobicity of bmHEC was varied with different substitution of benzoyl group to HEC macromolecules. In general, the low-shear viscosity of 1 wt % bmHEC aqueous solution is increased with added SDS surfactant having concentration from 0 to 0.5 wt %, and then decreased significantly with a further addition of surfactant to 3 wt %. The activation energy of transient network formation in 1 wt % bmHEC aqueous solution present with SDS surfactant is found to be dependent with SDS concentration, which varies from 32.7 to 69.80 kJ/mol. The maximum activation energy takes place when 0.5 wt % SDS is added, which coincides with that of the maximal viscosity. The 2D NOESY displays that the surfactants actually interact with bmHEC not only on the hydrophobes, namely benzoyl groups, but also the polymer backbone, i.e., glucose units. In contrast, no interaction is revealed by 2D NOESY in the aqueous system containing SDS surfactant and HEC polymer.

High performance of transferring lithium ion for polyacrylonitrile-interpenetrating crosslinked polyoxyethylene network as gel polymer electrolyte.

A polyacrylonitrile (PAN)-interpenetrating cross-linked polyoxyethylene (PEO) network (named XANE) was synthesized acting as separator and as gel polymer electrolytes simultaneously. SEM images show that the surface of the XANE membrane is nonporous, comparing to the surface of the commercial separator to be porous. This property results in excellent electrolyte uptake amount (425 wt %), and electrolyte retention for XANE membrane, significantly higher than that of commercial separator (200 wt %). The DSC result indicates that the PEO crystallinity is deteriorated by the cross-linked process and was further degraded by the interpenetration of the PAN. The XANE membrane shows significantly higher ionic conductivity (1.06-8.21 mS cm(-1)) than that of the commercial Celgard M824 separator (0.45-0.90 mS cm(-1)) ascribed to the high electrolyte retention ability of XANE (from TGA), the deteriorated PEO crystallinity (from DSC) and the good compatibility between XANE and electrode (from measuring the interfacial-resistance). For battery application, under all charge/discharge rates (from 0.1 to 3 C), the specific half-cell capacities of the cell composed of the XANE membrane are all higher than those of the aforementioned commercial separator. More specifically, the cell composed of the XANE membrane has excellent cycling stability, that is, the half-cell composed of the XANE membrane still exhibited more than 97% columbic efficiency after 100 cycles at 1 C. The above-mentioned advantageous properties and performances of the XANE membrane allow it to act as both an ionic conductor as well as a separator, so as to work as separator-free gel polymer electrolytes.

NMR studies on effects of tetraalkylammonium bromides on micellization of sodium dodecylsulfate.

The effects of tetraalkylammonium bromides (TAABs) on the micellization of sodium dodecylsulfate (SDS) are studied using pyrene solubilization and several nuclear magnetic resonance (NMR) techniques. Two-dimensional nuclear Overhauser effect spectroscopy (2D NOESY) experiments confirm that tetraalkylammonium (TAA(+)) ions associate with SDS to form mixed micelles. TAA(+) ions attach to the surface of the mixed micelles and become inserted into the hydrophobic core of the mixed micelles. Because TAA(+) ions appear in the hydrophobic interior of the TAA-SDS mixed micelles, the micropolarity inside the mixed micelles sensed by pyrene might not reflect the true hydrophobicity of the micellar core. Using proton chemical shift analysis, the degree of hydration on the surface of the mixed micelles is determined from the chemical shift change of SDS α-CH2 protons. The self-diffusion coefficients of SDS and TAA(+) ions in the TAAB/SDS/D2O solutions are measured by using pulse-field gradient NMR, and the fraction of TAA(+) ions associated with the SDS to form the mixed micelles is calculated from the self-diffusion data. Moreover, secondary micelle formation for SDS and TAA(+) ions is observed on the basis of (1)H chemical shift analysis and the self-diffusion data. The 2D NOESY experiments also reveal unusual tumbling behavior of SDS alkyl protons. For Pr4NBr/SDS and Bu4NBr/SDS solutions, positive and negative nuclear Overhauser effects are simultaneously observed among the SDS alkyl protons.

Lauroyl/palmitoyl glycol chitosan gels enhance skin delivery of magnesium ascorbyl phosphate.

Palmitoyl glycol chitosan (GCP) hydrogel has been reported as erodible controlled-release systems for the delivery of both hydrophilic and hydrophobic molecules. In this study we prepared lauroyl/palmitoyl glycol chitosan (GCL/GCP) in gel form and evaluated their application for skin delivery of the hydrophilic compound, magnesium ascorbyl phosphate (MAP), which is widely used in cosmetic formulations. Release of MAP from the polymer gels was significantly decreased with increasing concentration of GCL/GCP in the formulations in comparison with glycol chitosan (GC). In both aqueous and 10% ethanol vehicles, MAP flux was increased 1.58- to 3.96-fold of 1% GC from 1% GCL/GCP. Increase in MAP flux was correlated to the increase in GCL/GCP concentration prepared in 10% ethanol vehicle. GCL/GCP, in either water or 10% ethanol vehicles, increased the skin penetration and skin deposition of MAP in comparison with GC, hydroxypropylmethylcellulose, and carbopol, while sustaining its release from the polymer gels. Both the enhancement in skin penetration/deposition and sustained release of MAP were depended on polymer concentration. Also, with increase in polymer concentration, epidermal to dermal drug deposition ratio tended to increase, which will be beneficial to its activity in the epidermis, such as inhibition of tyrosinase and protection from UV damage. These data suggested both GCL and GCP can be applied as delivery vehicles to improve percutaneous absorption of MAP.

Poly(ethylene oxide)-co-poly(propylene oxide)-based gel electrolyte with high ionic conductivity and mechanical integrity for lithium-ion batteries.

Using gel polymer electrolytes (GPEs) for lithium-ion batteries usually encounters the drawback of poor mechanical integrity of the GPEs. This study demonstrates the outstanding performance of a GPE consisting of a commercial membrane (Celgard) incorporated with a poly(ethylene oxide)-co-poly(propylene oxide) copolymer (P(EO-co-PO)) swelled by a liquid electrolyte (LE) of 1 M LiPF6 in carbonate solvents. The proposed GPE stably holds LE with an amount that is three times that of the Celgard-P(EO-co-PO) composite. This GPE has a higher ionic conductivity (2.8×10(-3) and 5.1×10(-4) S cm(-1) at 30 and -20 °C, respectively) and a wider electrochemical voltage range (5.1 V) than the LE-swelled Celgard because of the strong ion-solvation power of P(EO-co-PO). The active ion-solvation role of P(EO-co-PO) also suppresses the formation of the solid-electrolyte interphase layer. When assembling the GPE in a Li/LiFePO4 battery, the P(EO-co-PO) network hinders anionic transport, producing a high Li+ transference number of 0.5 and decreased the polarization overpotential. The Li/GPE/LiFePO4 battery delivers a discharge capacity of 156-135 mAh g(-1) between 0.1 and 1 C-rates, which is approximately 5% higher than that of the Li/LE/LiFePO4 battery. The IR drop of the Li/GPE/LiFePO4 battery was 44% smaller than that of the Li/LE/LiFePO4. The Li/GPE/LiFePO4 battery is more stable, with only a 1.2% capacity decay for 150 galvanostatic charge-discharge cycles. The advantages of the proposed GPE are its high stability, conductivity, Li+ transference number, and mechanical integrity, which allow for the assembly of GPE-based batteries readily scalable to industrial levels.