Rapid method to measure diffusion of paramagnetic species: Mn2+ in poly(ethylene-co-methacrylic acid) ionomers

2002 ◽  
Vol 17 (10) ◽  
pp. 2736-2743 ◽  
Author(s):  
Neena K. Tierney ◽  
Richard A. Register
Keyword(s):  
Methacrylic Acid ◽  
Diffusion Coefficients ◽  
Fickian Diffusion ◽  
Paramagnetic Species ◽  
Local Concentration ◽  
Spin Resonance ◽  
Broad Signal ◽  
Poly Ethylene ◽  
Concentration Diffusion

We present a facile method to measure Fickian diffusion coefficients of paramagnetic species in materials, using electron spin resonance (ESR) spectroscopy. The method requires no postannealing sample preparation, is adaptable to in situ measurement, and requires only that the spectrum of the paramagnetic species change monotonically with its local concentration. We illustrated this method with poly(ethylene-co-methacrylic acid) ionomers, using laminates prepared from the same copolymer neutralized with either paramagnetic Mn2+ or diamagnetic Zn2+. For Mn2+, the exchange interaction between neighboring Mn2+ caused the six-line hyperfine pattern to transform to a single broad signal, providing the measurement of local concentration. Diffusion coefficients of Mn2+ in this ionomer pair measured by ESR were compared with those for Zn2+ measured by conventional electron probe microanalysis and found to be in satisfactory agreement.

scholarly journals Novel Approaches to In-Situ ATR-FTIR Spectroscopy and Spectroscopic Imaging for Real-Time Simultaneous Monitoring Curing Reaction and Diffusion of the Curing Agent at Rubber Nanocomposite Surface

Polymers ◽  
2021 ◽  
Vol 13 (17) ◽  
pp. 2879
Author(s):  
Shun Muroga ◽  
Yu Takahashi ◽  
Yuta Hikima ◽  
Seisuke Ata ◽  
Sergei G. Kazarian ◽  
...  
Keyword(s):  
Ftir Spectroscopy ◽  
Real Time ◽  
Diffusion Coefficients ◽  
Heated Surface ◽  
Fickian Diffusion ◽  
Curing Agent ◽  
Ftir Imaging ◽  
Curing Reaction ◽  
Curing Agents

Here, we propose a novel attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy method for simultaneously monitoring the curing reaction and the diffusion behavior of curing agents at the surface of rubber in real-time. The proposed scheme was demonstrated by fluorine rubber (FKM) and FKM/carbon nanotube (CNT) nanocomposites with a target curing agent of triallyl-isocyanurate (TAIC). The broadening and the evolution of the C=O stretching of TAIC were quantitatively analyzed to characterize the reaction and the diffusion. Changes in the width of the C=O stretching indicated the reaction rate at the surface was even faster than that of the bulk as measured by a curemeter. The diffusion coefficient of the curing agent in the course of heating was newly calculated by the initial increase in the absorbance and our model based on Fickian diffusion. The diffusion coefficients of TAIC during curing were evaluated, and its temperature and filler dependency were identified. Cross-sectional ATR-FTIR imaging and in situ ATR-FTIR imaging measurements supported the hypothesis of the unidirectional diffusion of the curing agent towards the heated surface. It was shown that our method of in situ ATR-FTIR can monitor the degrees of cure and the diffusion coefficients of curing agents simultaneously, which cannot be achieved by conventional methods, e.g., rheological measurements.

Electron spin resonance studies of manganese(II) and copper(II) salts of poly(ethylene-co-methacrylic acid)s

1988 ◽  
Vol 26 (5) ◽  
pp. 997-1008 ◽  
Author(s):  
Miyuki Takei ◽  
Yoshiharu Tsujita ◽  
Shigetaka Shimada ◽  
Hisakatsu Ichihara ◽  
Motohiro Enokida ◽  
...  
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Methacrylic Acid ◽  
Spin Resonance ◽  
Poly Ethylene

scholarly journals Poly(ethylene glycol)-b-poly(1,3-trimethylene carbonate) Copolymers for the Formulation of In Situ Forming Depot Long-Acting Injectables

Pharmaceutics ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 605
Author(s):  
Marie-Emérentienne Cagnon ◽  
Silvio Curia ◽  
Juliette Serindoux ◽  
Jean-Manuel Cros ◽  
Feifei Ng ◽  
...  
Keyword(s):  
Ethylene Glycol ◽  
Surface Erosion ◽  
Sustained Delivery ◽  
Trimethylene Carbonate ◽  
Poly Ethylene Glycol ◽  
In Situ Forming ◽  
Poly Ethylene ◽  
Long Acting

This article describes the utilization of (methoxy)poly(ethylene glycol)-b-poly(1,3-trimethylene carbonate) ((m)PEG–PTMC) diblock and triblock copolymers for the formulation of in situ forming depot long-acting injectables by solvent exchange. The results shown in this manuscript demonstrate that it is possible to achieve long-term drug deliveries from suspension formulations prepared with these copolymers, with release durations up to several months in vitro. The utilization of copolymers with different PEG and PTMC molecular weights affords to modulate the release profile and duration. A pharmacokinetic study in rats with meloxicam confirmed the feasibility of achieving at least 28 days of sustained delivery by using this technology while showing good local tolerability in the subcutaneous environment. The characterization of the depots at the end of the in vivo study suggests that the rapid phase exchange upon administration and the surface erosion of the resulting depots are driving the delivery kinetics from suspension formulations. Due to the widely accepted utilization of meloxicam as an analgesic drug for animal care, the results shown in this article are of special interest for the development of veterinary products aiming at a very long-term sustained delivery of this therapeutic molecule.

scholarly journals Au Modified F-TiO2 for Efficient Photocatalytic Synthesis of Hydrogen Peroxide

Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 3844
Author(s):  
Lijuan Li ◽  
Bingdong Li ◽  
Liwei Feng ◽  
Xiaoqiu Zhang ◽  
Yuqian Zhang ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Reaction System ◽  
Reaction Medium ◽  
Pure Tio2 ◽  
H2o2 Production ◽  
Tio2 Photocatalyst ◽  
H2o2 Decomposition ◽  
Spin Resonance ◽  
Photocatalytic Synthesis

In this work, Au-modified F-TiO2 is developed as a simple and efficient photocatalyst for H2O2 production under ultraviolet light. The Au/F-TiO2 photocatalyst avoids the necessity of adding fluoride into the reaction medium for enhancing H2O2 synthesis, as in a pure TiO2 reaction system. The F− modification inhibits the H2O2 decomposition through the formation of the ≡Ti–F complex. Au is an active cocatalyst for photocatalytic H2O2 production. We compared the activity of TiO2 with F− modification and without F− modification in the presence of Au, and found that the H2O2 production rate over Au/F-TiO2 reaches four times that of Au/TiO2. In situ electron spin resonance studies have shown that H2O2 is produced by stepwise single-electron oxygen reduction on the Au/F-TiO2 photocatalyst.

scholarly journals Synthesis of Poly(methacrylic acid-co-butyl acrylate) Grafted onto Functionalized Carbon Nanotube Nanocomposites for Drug Delivery

Polymers ◽  
2021 ◽  
Vol 13 (4) ◽  
pp. 533 ◽  
Author(s):  
Josué A. Torres-Ávalos ◽  
Leonardo R. Cajero-Zul ◽  
Milton Vázquez-Lepe ◽  
Fernando A. López-Dellamary ◽  
Antonio Martínez-Richa ◽  
...  
Keyword(s):  
Carbon Nanotubes ◽  
Drug Delivery ◽  
Methacrylic Acid ◽  
Butyl Acrylate ◽  
Chemical Vapor ◽  
Vis Spectroscopy ◽  
Ir And Raman Spectroscopies ◽  
Ft Ir

Design of a smart drug delivery system is a topic of current interest. Under this perspective, polymer nanocomposites (PNs) of butyl acrylate (BA), methacrylic acid (MAA), and functionalized carbon nanotubes (CNTsf) were synthesized by in situ emulsion polymerization (IEP). Carbon nanotubes were synthesized by chemical vapor deposition (CVD) and purified with steam. Purified CNTs were analyzed by FE-SEM and HR-TEM. CNTsf contain acyl chloride groups attached to their surface. Purified and functionalized CNTs were studied by FT-IR and Raman spectroscopies. The synthesized nanocomposites were studied by XPS, 13C-NMR, and DSC. Anhydride groups link CNTsf to MAA–BA polymeric chains. The potentiality of the prepared nanocomposites, and of their pure polymer matrices to deliver hydrocortisone, was evaluated in vitro by UV–VIS spectroscopy. The relationship between the chemical structure of the synthesized nanocomposites, or their pure polymeric matrices, and their ability to release hydrocortisone was studied by FT-IR spectroscopy. The hydrocortisone release profile of some of the studied nanocomposites is driven by a change in the inter-associated to self-associated hydrogen bonds balance. The CNTsf used to prepare the studied nanocomposites act as hydrocortisone reservoirs.

scholarly journals Bio-based polyurethane nanocomposite thin coatings from two comparable POSS with eight same vertex groups for controlled release urea

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Lixia Li ◽  
Meng Wang ◽  
Xiandong Wu ◽  
Wenping Yi ◽  
Qiang Xiao
Keyword(s):  
In Situ Polymerization ◽  
Polyhedral Oligomeric Silsesquioxanes ◽  
Poly Ethylene Glycol ◽  
Thin Coatings ◽  
Polyurethane Coatings ◽  
Coated Urea ◽  
Poly Ethylene ◽  
Coated Fertilizer ◽  
Polyurethane Matrix

AbstractNanocomposite modification has attracted much attention in improving properties of bio-based polymer coating material for coated fertilizer. Herein two comparable polyhedral oligomeric silsesquioxanes (POSS), with eight poly(ethylene glycol) (PEG) and octaphenyl groups attached to the cage, respectively, were successfully incorporated into thin castor oil-based polyurethane coatings via in-situ polymerization on the urea surface. The nanostructure coatings are environmentally friendly, easy to prepare, and property-tunable. The results show that the vertex group of POSS had a pronounced influence on dispersion level and interaction between polyurethane and POSS that well-tuned the release pattern and period of coated urea, even at the coating rate as low as of 2 wt%. The liquid POSS with long and flexible PEG groups had better compatibility and dispersibility in polyurethane matrix than the solid POSS with rigid octaphenyl groups, as evidenced by SEM/EDS. The unique properties were resulted from the different extents of physical crosslinkings. This modification of bio-based polyurethane coating with POSS provided an alternative method of regulating and controlling the properties of coated fertilizer.

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