Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

Heinze, Marcus; Starke, S.; Händler, Marcel; Komber, Hartmut; Drache, Marco; Moszner, Norbert; Voit, Brigitte; Pospiech, Doris

doi:10.1002/app.48256

Cited by 3 publications

(4 citation statements)

References 24 publications

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“…The data are summarized in Table S1. Increased contents of both ITA and ECPPA, respectively, required longer reaction times, which is due to the slower reactivity of both monomers with respect to HEMA . Samples consisting of exclusively poly(HEMA) (100/0/0) were completely converted after 10 min (Figure S2), whereas hydrogels of poly(HEMA/ITA/ECPPA) (85/5/10) with 5 mol % cross-linker BAAP required a UV exposure time of 30 min.…”

Section: Resultsmentioning

confidence: 99%

Chemical Design of Hydrogels with Immobilized Laccase for the Reduction of Persistent Trace Compounds in Wastewater

Horn

Pospiech

Allertz

et al. 2021

ACS Appl. Polym. Mater.

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Hydrogels with immobilized enzymes are increasingly applied in biocatalytic industrial processes. Here, polymer hydrogels containing 2-hydroxyethyl methacrylate (HEMA), itaconic acid (ITA), (2-((2-(ethoxycarbonyl)prop-2-en-1-yl)oxy)ethyl) phosphonic acid (ECPPA), and N,N′-diethyl-1,3-bis(acrylamido)propane (BAAP) as the cross-linker are synthesized by UV-initiated radical polymerization. Laccase from Trametes versicolor (LAC) is modified by reaction with itaconic anhydride (ITAn) yielding the LAC-immobilized monomer ITA-LAC with enhanced enzyme activity. ITA-LAC paves the way to an in situ method for enzyme immobilization. Hydrogels with HEMA, ECPPA, and BAAP with stepwise varied chemical composition and functionalization are prepared. The influence of the composition on the morphology, the swelling behavior, the mechanical stability, and the enzymatic activity is studied. The polymerization is monitored by the conversion of double bonds with in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. The polymerization of HEMA is complete after 10 min of UV exposure, whereas hydrogels of HEMA/ITA/ECPPA (85/5/10) with 5 mol % cross-linker require 30 min. These hydrogels are compared with those containing ITA-LAC instead of ITA. The covalent binding of LAC is proven by ATR-FTIR spectroscopy and results in an enhanced enzyme activity. The incorporation of ECPPA induces pH-dependent swelling with an equilibrium degree of swelling of up to 6 at pH 8. Only a weak influence of temperature on the degree of swelling is found. The morphology strongly depends on the hydrogel composition. LAC-ITA hydrogels are characterized by an open morphology providing access to catalytic centers. The enzyme-immobilized hydrogels are used as granules as well as coatings on porous Al2O3 ceramic substrates as biocatalysts to convert models for organic trace compounds [bisphenol A (BPA), diclofenac, p-chlorophenol (pCP), 17α-ethinylestradiol (EED), triclosan, paracetamol, and 4-tert-octylphenol]. The highest conversion after 24 h in water is achieved for triclosan (>90%), while pCP, BPA, and EED reach a conversion between 60% and 70%. The conversions are even higher in citrate buffer.

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Section: Resultsmentioning

confidence: 99%

Chemical Design of Hydrogels with Immobilized Laccase for the Reduction of Persistent Trace Compounds in Wastewater

Horn

Pospiech

Allertz

et al. 2021

ACS Appl. Polym. Mater.

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“…They increased the channel diameter of the microreactor (inner diameter ¼ 0.5 mm) to fit the nanoscale pilot reactor (diameter ¼ 2 mm), considering the mixing efficiency, residence time distribution, and heat transfer. 25,26 Bazzoni et al demonstrated the inline monitoring of a flow photochemical reaction using one-dimensional (1D) and ultrafast two-dimensional (2D) NMR methods in a high magnetic field. 27 The reaction mixture exiting the flow reactor flowed through the NMR spectrometer and was directly analyzed.…”

Section: Kinetic and Thermodynamic Studiesmentioning

confidence: 99%

“…They increased the channel diameter of the microreactor (inner diameter = 0.5 mm) to fit the nanoscale pilot reactor (diameter = 2 mm), considering the mixing efficiency, residence time distribution, and heat transfer. 25 26…”

Section: Introductionmentioning

confidence: 99%

A Review of Inline Infrared and Nuclear Magnetic Resonance Applications in Flow Chemistry

Zhang,

2023

Pharmaceutical Fronts

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As a safe and efficient synthesis technique, flow chemistry has recently gained attention in the pharmaceutical, materials, and environmental protection industries. However, researchers always face challenges in handling samples and selecting sufficiently flexible analytical techniques. Generally, real-time process analysis is crucial for monitoring reactions. The combination of flow chemistry with real-time process analysis can be beneficial for studying reaction kinetics and thermodynamics, monitoring, and control of the chemical synthesis processes, reaction optimization of macro and microreactors, and qualitative and quantitative analyses of compounds. Thus far, studies investigating the combination of flow chemistry with inline monitoring have included ultraviolet–infrared spectroscopy, Raman spectroscopy, gas chromatography, mass spectrometry, liquid chromatography, nuclear magnetic resonance (NMR) spectroscopy, and other automated conventional or unconventional methods. This review sheds light on applying inline infrared and inline NMR spectroscopies in flow chemistry.

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“…One of these monomers is (2-((2-(ethoxycarbonyl) allyl)oxy)ethyl)phosphonic acid (ECPA), which shows improved hydrolytic stability under acidic conditions since the phosphonic acid is linked to the methacrylate via an ether bridge [9,14]. The copolymerization behavior of this monomer with HEMA as well as itaconic acid has been reported recently [24,25].…”

Section: Introductionmentioning

confidence: 99%

Polymer Networks for Enrichment of Calcium Ions

et al. 2021

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In this study, solvogels containing (2-((2-(ethoxycarbonyl)prop-2-en-1-yl)oxy)-ethyl) phosphonic acid (ECPA) and N,N′-diethyl-1,3-bis-(acrylamido)propane (BNEAA) as the crosslinker are synthesized by UV induced crosslinking photopolymerization in various solvents. The polymerization of the ECPA monomer is monitored by the conversion of double bonds with in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. The morphology of the networks is characterized by in situ photorheology, solid state NMR spectroscopy, and scanning electron microscopy (SEM) of the dried gels. It is demonstrated that the storage modulus is not only determined by the crosslinker content in the gel, but also by the solvent used for preparation. The networks turn out to be porous structures with G′ being governed by a rigid, phase-separated polymer phase rather than by entropic elasticity. The external and internal pKa values of the poly(ECPA-co-BNEAA) gels were determined by titration with a specially designed method and compared to the calculated values. The polymer-immobilized phosphonic acid groups in the hydrogels induce buffering behavior into the system without using a dissolved buffer. The calcium accumulation in the gels is studied by means of a double diffusion cell filled with calcium ion-containing solutions. The successful accumulation of hydroxyapatite within the gels is shown by a combination of SEM, energy-dispersive X-ray spectroscopy (EDX) and wide-angle X-ray scattering (WAXS).

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Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

Cited by 3 publications

References 24 publications

Chemical Design of Hydrogels with Immobilized Laccase for the Reduction of Persistent Trace Compounds in Wastewater

Chemical Design of Hydrogels with Immobilized Laccase for the Reduction of Persistent Trace Compounds in Wastewater

A Review of Inline Infrared and Nuclear Magnetic Resonance Applications in Flow Chemistry

Polymer Networks for Enrichment of Calcium Ions

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