Antibacterial membranes based on chitosan and quaternary ammonium salts modified nanocrystalline cellulose

Etherification of nanocrystalline cellulose (NCC) with three kinds of quaternary ammonium salts epoxypropyltrimethylammonium chloride, N,N‐dimethyl‐N‐dodecyl‐N‐(1,2‐epoxypropyl) ammonium chloride (DMDEPAC), and N,N‐dimethyl‐N‐octadecyl‐N‐(1,2‐epoxypropyl) ammonium chloride (DMOEPAC) was successfully performed via a nucleophilic addition reaction. The synthesized DMDEPAC and DMOEPAC were characterized by nuclear magnetic resonance. The modified NCC particles, NCC epoxypropyltrimethylammonium chloride, NCC‐DMDEPAC, and NCC‐DMOEPAC, were characterized by energy dispersive spectrometer. Nanocomposite films based on chitosan (CS) containing quaternary ammonium salts modified NCC were prepared with nanoparticle loadings of 5.0, 7.5, and 10.0%, respectively. The effect of nanoparticle content on the tensile strength of composite films was studied. The results indicated that the films with 5.0% nanoparticle loading exhibited the biggest increase in tensile strength. Surface morphology, smoothness, and antibacterial properties of composite films containing 5% modified NCC were also studied. CS/NCC‐DMDEPAC‐5.0 and CS/NCC‐DMOEPAC‐5.0 displayed excellent biocidal abilities against both Gram‐positive Staphylococcus aureus (ATCC 6538) and Gram‐negative Escherichia coli O157:H7 (ATCC 43895). The bio‐based nanocomposite films with increased mechanical strength and excellent antibacterial properties show great potential as food packaging materials. Copyright © 2017 John Wiley & Sons, Ltd.     

Quantitative Medium-Resolution NMR Spectroscopy Under Non-Equilibrium Conditions,Studied on the Example of an Esterification Reaction

Medium-resolution nuclear magnetic resonance spectroscopy is a promising tool for the monitoring of liquid reactions. For process analytical applications, the requirements of robustness and insensitivity of the spectrometer in relation to high temperatures and pressures are challenging. Within this study, a flow probe using a glass dewar is presented. Temperatures of flowing samples up to 130 °C and pressures up to 40 bar were successfully applied, and the corresponding temperature loss of the flowing sample at 2 ml min^?1 was <2.4 °C at 130 °C. Furthermore, if the process requires a measurement in a non-equilibrium state of magnetization, a comprehensive data treatment is given. For this purpose, the influences of the flow and T ₁ of the substances under investigation are studied in detail on the example of a homogeneously catalyzed esterification. In addition, data analysis schemes were designed such that the experiments directly revealed mole fractions from the spectra. Limited spectral resolutions and low signal-to-noise ratio still did not obstruct quantitative interpretation of the experiments.     

Structure and Properties of Ethene Copolymers Synthesized by Metallocene Catalysts

Abstract

The microstructure of ethylene copolymers based on 1-hexene, 1-octene, and norbornene as comonomers was studied and related to its melting, crystallization, and glass transition behavior as well as to tensile strength.     

Aryl‐Phosphonate Lanthanide Complexes and Their Fluorinated Derivatives: Investigation of Their Unusual Relaxometric Behavior and Potential Application as Dual Frequency 1H/19F MRI Probes

A series of low molecular weight lanthanide complexes were developed that have high ¹H longitudinal relaxivities (r₁) and the potential to be used as dual frequency ¹H and ¹⁹F MR probes. Their behavior was investigated in more detail through relaxometry, pH‐potentiometry, luminescence, and multinuclear NMR spectroscopy. Fitting of the ¹H NMRD and ¹⁷O NMR profiles demonstrated a very short water residence lifetime (<10 ns) and an appreciable second sphere effect. At lower field strengths (20 MHz), two of the complexes displayed a peak in r₁ (21.7 and 16.3 mM ^?1 s^?1) caused by an agglomeration, that can be disrupted through the addition of phosphate anions. NMR spectroscopy revealed that at least two species are present in solution interconverting through an intramolecular binding process. Two complexes provided a suitable signal in ¹⁹F NMR spectroscopy and through the selection of optimized imaging parameters, phantom images were obtained in a MRI scanner at concentrations as low as 1 mM . The developed probes could be visualized through both ¹H and ¹⁹F MRI, showing their capability to function as dual frequency MRI contrast agents.     

Die Selivanov‐Probe auf Fructose

The Seliwanoff's test is a useful tool in biochemistry and food chemistry as test for fructose and other hexoketoses. This article depicts the life and work of Russian chemist named F. F. Selivanov, who was born in aristocratic family, was affected by revolutionary Narodniki movement, and attended the universities in Russia, Switzerland and Germany. His life is a good example of connections between Russian and German agrochemical centres in XIX century. His major achievements are the test for fructose and the first synthesis of N‐Bromosuccinimide. He is also known as a doctoral supervisor of A.E. Arbuzov, the discoverer of Michaelis‐Arbuzov reaction.     

pH Tuning of Water-Soluble Arylazopyrazole Photoswitches

Arylazopyrazoles are an emerging class of photoswitches with redshifted switching wavelength, high photostationary states, long thermal half-lives and facile synthetic access. Understanding pathways for a simple modulation of the thermal half-lives, while keeping other parameters of interest constant, is an important aspect for out-of-equilibrium systems design and applications. Here, it is demonstrated that the thermal half-life of a water-soluble PEG-tethered arylazo-bis(o-methylated)pyrazole (AAP) can be tuned by more than five orders of magnitude using simple pH adjustment, which is beyond the tunability of azobenzenes. The mechanism of thermal relaxation is investigated by thorough spectroscopic analyses and density functional theory (DFT) calculations. Finally, the concepts of a tunable half-life are transferred from the molecular scale to the material scale. Based on the photochromic characteristics of E- and Z-AAP, transient information storage is showcased in form of light-written patterns inside films cast from different pH, which in turn leads to different times of storage. With respect to prospective precisely tunable materials and time-programmed out-of-equilibrium systems, an externally tunable half-life is likely advantageous over changing the entire system by the replacement of the photoswitch.     

Topochemical acetylation of cellulose nanopaper structures for biocomposites: mechanisms for reduced water vapour sorption

Moisture sorption decreases dimensional stability and mechanical properties of polymer matrix biocomposites based on plant fibers. Cellulose nanofiber reinforcement may offer advantages in this respect. Here, wood-based nanofibrillated cellulose (NFC) and bacterial cellulose (BC) nanopaper structures, with different specific surface area (SSA), ranging from 0.03 to 173.3 m²/g, were topochemically acetylated and characterized by ATR-FTIR, XRD, solid-state CP/MAS ¹³C-NMR and moisture sorption studies. Polymer matrix nanocomposites based on NFC were also prepared as demonstrators. The surface degree of substitution (surface-DS) of the acetylated cellulose nanofibers is a key parameter, which increased with increasing SSA. Successful topochemical acetylation was confirmed and significantly reduced the moisture sorption in nanopaper structures, especially at RH = 53 %. BC nanopaper sorbed less moisture than the NFC counterpart, and mechanisms are discussed. Topochemical NFC nanopaper acetylation can be used to prepare moisture-stable nanocellulose biocomposites.