Wavelength-Dependent Activation of Photoacids and Bases.

Photoacids and bases allow remote control over pH in reaction solutions, which is of fundamental importance to an array of applications. Herein, we determine the wavelength-by-wavelength resolved photoreactivity of triarylsulfonium hexafluorophosphate salts as a representative photoacid generator and p-(benzoyl)benzyl triethylammonium tetraphenylborate as a photobase generator, constructing a wavelength-resolved photochemical action plot for each of the compounds. We monitor the pH change of the solution on-line within the cavity of the laser vial and demonstrate a marked mismatch between the absorption spectrum of the photoacid and base with the photochemical action plot, unveiling reactivity at very low absorptivities. Our findings are of critical importance for the use of photoacids and bases, unambiguously demonstrating that absorption is no guide to chemical reactivity with critical consequences for the wavelength employed in applications of photoacids and bases.

Structural basis for the unique molecular properties of broad-range phospholipase C from Listeria monocytogenes.

Listeriosis is one of the most serious foodborne diseases caused by the intracellular bacterium Listeria monocytogenes. Its two major virulence factors, broad-range phospholipase C (LmPC-PLC) and the pore-forming toxin listeriolysin O (LLO), enable the bacterium to spread in the host by destroying cell membranes. Here, we determine the crystal structure of LmPC-PLC and complement it with the functional analysis of this enzyme. This reveals that LmPC-PLC has evolved several structural features to regulate its activity, including the invariant position of the N-terminal tryptophan (W1), the structurally plastic active site, Zn2+-dependent activity, and the tendency to form oligomers with impaired enzymatic activity. We demonstrate that the enzymatic activity of LmPC-PLC can be specifically inhibited by its propeptide added in trans. Furthermore, we show that the phospholipase activity of LmPC-PLC facilitates the pore-forming activity of LLO and affects the morphology of LLO oligomerization on lipid membranes, revealing the multifaceted synergy of the two virulence factors.

Dynamic Properties of Di(cyclopentadienecarboxylic Acid) Dimethyl Esters.

Di(cyclopentadienecarboxylic acid) dimethyl ester (DCPDME) is a potential dynamic covalent system. When such molecules are used as dynamic crosslinkers in polymers, understanding the reversibility of cyclopentadiene dimerization is crucial to determine optimal melt processing conditions. To this end, we synthesized DCPDME, which consists of three regioisomers with different physicochemical properties, which were investigated by isolating them and further characterizing them using 1H NMR, FTIR and DSC. There have been many attempts to improve the synthesis process to increase the reaction yield and purity of isomer 3, and this goal remains a challenge today. In this work, we show that pure isomers 1 and 2 irreversibly convert to the more stable DCPDME isomer 3 at temperatures between 120 and 140 °C in N2. This shows that isolation of the pure isomer 3 from the DCPDME isomer mixture is not necessary. The DCPDME isomer 3 is reversibly cleaved to the monomeric cyclopentadienecarboxylic acid methyl ester (CPME), as confirmed with GC-MS and the resulting mass spectrum. The conversion of DCPDME isomers 1 and 2 to isomer 3 was confirmed by heating the synthesized mixture of DCPDME isomers at 135 °C for 5 min in N2, producing an almost pure isomer 3 which increased its synthesis yield by 35%.

Chemical Recycling of Flexible Polyurethane Foams by Aminolysis to Recover High-Quality Polyols.

Polyurethane foams (PUFs) are widely used commodity materials, but most of them end up in landfills at the end of their life, which is not in line with the circular economy approach. Here, we introduce microwave-assisted aminolysis with amine reagents that contain primary and tertiary amino groups in the structure. These reagents enable complete degradation of the urethane groups in the structure of the flexible PUFs with a much lower amount of degradation reagent than is typically required for solvolysis reactions. The purified, recovered polyols are close equivalents to the corresponding virgin polyols in terms of their structural and molar mass characteristics. Therefore, they can be used for the production of high-quality PUFs without having to adapt the synthesis process. The flexible PUFs made from recovered polyols have comparable mechanical properties to those made from virgin polyols.

Determination of End-Group Functionality of Propylene Oxide-Based Polyether Polyols Recovered from Polyurethane Foams by Chemical Recycling.

Chemical recycling of polyurethane foams (PUFs) leads to partially aromatic, amino-functionalized polyol chains when the urethane groups in the PUF structure are incompletely degraded. Since the reactivity of amino and hydroxyl groups with isocyanate groups is significantly different, information on the type of the end-group functionality of recycled polyols is important to adjust the catalyst system accordingly to produce PUFs from recycled polyols of suitable quality. Therefore, we present here a liquid adsorption chromatography (LAC) method using a SHARC 1 column that separates polyol chains according to their end-group functionality based on their ability to form hydrogen bonds with the stationary phase. To correlate end-group functionality of recycled polyol with chain size, LAC was coupled with size-exclusion chromatography (SEC) to form a two-dimensional liquid chromatography system. For accurate identification of peaks in LAC chromatograms, the results were correlated with those obtained by characterization of recycled polyols using nuclear magnetic resonance, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and SEC coupled with a multi-detection system. The developed method allows the quantification of fully hydroxyl-functionalized chains in recycled polyols using an evaporative light scattering detector and appropriate calibration curve.

Synthesis of Optically and Redox Active Polyenaminones from Diamines and α,α'-Bis[(dimethylamino)methylidene]cyclohexanediones.

New oligo- and polyenaminones with Mw ~ 7-50 KDa were prepared in high yields by transaminative amino-enaminone polymerization of regioisomeric bis[(dimethylamino)methylidene]cyclohexanediones with alkylene and phenylenediamines. The polymers obtained are practically insoluble in aqueous and organic solvents and exhibit film-forming properties, UV light absorption at wavelengths below 500 nm, and redox activity. These properties indicate a promising application potential of these polymers, which could find use in optical and optoelectronic applications and in energy storage devices.

Water as a monomer: synthesis of an aliphatic polyethersulfone from divinyl sulfone and water.

Using water as a monomer in polymerization reactions presents a unique and exquisite strategy towards more sustainable chemistry. Herein, the feasibility thereof is demonstrated by the introduction of the oxa-Michael polyaddition of water and divinyl sulfone. Upon nucleophilic or base catalysis, the corresponding aliphatic polyethersulfone is obtained in an interfacial polymerization at room temperature in high yield (>97%) within an hour. The polyethersulfone is characterized by relatively high molar mass averages and a dispersity around 2.5. The polymer was tested as a solid polymer electrolyte with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as the salt. Free-standing amorphous membranes were prepared by a melt process in a solvent-free manner. The polymer electrolyte containing 15 wt% LiTFSI featured an oxidative stability of up to 5.5 V vs. Li/Li+ at 45 °C and a conductivity of 1.45 × 10-8 S cm-1 at room temperature.

Cellulose Structures as a Support or Template for Inorganic Nanostructures and Their Assemblies.

Cellulose is the most abundant natural polymer and deserves the special attention of the scientific community because it represents a sustainable source of carbon and plays an important role as a sustainable energent for replacing crude oil, coal, and natural gas in the future. Intense research and studies over the past few decades on cellulose structures have mainly focused on cellulose as a biomass for exploitation as an alternative energent or as a reinforcing material in polymer matrices. However, studies on cellulose structures have revealed more diverse potential applications by exploiting the functionalities of cellulose such as biomedical materials, biomimetic optical materials, bio-inspired mechanically adaptive materials, selective nanostructured membranes, and as a growth template for inorganic nanostructures. This article comprehensively reviews the potential of cellulose structures as a support, biotemplate, and growing vector in the formation of various complex hybrid hierarchical inorganic nanostructures with a wide scope of applications. We focus on the preparation of inorganic nanostructures by exploiting the unique properties and performances of cellulose structures. The advantages, physicochemical properties, and chemical modifications of the cellulose structures are comparatively discussed from the aspect of materials development and processing. Finally, the perspective and potential applications of cellulose-based bioinspired hierarchical functional nanomaterials in the future are outlined.

Influence of Microstructure on the Elution Behavior of Gradient Copolymers in Different Modes of Liquid Interaction Chromatography.

We studied the influence of microstructure on the chromatographic behavior of gradient copolymers with different gradient strengths and block copolymer with completely segregated blocks by using gradient liquid adsorption chromatography (gLAC) and liquid chromatography at critical conditions (LCCC) for one of the copolymer constituents. The copolymers consist of repeating units of poly(propylene oxide) and poly(propylene phthalate) and have comparable average chemical composition and molar mass, and a narrow molar mass distribution to avoid as much as possible the influence of these parameters on the elution behavior of the copolymers. On both reversed stationary phases, the elution volume of gradient copolymers increases with the increasing strength of the gradient. The results indicate that for both modes of liquid interaction chromatography, it is important to consider the effect of microstructure on the elution behavior of the gradient copolymers in addition to the copolymer chemical composition and molar mass in the case of gLAC and the length of the chromatographically visible copolymer constituent in the case of LCCC.

Insight into Chemical Recycling of Flexible Polyurethane Foams by Acidolysis.

Acidolysis is emerging as a promising method for recycling polyurethane foam (PUF) waste. Here, we present highly efficient acidolysis of PUFs with adipic acid (AA) by heating the reaction mixtures with microwaves. The influence of experimental conditions, such as reaction temperature, time, and amount of the degradation reagent, on the polyol functionality, molecular weight characteristics, the presence of side products, and the degree of degradation of the remaining PUF hard segments was studied by matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS), nuclear magnetic resonance (NMR), size-exclusion chromatography (SEC) coupled to a multidetection system, and Fourier transform infrared (FT-IR) spectroscopy. The purified recycled polyols were used for the synthesis of flexible PUFs. The morphology and mechanical properties of the PUFs show that the degree of functionalization of the polyol by the carboxylic end groups, which is higher for larger amounts of AA used to degrade the PUFs, significantly affects the quality and performance of the flexible PUFs from the recycled polyols.

Integral analysis of hydrodynamic cavitation effects on waste activated sludge characteristics, potentially toxic metals, microorganisms and identification of microplastics.

Wastewater treatment plants, the last barrier between ever-increasing human activities and the environment, produce huge amounts, of unwanted semi-solid by-product - waste activated sludge. Anaerobic digestion can be used to reduce the amount of sludge. However, the process needs extensive modernisation and refinement to realize its full potential. This can be achieved by using efficient pre-treatment processes that result in high sludge disintegration and solubilization. To this end, we investigated the efficiency of a novel pinned disc rotational generator of hydrodynamic cavitation. The results of physical and chemical evaluation showed a reduction in mean particle size up to 88%, an increase in specific surface area up to 300% and an increase in soluble COD, NH4-N, NO3-N, PO4-P up to 155.8, 126.3, 250 and 29.7%, respectively. Microscopic images confirmed flocs disruption and damage to yeast cells and Epistilys species due to mechanical effects of cavitation such as microjets and shear forces. The observed cell ruptures and cracks were sufficient for the release of small soluble biologically relevant dissolved organic molecules into the bulk liquid, but not for the release of microbial DNA. Cavitation treatment also decreased total Pb concentrations by 70%, which was attributed to the reactions triggered by the chemical effects of cavitation. Additionally, the study confirmed the presence of microplastic particles and fibers of polyethylene, polyethylene terephthalate, polypropylene, and nylon 6 in the waste activated sludge.

Highly Porous Poly(arylene cyano-vinylene) Beads Derived through the Knoevenagel Condensation of the Oil-in-Oil-in-Oil Double Emulsion Templates.

Conjugated porous polymers through the emulsion-templating polymerization process are typically prepared as monoliths, and the emulsions are cured via metal-catalyzed cross-coupling reactions. Herein, we report the design and synthesis of well-defined, millimeter-sized conjugated porous polymer beads by combining an oil-in-oil-in-oil (O/O/O) double emulsion as a de novo template and an amino-catalyzed Knoevenagel condensation reaction as a polymerization chemistry to cure such emulsions. The 1,4-phenylenediacetonitrile is reacted with aromatic multialdehydes in the presence of piperidine, and a series of metal-free poly(arylene cyano-vinylene) beads are prepared. All beads exhibit 3D-interconnected microcellular morphology and substantial semiconducting properties, such as strong light harvesting ability in the visible light region with electrochemical band gaps in the range of 2.05-2.33 eV. Finally, the promising photocatalytic activity of these conjugated beads is demonstrated for a model sulfoxidation reaction under visible light irradiation, and near quantitative conversions with excellent chemoselectivities (>99%) are obtained.

Noncovalent Protection for Direct Synthesis of α-Amino-ω-hydroxyl Poly(ethylene oxide).

The synthesis of poly(ethylene oxide) (PEO) with amino end group, a key functionality for PEGylation, is a long-standing challenge. Multistep routes based on postmodification or covalent protection have been adopted to circumvent ethoxylation of the amino group by ethylene oxide (EO). Here, we report a noncovalent protection strategy for one-step synthesis of PEO amine. An amino (di)alcohol is mixed with a small amount of mild phosphazene base and excess triethylborane (Et3B) before addition of EO. The complexation of the amino group with Et3B guarantees that polymerization of EO occurs selectively from the hydroxyl group through the bicomponent metal-free catalysis. Simply by precipitation in diethyl ether, the protective Et3B as well as the catalyst can be removed to afford α-amino-ω-hydroxyl PEO with controlled molar mass, low dispersity, and complete end functionality. The effect of initiator structure and retention of Et3B on the storage (oxidative) stability of PEO amine is also revealed.

Enrichment of plasma extracellular vesicles for reliable quantification of their size and concentration for biomarker discovery.

Human plasma is a complex fluid, increasingly used for extracellular vesicle (EV) biomarker studies. Our aim was to find a simple EV-enrichment method for reliable quantification of EVs in plasma to be used as biomarker of disease. Plasma of ten healthy subjects was processed using sedimentation rate- (sucrose cushion ultracentrifugation-sUC) and size- (size exclusion chromatography-SEC) based methods. According to nanoparticle tracking analysis (NTA), asymmetrical flow field-flow fractionation coupled to detectors (AF4-UV-MALS), miRNA quantification, transmission electron microscopy and enzyme-linked immunosorbent assay, enrichment of EVs from plasma with sUC method lead to high purity of EVs in the samples. High nanoparticle concentrations after SEC resulted from substantial contamination with lipoproteins and other aggregates of EV-like sizes that importantly affect downstream EV quantification. Additionally, sUC EV-enrichment method linked to quantification with NTA or AF4-UV-MALS is repeatable, as the relative standard deviation of EV size measured in independently processed samples from the same plasma source was 5.4% and 2.1% when analyzed by NTA or AF4-UV-MALS, respectively. In conclusion, the sUC EV-enrichment method is compatible with reliable measurement of concentration and size of EVs from plasma and should in the future be tested on larger cohorts in relation to different diseases. This is one of the first studies using AF4-UV-MALS to quantify EVs in blood plasma, which opens new possible clinical utility for the technique.

Chemical Recycling of Aliphatic Polyamides by Microwave-Assisted Hydrolysis for Efficient Monomer Recovery.

We report on a simple and efficient chemical recycling process for aliphatic polyamides (PA 66, PA 1010, PA 11, and PA 12), whereby PAs are converted exclusively into their constituent monomers even in the presence of reinforcement additives, such as carbon- and glass-fibers. In this process, the rate of PA hydrolysis reaction, performed under microwave irradiation in the presence of HCl as an acid catalyst, depends on the PA type, the HCl/amide mole ratio, and the type and amount of reinforcement additives. PA 66 is completely converted into the constituent monomers at 200 °C and a 1.25 HCl/amide mole ratio in 10 min. Long-chain PAs (PA 11, PA 12, and PA 1010) and PAs containing glass- or carbon-fiber reinforcement additives need at the same experimental conditions longer reaction times. Alternatively, they can be completely hydrolyzed at 200 °C within a comparable reaction time at a higher HCl/amide mole ratio of 2.5. Complete and straightforward conversion of PAs into the constituent monomers in the absence of side reactions simplifies the isolation and purification of monomers and reinforcement additives, which have been recovered in high yields and quality comparable to those of commercially available chemicals.

Functional macroporous amphoteric polyelectrolyte monoliths with tunable structures and properties through emulsion-templated synthesis.

HYPOTHESIS: Macroporous polyampholyte hydrogels, simultaneously bearing both the anionic and cationic groups, demonstrate immense promise over the one-sign charged polyelectrolytes, owing to a unique phenomenon known as the ˝anti-polyelectrolyte˝ effect. Thus, they are extremely promising materials, since they remain solvated and functional even in harsh conditions. Furthermore, macroporous morphology significantly enhances polyampholyte response to external stimuli, since it accelerates the solvent transport through the hydrogel. EXPERIMENTS: A new templated-synthesis through "HIPE mixtures" is reported, where the two pre-formed high internal phase emulsions (HIPE) containing the oppositely charged monomers (2-acrylamido-2-methyl-1-propanesulfonic acid and (3-acrylamidopropyl)trimethylammonium chloride) were combined in the same mould, which after polymerization result in the formation of macroporous monoliths of different structures. The resulting frameworks were either copolymer or dual homopolymers in the form of bilayered or mixed porous structures. FINDINGS: The co- and mixed-amphoteric polyelectrolytes exhibit 'anti-polyelectrolyte' behaviour typical of polyampholytes, while the bilayered-structure behaves like a typical polyelectrolyte. Complete and simultaneous removal of both dyes from a dye mixture was observed for the bilayered- and mixed-amphoteric polyelectrolyte, while copoly-ampholyte showed only partial dye adsorption. These results clearly reveal the benefits of a mutual combination of the HIPE-templated structure and the oppositely charged amphoteric nature in one-piece material as a promising avenue toward advanced materials.

The Neurotropic Black Yeast Exophiala dermatitidis Induces Neurocytotoxicity in Neuroblastoma Cells and Progressive Cell Death.

The neurotropic and extremophilic black yeast Exophiala dermatitidis (Herpotrichellaceae) inhabits diverse indoor environments, in particular bathrooms, steam baths, and dishwashers. Here, we show that the selected strain, EXF-10123, is polymorphic, can grow at 37 °C, is able to assimilate aromatic hydrocarbons (toluene, mineral oil, n-hexadecane), and shows abundant growth with selected neurotransmitters (acetylcholine, gamma-aminobutyric acid, glycine, glutamate, and dopamine) as sole carbon sources. We have for the first time demonstrated the effect of E. dermatitidis on neuroblastoma cell model SH-SY5Y. Aqueous and organic extracts of E. dermatitidis biomass reduced SH-SY5Y viability by 51% and 37%, respectively. Melanized extracellular vesicles (EVs) prepared from this strain reduced viability of the SH-SY5Y to 21%, while non-melanized EVs were considerably less neurotoxic (79% viability). We also demonstrated direct interactions of E. dermatitidis with SH-SY5Y by scanning electron and confocal fluorescence microscopy. The observed invasion and penetration of neuroblastoma cells by E. dermatitidis hyphae presumably causes the degradation of most neuroblastoma cells in only three days. This may represent a so far unknown indirect or direct cause for the development of some neurodegenerative diseases such as Alzheimer's.

Zeolite Nanocrystals Embedded in Microcellular Carbon Foam as a High-Performance CO2 Capture Adsorbent with Energy-Saving Regeneration Properties.

Here, the facile synthesis of four-length-scaled (ultramicro-micro-meso-macroporous) hierarchically structured porous carbon nanocomposite by an emulsion-template strategy is reported. This previously unreported combination of zeolite nanocrystals embedded in the walls of microcellular carbon foams gives unique textural and structural properties, which result in their excellent ability to selectively capture CO2 owing to the presence of ultra-micropores. The zeolite-microcellular carbon foam synergism delivers an adsorbent with a significantly enhanced CO2 capture capacity of up to 5 mmol g-1 , CO2 /N2 selectivity of up to 80, and an outstanding multi-cycle capture performance under humid conditions (70 % performance retention after 30 regeneration cycles). More impressively, the electrically conductive carbon framework enables Joule heating and cooling, and thus fast and energy-efficient regeneration is possible, with an estimated energy consumption of only about 12 kWh.

Chemical Structure-Antioxidant Activity Relationship of Water-Based Enzymatic Polymerized Rutin and Its Wound Healing Potential.

The flavonoid rutin (RU) is a known antioxidant substance of plant origin. Its potential application in pharmaceutical and cosmetic fields is, however, limited, due to its low water solubility. This limitation can be overcome by polymerization of the phenolic RU into polyrutin (PR). In this work, an enzymatic polymerization of RU was performed in water, without the addition of organic solvents. Further, the chemical structure of PR was investigated using 1H NMR, and FTIR spectroscopy. Size-exclusion chromatography (SEC) was used to determine the molecular weight of PR, while its acid/base character was studied by potentiometric charge titrations. Additionally, this work investigated the antioxidant and free radical scavenging potential of PR with respect to its chemical structure, based on its ability to (i) scavenge non biological stable free radicals (ABTS), (ii) scavenge biologically important oxidants, such as O2•, NO•, and OH•, and (iii) chelate Fe2+. The influence of PR on fibroblast and HaCaT cell viability was evaluated to confirm the applicability of water soluble PR for wound healing application.

Porous Polystyrene Monoliths Prepared from in Situ Simultaneous Interpenetrating Polymer Networks: Modulation of Morphology by Polymerization Kinetics.

Semi-interpenetrating polymer networks (semi-IPNs) were prepared by in situ simultaneous orthogonal polymerizations, where the linear poly(ε-caprolactone) (PCL) was synthesized by ring-opening polymerization of ε-caprolactone and the poly(styrene-co-divinylbenzene) (PS) network was formed by free-radical polymerization of styrene/divinylbenzene. Semi-IPNs were used as the precursors for the preparation of porous PS monoliths. To this end, the PCL domains were selectively removed by hydrolysis under basic conditions. By changing the amount of organocatalyst used for the ring-opening polymerization of ε-caprolactone, the relative polymerization kinetics of both monomers was varied, which has a pronounced effect on the morphology of thus-obtained PS frameworks.