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Oxidation by RuO4 (generated in situ from RuO2 and NaIO4) of secondary amines such as Bn–NH–CH2R (1; R=H, Me) gave complex reaction mixtures, but mainly amides. In the presence of cyanide, the leading products were α-aminonitriles. Comparison of the oxidation products of 1 with those from the corresponding imines PhCH=N–CH2R and Bn–N=CH–R showed that formation of the indicated imines is the first main step in the oxidation of 1. A detailed mechanism is proposed.

This study presents for the first time the polymerization of methyl methacrylate (MMA) in the presence of poly(vinyl chloride) (PVC) that takes place by both SARA-ATRP and SET-LRP mechanisms. The two types of polymerizations that occur in the system are PMMA grafting to the PVC backbone and the formation of a new PMMA polymer, both occurring in the presence of a Cu 0 wire. The polymerizations were controlled as confirmed by the molecular weight evolution, polymerization kinetics, and variations in the dispersity value. The MMA polymerization in the presence of PVC at 60 and 70 °C leads to the formation of two polymer species characterized by an increase in the molecular weight with the conversion and a narrowing of the dispersity value with the reaction progress. To increase the degree of control over the polymerization, the same reaction was performed at room temperature, which allowed us to highlight the presence of the SARA-ATRP and SET-LRP mechanisms via subsequent polymer chain extensions. The results demonstrated that PMMA grafting on PVC polymers follows a SARA-ATRP mechanism, while the formation of a PMMA homopolymer entails a SET-LRP process. The influence of solvent nature on the polymerization reaction was studied by performing the grafting of N -isopropylacrylamide (NIPAM) onto the surface of PVC particles in aqueous media in the presence and in the absence of CuCl 2 . The polymerization reactions and the obtained materials were studied by gel permeation chromatography (GPC), 1 H NMR, DMA, scanning electron microscopy (SEM), and atomic force microscopy (AFM)., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Three-dimensional (3D) printing technology was able to generate great attention because of its unique methodology and for its major potential to manufacture detailed and customizable scaffolds in terms of size, shape and pore structure in fields like medicine, pharmaceutics and food. This study aims to fabricate an ink entirely composed of natural polymers, alginate, k-carrageenan and carboxymethyl cellulose (AkCMC). Extrusion-based 3D printing was used to obtain scaffolds based on a crosslinked interpenetrating polymer network from the alginate, k-carrageenan, carboxymethyl cellulose and glutaraldehide formulation using CaCl 2 , KCl and glutaraldehyde in various concentrations of acetic acid. The stabile bonding of the crosslinked scaffolds was assessed using infrared spectroscopy (FT-IR) as well as swelling, degradation and mechanical investigations. Moreover, morphology analysis (µCT and SEM) confirmed the 3D printed samples' porous structure. In the AkCMC-GA objects crosslinked with the biggest acetic acid concentration, the values of pores and walls are the highest, at 3.9 × 10 -2 µm -1 . Additionally, this research proves the encapsulation of vitamin B1 via FT-IR and UV-Vis spectroscopy. The highest encapsulation efficiency of vitamin B1 was registered for the AkCMC-GA samples crosslinked with the maximum acetic acid concentration. The kinetic release of the vitamin was evaluated by UV-Vis spectroscopy. Based on the results of these experiments, 3D printed constructs using AkCMC-GA ink could be used for soft tissue engineering applications and also for vitamin B1 encapsulation.

This work reports the development of a marine-derived polysaccharide formulation based on k-Carrageenan and sodium alginate in order to produce a novel scaffold for engineering applications. The viscoelastic properties of the bicomponent inks were assessed via rheological tests prior to 3D printing. Compositions with different weight ratios between the two polymers, without any crosslinker, were subjected to 3D printing for the first time, to the best of our knowledge, and the fabrication parameters were optimized to ensure a controlled architecture. Crosslinking of the 3D-printed scaffolds was performed in the presence of a chloride mixture (CaCl 2 :KCl = 1:1; v / v ) of different concentrations. The efficiency of the crosslinking protocol was evaluated in terms of swelling behavior and mechanical properties. The swelling behavior indicated a decrease in the swelling degree when the concentration of the crosslinking agent was increased. These results are consistent with the nanoindentation measurements and the results of the macro-scale tests. Moreover, morphology analysis was also used to determine the pore size of the samples upon freeze-drying and the uniformity and micro-architectural characteristics of the scaffolds. Overall, the registered results indicated that the bicomponent ink, Alg/kCG = 1:1 may exhibit potential for tissue-engineering applications.

The saponification value of fats and oils is one of the most common quality indices, reflecting the mean molecular weight of the constituting triacylglycerols. Proton nuclear magnetic resonance ( 1 H-NMR) spectra of fats and oils display specific resonances for the protons from the structural patterns of the triacylglycerols (i.e., the glycerol backbone), methylene (-CH 2 -) groups, double bonds (-CH=CH-) and the terminal methyl (-CH 3 ) group from the three fatty acyl chains. Consequently, chemometric equations based on the integral values of the 1 H-NMR resonances allow for the calculation of the mean molecular weight of triacylglycerol species, leading to the determination of the number of moles of triacylglycerol species per 1 g of fat and eventually to the calculation of the saponification value (SV), expressed as mg KOH/g of fat. The algorithm was verified on a series of binary mixtures of tributyrin (TB) and vegetable oils (i.e., soybean and rapeseed oils) in various ratios, ensuring a wide range of SV. Compared to the conventional technique for SV determination (ISO 3657:2013) based on titration, the obtained 1 H-NMR-based saponification values differed by a mean percent deviation of 3%, suggesting the new method is a convenient and rapid alternate approach. Moreover, compared to other reported methods of determining the SV from spectroscopic data, this method is not based on regression equations and, consequently, does not require calibration from a database, as the SV is computed directly and independently from the 1 H-NMR spectrum of a given oil/fat sample.

This work pledge to extend the therapeutic windows of hybrid nanoparticulate systems by engineering mannose-decorated hybrid nanoparticles based on poly lactic-co-glycolic acid (PLGA) and vegetable oil for efficient delivery of two lipophilic anti-inflammatory therapeutics (Celecoxib-CL and Indomethacin-IMC) to macrophages. The mannose surface modification of nanoparticles is achieved via O-palmitoyl-mannose spacer during the emulsification and nanoparticles assembly process. The impact of targeting motif on the hydrodynamic features (R H , PdI), stability (ζ-potential), drug encapsulation efficiency (DEE) is thoroughly investigated. Besides, the in vitro biocompatibility (MTT, LDH) and susceptibility of mannose-decorated formulations to macrophage as well their immunomodulatory activity (ELISA) are also evaluated. The monomodal distributed mannose-decorated nanoparticles are in the range of nanometric size (R H < 115 nm) with PdI < 0.20 and good encapsulation efficiency (DEE = 46.15% for CL and 76.20% for IMC). The quantitative investigation of macrophage uptake shows a 2-fold increase in fluorescence (RFU) of cells treated with mannose-decorated formulations as compared to non-decorated ones (p < 0.001) suggesting an enhanced cell uptake respectively improved macrophage targeting while the results of ELISA experiments suggest the potential immunomodulatory properties of the designed mannose-decorated hybrid formulations., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Nuclear magnetic resonance (NMR) metabolomics is currently popular enough to attract both specialized and non-specialized NMR groups involving both analytical trained personnel and newcomers, including undergraduate students. Recent interlaboratory studies performed by established NMR metabolomics groups demonstrated high reproducibility of the state-of-the-art NMR equipment and SOPs. There is, however, no assessment of NMR reproducibility when mixing both analytical experts and newcomers. An interlaboratory assessment of NMR quantitation reproducibility was performed using two NMR instruments belonging to different laboratories and involving several operators with different backgrounds and metabolomics expertise for the purpose of assessing the limiting factors for data reproducibility in a multipurpose NMR environment. The variability induced by the operator, automatic pipettes, NMR tubes and NMR instruments was evaluated in order to assess the limiting factors for quantitation reproducibility. The results estimated the expected reproducibility data in a real-life multipurpose NMR laboratory to a maximum 4% variability, demonstrating that the current NMR equipment and SOPs may compensate some of the operator-induced variability.

The main objective was to produce 3D printable hydrogels based on GelMA and hydroxyapatite doped with cerium ions with potential application in bone regeneration. The first part of the study regards the substitution of Ca 2+ ions from hydroxyapatite structure with cerium ions (Ca 10-x Ce x (PO 4 ) 6 (OH) 2 , xCe = 0.1, 0.3, 0.5). The second part followed the selection of the optimal concentration of HAp doped, which will ensure GelMA-based scaffolds with good biocompatibility, viability and cell proliferation. The third part aimed to select the optimal concentrations of GelMA for the 3D printing process (20%, 30% and 35%). In vitro biological assessment presented the highest level of cell viability and proliferation potency of GelMA-HC5 composites, along with a low cytotoxic potential, highlighting the beneficial effects of cerium on cell growth, also supported by Live/Dead results. According to the 3D printing experiments, the 30% GelMA enriched with HC5 was able to generate 3D scaffolds with high structural integrity and homogeneity, showing the highest suitability for the 3D printing process. The osteogenic differentiation experiments confirmed the ability of 30% GelMA-3% HC5 scaffold to support and efficiently maintain the osteogenesis process. Based on the results, 30% GelMA-3% HC5 3D printed scaffolds could be considered as biomaterials with suitable characteristics for application in bone tissue engineering.

The present research work is focused on the design and investigation of electrospun composite membranes based on citric acid-functionalized chitosan (CsA) containing reduced graphene oxide-tetraethylene pentamine (CsA/rGO-TEPA) as materials with opportune bio-properties for applications in wound dressings. The covalent functionalization of chitosan (CS) with citric acid (CA) was achieved through the EDC/NHS coupling system and was checked by 1 H-NMR spectroscopy and FTIR spectrometry. The mixtures to be electrospun were formulated by adding three concentrations of rGO-TEPA into the 1/1 ( w / w ) CsA/poly (ethylene oxide) (PEO) solution. The effect of rGO-TEPA concentration on the morphology, wettability, thermal stability, cytocompatibility, cytotoxicity, and anti-biofilm activity of the nanofibrous membranes was extensively investigated. FTIR and Raman results confirmed the covalent and non-covalent interactions that appeared between the system's compounds, and the exfoliation of rGO-TEPA sheets within the CsA in the presence of PEO (CsA/P) polymer matrix, respectively. SEM analysis emphasized the nanofibrous architecture of membranes and the presence of rGO-TEPA sheets entrapped into the CsA nanofiber structure. The MTT cellular viability assay showed a good cytocompatibility with the highest level of cell development and proliferation registered for the CsA/P composite nanofibrous membrane with 0.250 wt.% rGO-TEPA. The designed nanofibrous membranes could have potential applications in wound dressings, given that they showed a good anti-biofilm activity against Gram-negative Pseudomonas aeruginosa and Gram-positive Staphylococcus aureus bacterial strains.

The development of materials for 3D printing adapted for tissue engineering represents one of the main concerns nowadays. Our aim was to obtain suitable 3D-printed scaffolds based on methacrylated gelatin (GelMA). In this respect, three degrees of GelMA methacrylation, three different concentrations of GelMA (10%, 20%, and 30%), and also two concentrations of photoinitiator (I-2959) (0.5% and 1%) were explored to develop proper GelMA hydrogel ink formulations to be used in the 3D printing process. Afterward, all these GelMA hydrogel-based inks/3D-printed scaffolds were characterized structurally, mechanically, and morphologically. The presence of methacryloyl groups bounded to the surface of GelMA was confirmed by FTIR and 1 H-NMR analyses. The methacrylation degree influenced the value of the isoelectric point that decreased with the GelMA methacrylation degree. A greater concentration of photoinitiator influenced the hydrophilicity of the polymer as proved using contact angle and swelling studies because of the new bonds resulting after the photocrosslinking stage. According to the mechanical tests, better mechanical properties were obtained in the presence of the 1% initiator. Circular dichroism analyses demonstrated that the secondary structure of gelatin remained unaffected during the methacrylation process, thus being suitable for biological applications.

We introduce a new symmetry-based method for structural investigations of areas surrounding water-exchanging hydrogens in biomolecules by liquid-state nuclear magnetic resonance spectroscopy. Native structures of peptides and proteins can be solved by NMR with fair resolution, with the notable exception of labile hydrogen sites. The reason why biomolecular structures often remain elusive around exchangeable protons is that the dynamics of their exchange with the solvent hampers the observation of their signals. The new spectroscopic method we report allows to locate water-originating hydrogens in peptides and proteins via their effect on nuclear magnetic transitions similar to electronic phosphorescence, long-lived coherences. The sign of long-lived coherences excited in coupled protons can be switched by the experimenter. The different effect of water-exchanging hydrogens on long-lived coherences with opposed signs allows to pinpoint the position of these labile hydrogen atoms in the molecular framework of peptides and proteins.

Protein and peptide interactions are characterized in the liquid state by multidimensional NMR spectroscopy experiments, which can take hours to record. We show that starting from hyperpolarized HDO, two-dimensional (2D) proton correlation maps of a peptide, either free in solution or interacting with liposomes, can be acquired in less than 60 s. In standard 2D NMR spectroscopy without hyperpolarization, the acquisition time required for similar spectral correlations is on the order of hours. This hyperpolarized experiment enables the identification of amino acids featuring solvent-interacting hydrogens and provides fast spectroscopic analysis of peptide conformers. Sensitivity-enhanced 2D proton correlation spectroscopy is a useful and straightforward tool for biochemistry and structural biology, as it does not recur to nitrogen-15 or carbon-13 isotope enrichment.

Starting from Kryptofix 22 two different branches were covalently attached through the nitrogen atoms, one containing a fluorescent moiety and the other the stable free radical TEMPO. The novel derivative exhibits fluorescence and paramagnetic properties, while the diaza-crown part ensures the affinity for alkaline metal-ions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Background: Capsules containing a dye were prepared by the LbL method with iron oxide nanoparticles (50 nm) in different layers of the shell., Method: The capsules were dispersed in a gel and subjected to focused ultrasonic irradiation at three different powers and exposure times., Result: It was found that the inclusion of iron oxide magnetic nanoparticles in any of the polyelectrolyte shells (4, 6, 8 and 10) strengthened the capsules with respect to capsules without nanoparticles. Incorporation of nanoparticles in shell 8 provided the most resistance to fragmentation under focused ultrasonic irradiation. The relative degree of capsule stability is dependent on both the power of the ultrasound and the exposure time., Conclusion: The presence of iron oxide nanoparticles not only conferred more resistance to fragmentation but also provided a route to protein labelled dye release through sonoporation that was not present for capsules without nanoparticles., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Water uptake in vesicles and the subsequent exchange between water protons and amide -NH protons in amino acids can be followed by a new, highly sensitive, type of magnetic resonance spectroscopy: dynamic nuclear polarisation (DNP)-enhanced NMR in the liquid state. Water hydrogen atoms are detected prior to and after their transfer to molecular sites in peptides and proteins featuring highly-accessible proton-exchangeable groups, as is the case for the -NH groups of intrinsically disordered proteins. The detected rates for amide proton-water proton exchange can be modulated by membrane-crossing rates, when a membrane channel is interposed. We hyperpolarised water proton spins via dynamic nuclear polarisation followed by sample dissolution (d-DNP) and transferred the created polarisation to -NH groups with high solvent accessibility in an intrinsically disordered protein domain. This domain is the membrane anchor of c-Src kinase, whose activity controls cell proliferation. The hindrance of effective water proton transfer rate constants observed in free solvent when a membrane-crossing step is involved is discussed. This study aims to assess the feasibility of recently-introduced hyperpolarised (DNP-enhanced) NMR to assess water membrane crossing dynamics.

Long-lived states of nuclear spin order were used for the first time to probe interactions between molecules and diamagnetic metal ions. Proton spin states with lifetimes twice as long as the spin-lattice relaxation time constants of the same nuclei were promoted on the methoxyphenyl and tolyl substituents of a 1,3,4-oxadiazole derivative. The transient interaction of this oxadiazole derivative with silver(I) ions significantly speeds up the relaxation rate constants of proton long-lived states. The interactions between silver and organic compounds lead to the formation of coordination polymers that can be used for the preparation of bio-compatible materials., (Copyright © 2017 Elsevier Inc. All rights reserved.)

A bench scale continuous process for the manufacture of biodiesel from neat vegetable oils under high power low frequency ultrasonic irradiation was investigated. The experimental studies explored variations in alcohol-oil stoichiometry and type of oil. Important parameters such as residence time and reaction volume were considered. The highest conversion was achieved when short residence time was employed. The transesterification under ultrasonic irradiation is mainly influenced by the residence time in the reactor and alcohol-oil molar ratio.

The batch transesterification of vegetable oil with methanol, in the presence of potassium hydroxide as catalyst, by means of low frequency ultrasound (40 kHz) was studied with the aim of gaining more knowledge on intimate reaction mechanism. The concentration of fatty acid methyl esters, of mono-, di- and triglycerides of the actual reaction mixture were determined at short reaction time by HPLC. The effect of ultrasounds on the lipids transesterification correlated with triglyceride structures is discussed. It was found that under ultrasonic activation the rate-determining reaction switches from DG-->MG (classical mechanic agitation) to MG+ROH-->Gly+ME (ultrasonically driven transesterification).

The profile of fatty acid methyl esters (FAME) of different vegetable oils produced under ultrasonic irradiation and conventional heating were compared. In the presence of potassium hydroxide as catalyst, the distribution of FAME was quite similar for both procedures, while in the case of sodium hydroxide ultrasonic irradiation gave better results. The FAME profile resulted from the reaction catalyzed by sulfuric acid was almost the same with the one resulted from the reaction catalyzed by KOH, while boron trifluoride can give rise to many artifacts, thus is not a reliable catalyst.

The transesterification of vegetable oil with short-chain alcohols, in the presence of base-catalyst, by means of low frequency ultrasound (28 and 40 kHz) in order to obtain biodiesel fuel was studied. By using ultrasounds the reaction time is much shorter (10-40 min) than for mechanical stirring. The quantity of required catalyst is 2 or 3 times lower. The molar ratio of alcohol/oil used is only 6:1. Normal chain alcohols react fast, while secondary and tertiary alcohols show some or no conversion after 60 min of reaction. Surprisingly, 40 kHz ultrasounds are much more effective in the reduction of the reaction time (10-20 min). Twenty eight kilohertz give slightly better yields (98-99%), but longer reaction time, while higher frequencies are not useful at all for the transesterification of fatty acids.

The effect of PdSO4, PdCl2 and Pd(0) on the degradation of chlorobenzene in aqueous solution within 10 min under 200 kHz ultrasonic irradiation, was investigated. The reaction products remaining in the aqueous mixture were analyzed and quantified. The mechanism of chlorobenzene decomposition having benzene as key intermediate is discussed.

Ultrasonic inactivation of Escherichia coli XL1-Blue has been investigated by high-intensity ultrasonic waves from horn type sonicator (27.5 kHz) utilizing the "squeeze-film effect". The amplitude of the vibration face contacting the sample solution was used as an indication of the ultrasonic power intensity. The inactivation of the E. coli cells by ultrasonic irradiation shows pseudo first-order behavior. The inactivation rate constant gradually increased with increasing amplitude of the vibration face and showed rapid increase above 3 microm (p-p). In contrast, the H2O2 formation was not observed below 3 microm (p-p), indicating that the ultrasonic shock wave might be more important than indirect effect of OH radicals formed by ultrasonic cavitation in this system. The optimal thickness of the squeeze film was determined as 2 mm for the E. coli inactivation. More than 99% of E. coli cells was inactivated within 180-s sonication at the amplitude of 3 microm (p-p) and 2 mm of the thickness of the squeeze film.

We have investigated the inactivation of Saccharomyces cerevisiae (yeast cells) by ultrasonic irradiation. The amplitude on the vibration face contacting the sample solution was used as an indication of the ultrasonic power intensity. The effects of the amplitude on the vibration face and the initial cell numbers on the sonolytic inactivation of yeast cells have been investigated using a horn-type sonicator (27.5 kHz). The inactivation of the yeast cells by ultrasonic irradiation shows pseudo first-order behavior. The inactivation rate constant varied from 0.0007 to 0.145 s(-1) when the amplitude on the vibration face was in the range of 1-7 microm(p-p). The change in the inactivation rate constant as a function of the amplitude on the vibration face was similar to that of the OH radical formation rate under the same conditions. The threshold of this sonicator was 3 microm(p-p) with the amplitude on the vibration face. The initial cell numbers (from 10(2) to 10(5) mL(-1)) had an influence on the inactivation of the yeast cells by ultrasonic irradiation. The inactivation rate constants varied from 0.023 to 6.4 x 10(-3) s(-1), and the inactivation by ultrasonic irradiation was fastest at the lowest initial cell numbers. In a squeeze-film-type sonicator (26.6 kHz), 90% inactivation of the yeast cells was achieved by ultrasonic irradiation for 60 min.

The reaction of 5H,5Cl-dibenzo[a,d]cycloheptatriene with nitrobenzene was investigated under both thermal (210 degrees C) and ultrasonic (50 degrees C, 40 kHz) activation. The reaction products of both procedures are similar, but their amounts depend on the activation source. To account for the products a common electron transfer reaction is postulated through the dibenzotropylium cation. The differences between the thermal and ultrasonic process is thought to arise from the role of nitrobenzene as oxidant. Under thermal conditions this occurs throughout the reaction mixture but under sonication it occurs only in the cavitation bubble and in its immediate vicinity.

The influence of ultrasounds (200 kHz frequency) on the decomposition of chlorobenzene (CB) in a water solution (around 100 ppm concentration) containing iron or palladium sulfates was investigated. The intermediates of the sonolysis were identified, thus allowing a deeper insight into the degradation mechanism. It was established that CB degradation starts by pyrolysis inside the cavitation bubbles. The initial sonolysis product is benzene, formed in a reaction occurring outside the cavitation from phenyl radicals and the hydrogen atoms sonolytically generated from the water. Polyphenols as products of the CB sonochemical degradation are reported for the first time. The palladium salt was found to be a useful and sensitive indicator for differentiating the sites and mechanisms of the product formation. An alternative mechanism for the CB sonolysis is advanced, explaining the formation of phenols, polyphenols, chlorophenols and benzene.