Computational study of the dissolution of cellulose into single chains: the role of the solvent and agitation

We investigate the dissolution mechanism of cellulose using molecular dynamics simulations in both water and a mixture solvent consisting of water with Na$$^+$$ + , OH$$^-$$ - and urea. As a first computational study of its kind, we apply periodic external forces that mimic agitation of the suspension. Without the agitation, the bundles do not dissolve, neither in water nor solvent. In the solvent mixture the bundle swells with significant amounts of urea entering the bundle, as well as more water than in the bundles subjected to pure water. We also find that the mixture solution stabilizes cellulose sheets, while in water these immediately collapse into bundles. Under agitation the bundles dissolve more easily in the solvent mixture than in water, where sheets of cellulose remain that are bound together through hydrophobic interactions. Our findings highlight the importance of urea in the solvent, as well as the hydrophobic interactions, and are consistent with experimental results. Graphical abstract

Improvement of the Solubilization and Extraction of Curcumin in an Edible Ternary Solvent Mixture

A water-free, ternary solvent mixture consisting of a natural deep eutectic solvent (NADES), ethanol, and triacetin was investigated concerning its ability to dissolve and extract curcumin from Curcuma longa L. To this purpose, 11 NADES based on choline chloride, acetylcholine, and proline were screened using UV–vis measurements. A ternary phase diagram with a particularly promising NADES, based on choline chloride and levulinic acid was recorded and the solubility domains of the monophasic region were examined and correlated with the system’s structuring via light scattering experiments. At the optimum composition, close to the critical point, the solubility of curcumin could be enhanced by a factor of >1.5 with respect to acetone. In extraction experiments, conducted at the points of highest solubility and evaluated via HPLC, a total yield of ~84% curcuminoids per rhizome could be reached. Through multiple extraction cycles, reusing the extraction solvent, an enrichment of curcuminoids could be achieved while altering the solution. When counteracting the solvent change, even higher concentrated extracts can be obtained.

Simultaneous Distillation–Extraction of Essential Oils from Rosmarinus officinalis L.

The present study describes a procedure to isolate essential oils from Rosmarinus officinalis L. using simultaneous distillation–extraction (SDE). Rosmarinus officinalis L. can be used for medicinal purposes, as well in the cooking and cosmetics industries. SDE technique extraction combines a steam distillation combined with a continuous extraction using a solvent or a co-solvent mixture, providing faster extractions with low extraction solvent volumes. The effect of the solvent nature and the extraction time on the simultaneous distillation–extraction efficiency was evaluated. The best performance was achieved using pentane as a solvent for 1 h of extraction. The essential oils obtained by simultaneous distillation–extraction extracts were analyzed by gas chromatography with flame ionization detection (GC-FID). Extraction efficiencies ranged from 40 to 70% for the majority of the compounds tested, and the precision (measured by the relative standard deviation) varied between 6 and 35%. Among the compounds analyzed the most abundant in the Rosmarinus officinalis L. sample were 1,8-cineole, (-) –borneol, α-pinene, (S)-(-)- α–terpineol, (-)-bornyl acetate, linalool, and 2,2,6-trimethylcyclohexanone. The SDE method proved to be a suitable option for obtaining extracts free from cuticular waxes or chlorophylls.

Preliminary Phytochemical Screening, Isolation, Characterization, Structural Elucidation and Antibacterial Activities of Leaves Extracts Rhus Vulgaris (Kimmo)

Background: Rhus vulgaris commonly known as sumac, a plant that is known to possess different therapeutic values including antioxidant and antibacterial activities. Medicines from plants contributed largely to human health. The aim of this study was to screen the phytochemical constituents, isolate, elucidate the structure and antibacterial activity of methanol extract from the leaves of Rhus vulgaris.Methods: The methanolic extract of Rhus vulgaris was subjected to column chromatography and eluted with solvent mixture of methanol: chloroform (1:8) ratio. The eluted fractions were run in the TLC mobile phase with the different solvent ratio. Based on the TLC profile the fractions with similar Rf values were pooled together. The structure of the isolated compound was characterized based on the spectral data (IR, 1H NMR, 13C NMR, and DEPT) and extracts from Rhus vulgaris has been shown to have antibacterial activity were tested against four strains bacteria Streptococcus aureus(gram-positive) and Escherichia coli, Salmonella typhimurium, and K. pneumoniae (gram-negative) using Agar well diffusion method.Result: The results showed that the methanol extracts were active against all the tested bacteria. The structure of this compound 1-p-tolyl pentadeca-7,9-dien-1-ol was characterized by means of 1H NMR, 13C NMR, and IR spectral data.Conclusion: Therefore, it is concluded that the use of herbal plants and their recipes are the major source of drugs in a traditional medicinal system to cure different diseases.

Methylammonium Lead Tri-Iodide Perovskite Solar Cells with Varying Equimolar Concentrations of Perovskite Precursors

During recent years, power conversion efficiencies (PCEs) of organic-inorganic halide perovskite solar cells (PSCs) have shown remarkable progress. The emergence of various thin film deposition processes to produce perovskite films, notably using solution processing techniques, can be credited in part for this achievement. The engineering of chemical precursors using solution processing routes is a powerful approach for enabling low-cost and scalable solar fabrication processes. In the present study, we have conducted a systematic study to tune the equimolar precursor ratio of the organic halide (methylammonium iodide; MAI) and metal halide (lead iodide; PbI2) in a fixed solvent mixture of N,N-dimethylformamide (DMF):dimethylsulfoxide (DMSO). The surface morphology, optical characteristics, and crystallinity of the films produced with these four distinct solutions were investigated, and our analysis shows that the MAI:PbI2 (1.5:1.5) film is optimal under the current conditions. The PSCs fabricated from the (1.5:1.5) formulation were then integrated into the n-i-p solar cell architecture on fluorine-doped tin oxide (FTO) substrates, which exhibited a PCE of ~14.56%. Stability testing on this PSC device without encapsulation at 29 °C (ambient temperature) and 60% relative humidity (RH) under one-sun illumination while keeping the device at its maximum power point showed the device retained ~60% of initial PCE value after 10 h of continuous operation. Moreover, the recombination analysis between all four formulations showed that the bimolecular recombination and trap-assisted recombination appeared to be suppressed in the more optimal (1.5:1.5) PSC device when compared to the other formulations used in the n-i-p PSC architecture.

New Facile One-Pot Synthesis of Isobutyl Thiocarbamate in Recycling Solvent Mixture

The specific objectives of the presented study were related to the optimization of the production process of N-alkyl-, N,N-dialkyl-, and N-cycloalkyl-O-isobutyl thiocarbamate; trial industrial production of N-ethyl-O-isobutyl thiocarbamate; and the evaluation of flotation efficiency of N-ethyl-O-isobutyl thiocarbamate using a real ore sample. The optimization of thiocarbamate syntheses were performed by varying the molar ratio of isobutyl alcohol, carbon disulfide, potassium hydroxide, reaction time, and reaction temperature. In the first step, one-pot reaction took place to produce alkyl xanthate and was followed with chlorination to give alkyl chloroformate (O-alkyl carbonochloridothioate); finally, thiocarbamates were obtained by the reaction with corresponding amines. N-alkyl-O-ethyl thiocarbamate was synthesized as a comparative flotation agent. The structure of the synthesized compounds was confirmed by IR, 1H and 13C NMR, and MS instrumental methods, and the purity was determined by gas chromatographic method and elemental analysis. The optimized methods gave high-purity products in a significant yield that was also confirmed by semi-industrial production of N-ethyl-O-isobutyl thiocarbamate. The optimized thiocarbamate synthesis, without isolation of intermediates, is of great importance from the aspect of green technologies. Flotation efficiency test results, using real copper and zinc ores, showed the highest activity of N-ethyl-O-isobutyl thiocarbamate. The optimal one-pot thiocarbamate synthesis provides a simple procedure with a high conversion degree, and, thus, offers valuable technology applicable at the industrial scale.

Dual Properties of Polyvinyl Alcohol-Based Magnetorheological Plastomer with Different Ratio of DMSO/Water

Polyvinyl alcohol (PVA)-based magnetorheological plastomer (MRP) possesses excellent magnetically dependent mechanical properties such as the magnetorheological effect (MR effect) when exposed to an external magnetic field. PVA-based MRP also shows a shear stiffening (ST) effect, which is very beneficial in fabricating pressure sensor. Thus, it can automatically respond to external stimuli such as shear force without the magnetic field. The dual properties of PVA-based MRP mainly on the ST and MR effect are rarely reported. Therefore, this work empirically investigates the dual properties of this smart material under the influence of different solvent compositions (20:80, 40:60, 60:40, and 80:20) by varying the ratios of binary solvent mixture (dimethyl sulfoxide (DMSO) to water). Upon applying a shear stress with excitation frequencies from 0.01 to 10 Hz, the storage modulus (G′) for PVA-based MRP with DMSO to water ratio of 20:40 increases from 6.62 × 10−5 to 0.035 MPa. This result demonstrates an excellent ST effect with the relative shear stiffening effect (RSTE) up to 52,827%. In addition, both the ST and MR effect show a downward trend with increasing DMSO content to water. Notably, the physical state of hydrogel MRP could be changed with different solvent ratios either in the liquid-like or solid-like state. On the other hand, a transient stepwise experiment showed that the solvent’s composition had a positive effect on the arrangement of CIPs within the matrix as a function of the external magnetic field. Therefore, the solvent ratio (DMSO/water) can influence both ST and MR effects of hydrogel MRP, which need to be emphasized in the fabrication of hydrogel MRP for appropriate applications primarily with soft sensors and actuators for dynamic motion control.

HILIC -MS/MS Analysis of Adenosine in Patient Blood

Adenosine is a purine ribonucleoside with important roles in various physiological processes. A number of studies have indicated the importance of adenosine in cardiovascular diseases including syncope; however, the accurate determination of adenosine in human blood is challenging due to the molecule’s instability. In the present study, we report a simple method for the pre-treatment of blood samples and the development of a fast and efficient hydrophilic interaction chromatographic tandem mass spectrometry method for the analysis of adenosine in patient blood. During collection, samples were mixed directly with a solvent mixture containing 95% acetonitrile and 10 mM ammonium formate in a Vacutainer tube, resulting in successful prevention of adenosine metabolic processes and direct blood sample deproteinization. The method was validated according to bioanalytical industry guidelines and found to be accurate, repeatable, specific and sensitive with LLOQ 0.005 μg/mL, thus allowing its application in the analysis of real clinical samples.

Counterintuitive Single-Molecule Magnet Behaviour in Two Polymorphs of One-Dimensional Compounds Involving Chiral BINOL-Derived Bisphosphate Ligands

The coordination reaction of the [Dy(hfac)3(H2O)2] units (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate) with the [8′-(Diphenoxylphosphinyl)[1,1′-binaphthalen]-8-yl]diphenoxylphosphine oxide ligand (L) followed by a crystallisation in a 1:3 CH2Cl2:n-hexane solvent mixture led to the isolation of a new polymorph of formula [(Dy(hfac)3((S)-L))3]n (1). The X-ray structure on single crystal of 1 revealed the formation of a mono-dimensional coordination polymer with three crystallographically independent DyIII centres, which crystallised in the polar chiral P21 space group. Ac magnetic measurements highlighted single-molecule magnet behaviour under both zero and 1000 Oe applied magnetic field with magnetic relaxation through quantum tunneling of the magnetisation (QTM, zero field only) and Raman processes. Despite the three crystallographically independent DyIII centres adopting a distorted D4d coordination environment, a single slow magnetic relaxation contribution was observed at a slower rate than its previously studied [(Dy(hfac)3((S)-L))]n (2) polymorph.