Superior Valorisation of Juglans regia L. Leaves of Different Maturity through the Isolation of Bioactive Compounds.

Extracts rich in bioactive compounds from natural sources have received great interest due to their great impact on human health. The aim of this research is focused on the obtaining and characterization of several extracts from Juglans regia L. leaves in four different maturity phases: young green leaves (YGL), green leaves (GL), mature green leaves (MGL), and yellow leaves (YL), using different solvents: ethanol (e), water (w), or water:ethanol (1:1 (v/v)-m) by employing several methods: magnetic stirring (MS), ultrasound-assisted (UA), as well as maceration (M). The obtained extracts were quantitatively evaluated through spectrophotometric methods: Total Polyphenol Content (TPC-Folin-Ciocalteu assay) and Total Antioxidant Capacity (TEAC assay). Phytochemical screening by means of Fourier-Transform Ion-Cyclotron-Resonance High-Resolution Mass Spectrometry (FT-ICR-MS) indicated the presence of 40 compounds belonging to different phytochemical classes: phenolic acids, flavonoids, flavones, flavanones, flavonones, flavanols, vitamins, tereponoid, steroid, anthocyanidin, and other compounds. Based on TPC and TEAC assays, the water-ethanol mixture was found to be the proper extraction solvent, with the best results being obtained for YL plant material: 146.29 mg GAE/g DM (TPC) and 11.67 mM TE/g DM (TEAC). This type of extract may be used in various domains, such as the cosmetics industry, the biomedical field, and/or the design of functional foods, relying on their phytochemical composition.

Bioconjugation of Vegetable Oils with UV Absorbers: New Approach in Skin Photoprotection.

We reported the tunable synthesis of new vegetable oil-UV filter bioconjugates using sea buckthorn oil (SBO) and p-methoxycinnamic acid (p-MCA) as an alternative to the common UV filter, ethylhexyl-p-methoxycinnamate (octinoxate). The synthetic strategy is based on the sustainable ring-opening reaction of epoxidized SBO with p-MCA in heterogenous catalysis in eco-friendly solvents. The amount of UV-absorptive moieties grafted on the triglyceride backbone is controlled by different epoxidation degrees as determined by NMR spectroscopy. The performance of the new UV-absorber bioconjugates was assessed by in vitro sun protection factor (SPF) measurements after inclusion in SBO-ethylcellulose (EC) oleogels and comparison with the SPF value of the SBO-EC-octinoxate oleogel with equivalent p-MCA acid moieties (10% wt/wt). The concentration obtained for the SBO-EC oleogel formulated with the bioconjugate with the lowest degree of functionalization, namely 55%, represents 45% of the SPF determined for the SBO-EC-octinoxate oleogel, regardless of the concentration of measured solutions. The new concept of vegetable oil-UV-absorber bioconjugates has potential UV-B photoprotective properties when included in oleogel formulations and deserves further investigation of their properties and stability including association with UV-A absorbers, respectively.

Effects of Extraction Process Factors on the Composition and Antioxidant Activity of Blackthorn (Prunus spinosa L.) Fruit Extracts.

This study aimed at establishing the optimal conditions for the classic extraction of phenolic compounds from Prunus spinosa L. fruits. The effects of different parameters, i.e., ethanol concentration in the extraction solvent (mixture of ethanol and water), operation temperature, and extraction time, on process responses were evaluated. Total phenolic content (TPC), total anthocyanin content (TAC), antioxidant capacity (AC), and contents of protocatechuic acid (PA), caffeic acid (CA), vanillic acid (VA), rutin hydrate (RH), and quercetin (Q) of fruit extracts were selected as process responses. A synergistic effect of obtaining high values of TPC, TAC, AC, PA, and VA was achieved for the extraction in 50% ethanol at 60 °C for 30 min. At a higher level of process temperature, the extraction of protocatechuic acid and vanillic acid was enhanced, but the flavonoids, i.e., rutin hydrate and quercetin, were degraded. A lower temperature should be used to obtain a higher amount of flavonoids. TPC, TAC, AC, and phenolic acid contents (PA, CA, and VA) in the extract samples obtained at an ethanol concentration of 50-100%, a temperature of 30-60 °C, and an extraction time of 30 min were strongly directly correlated.

Quality Assurance and Cost Reduction in Histopathology Laboratories Using Tissue Microarrays.

In the context of cost increases of both labor and consumables, cheaper and faster histopathology methods are needed. We implemented in our research laboratory the use of tissue microarrays (TMA) for the parallel processing and analysis of tissue samples. In this study, we used seven pre-processed, paraffinated biomimetic sectionable support matrices serving as "recipient" paraffin blocks to embed a total of 196 tissue cores from formalin-fixed paraffin-embedded tissue samples (serving as "donor" paraffin blocks) from seven different rabbit organs. These tissue samples were obtained using four different processing protocols: two 6 h protocols with xylene as the transition solvent, and two using butanol instead (one 10 h in duration and the other 72 h long). While the samples from protocols 1 and 2 (with xylene) quite regularly generated peeling of some of the cores from the slides (most likely because of substandard paraffin infiltration), butanol processing performed flawlessly for both processing protocols. Our proposed technique of using TMAs in the research laboratory brings with it a significant reduction in time and consumable costs (up to 77 and 64%, respectively), but also new challenges for all the upstream processes.

Investigating the Synthesis and Characteristics of UV-Cured Bio-Based Epoxy Vegetable Oil-Lignin Composites Mediated by Structure-Directing Agents.

Bio-based composites were developed from the epoxy derivatives of Lallemantia iberica oil and kraft lignin (ELALO and EpLnK), using UV radiation as a low energy consumption tool for the oxiranes reaction. To avoid the filler sedimentation or its inhomogeneous distribution in the oil matrix, different structure-directing agents (SDA) were employed: 1,3:2,4-dibenzylidene-D-sorbitol (DBS), 12-hydroxystearic acid (HSA) and sorbitan monostearate (Span 60). The SDA and EpLnK effect upon the ELALO-based formulations, their curing reaction and the performance of the resulting materials were investigated. Fourier-transform Infrared Spectrometry (FTIR) indicates different modes of molecular arrangement through H bonds for the initial ELALO-SDA or ELALO-SDA-EpLnK systems, also confirming the epoxy group's reaction through the cationic mechanism for the final composites. Gel fraction measurements validate the significant conversion of the epoxides for those materials containing SDAs or 1% EpLnK; an increased EpLnK amount (5%), with or without SDA addition, conduced to an inefficient polymerization process, with the UV radiation being partially absorbed by the filler. Thermo-gravimetric and dynamic-mechanical analyses (TGA and DMA) revealed good properties for the ELALO-based materials. By loading 1% EpLnK, the thermal stability was improved to with 10 °C (for Td3%) and the addition of each SDA differently influenced the Tg values but also gave differences in the glassy and rubbery states when the storage moduli were interrogated, depending on their chemical structures. Water affinity and morphological studies were also carried out.

Lipoprofiling Assessed by NMR Spectroscopy in Patients with Acute Coronary Syndromes: Is There a Need for Fasting Prior to Sampling?

Most patients presenting in an emergency unit with acute coronary syndromes (ACS) (which include non-ST-elevation myocardial infarction (NSTEMI), ST-elevation MI (STEMI), and unstable angina) usually meet at least two cardiovascular risk factors, such as dyslipidemia, arterial hypertension, diabetes mellitus type 2, obesity, history of or current smoking, etc. Most ACS patients suffer from a type of dyslipidemia, and in addition to this there are ACS patients rushed into the emergency units for which the feeding status is unknown. Thus, we set out to evaluate the effect of fasting on 16 blood metabolite concentrations and 114 lipoprotein parameters on one control group and a group of statin-treated ACS patients hospitalized in a cardiovascular emergency unit, using Nuclear Magnetic Resonance (NMR) spectroscopy. The results indicated trends (in terms of number of cases, but not necessarily in terms of the magnitude of the effect) for as many as four metabolites and 48 lipoproteins. The effect was defined as a trend for results showing over 70% of the cases from either one or both groups that experienced parameter changes in the same direction (i.e., either increased or decreased). In terms of magnitude, the effect is rather low, leading to the overall conclusion that in cardiovascular (CV) emergency units, the blood samples analyzed in any feeding status would provide close results and very valuable information regarding prognosis and for fast decisions on patient's proper management.

Electrospun-Fibrous-Architecture-Mediated Non-Viral Gene Therapy Drug Delivery in Regenerative Medicine.

Gene-based therapy represents the latest advancement in medical biotechnology. The principle behind this innovative approach is to introduce genetic material into specific cells and tissues to stimulate or inhibit key signaling pathways. Although enormous progress has been achieved in the field of gene-based therapy, challenges connected to some physiological impediments (e.g., low stability or the inability to pass the cell membrane and to transport to the desired intracellular compartments) still obstruct the exploitation of its full potential in clinical practices. The integration of gene delivery technologies with electrospun fibrous architectures represents a potent strategy that may tackle the problems of stability and local gene delivery, being capable to promote a controlled and proficient release and expression of therapeutic genes in the targeted cells, improving the therapeutic outcomes. This review aims to outline the impact of electrospun-fibrous-architecture-mediated gene therapy drug delivery, and it emphatically discusses the latest advancements in their formulation and the therapeutic outcomes of these systems in different fields of regenerative medicine, along with the main challenges faced towards the translation of promising academic results into tangible products with clinical application.

Macrophage-targeted mannose-decorated PLGA-vegetable oil hybrid nanoparticles loaded with anti-inflammatory agents.

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 (RH, 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 (RH < 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.

A Real-Life Reproducibility Assessment for NMR Metabolomics.

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.

Microwave-Assisted Sol-Gel Preparation of the Nanostructured Magnetic System for Solid-Phase Synthesis.

This work describes a new synthesis method for core-shell magnetite nanoparticles with a secondary silica shell, functionalized with a linker system (Fe3O4-PABA-SiO2-linker) using a microwave-assisted heating technique. The functionalized solid nanomaterial was used for the nanophase synthesis of peptides (Fmoc route) as a solid support. The co-precipitation method was selected to obtain magnetite nanoparticles and sol-gel technique for silica coating using a microwave-assisted (MW) procedure. The magnetic properties of the nanoparticle core offer the advantage of a quick and easy alternative for the magnetic separation of the product from the reaction mixture, facilitating all the intermediary washing and separation operations. The intermediate and final materials were analyzed by advanced characterization methods. The effectiveness of the nanophase peptide synthesis using this nanostructured material as solid support was demonstrated for a short peptide sequence.

Composite Materials from Renewable Resources as Sustainable Corrosion Protection Coatings.

Epoxidized linseed oil (ELO) and kraft lignin (LnK) were used to obtain new sustainable composites as corrosion protection layers through a double-curing procedure involving UV radiation and thermal curing to ensure homogeneous distribution of the filler. The crosslinked structures were confirmed by Fourier-transform infrared spectrometry (FTIR), by comparative monitorization of the absorption band at 825 cm-1, attributed to the stretching vibration of epoxy rings. Thermal degradation behavior under N2 gas indicates that the higher LnK content, the better thermal stability of the composites (over 30 °C of Td10% for ELO + 15% LnK), while for the experiment under air-oxidant atmosphere, the lower LnK content (5%) conducted to the more thermo-stable material. Dynamic-mechanic behavior and water affinity of the new materials were also investigated. The increase of the Tg values with the increase of the LnK content (20 °C for the composite with 15% LnK) denote the reinforcement effect of the LnK, while the surface and bulk water affinity were not dramatically affected. All the obtained composites were tested as carbon steel corrosion protection coatings, resulting in significant increase of corrosion inhibition efficiency (IE) of 140-380%, highlighting the great potential of the bio-based ELO-LnK composites as a future perspective for industrial application.

Harnessing a byproduct from wastewater treatment to obtain improved starch/poly(vinyl alcohol) composites.

A rational method to harness a triglyceride-based by-product containing chicken fat traces, extracted from the simulated slaughterhouses wastewater was adopted. Methacrylated linseed oil was used as photo-reactive monomer to "catch" the grease molecules, resulting in a polymeric network (PFrec), further embedded in starch/poly(vinyl alcohol) (St/PVA)-based composites, with or without plasticizer (glycerol-Gly), with enhanced properties. Hydrophobic additive improved the thermal stability of St/PVA blends, an 18 °C increase of Td3 % being registered for PFrec-loaded sample. Mechanical tests revealed that association of PFrec with Gly improved the flexibility and also reinforced the systems, although, no plasticizing effect was observed at PFrec addition. Solubility determinations for the St/PVA-based composite films showed that hydrophobic PFrec increased the water resistance with at least 40 %. According to contact angle measurements a good dispersion of PFrec in the St/PVA network was mediated at the interface by hydrophilic Gly molecules.

A universal approach for the synthesis of two-dimensional binary compounds.

Only a few of the vast range of potential two-dimensional materials (2D) have been isolated or synthesised to date. Typically, 2D materials are discovered by mechanically exfoliating naturally occurring bulk crystals to produce atomically thin layers, after which a material-specific vapour synthesis method must be developed to grow interesting candidates in a scalable manner. Here we show a general approach for synthesising thin layers of two-dimensional binary compounds. We apply the method to obtain high quality, epitaxial MoS2 films, and extend the principle to the synthesis of a wide range of other materials-both well-known and never-before isolated-including transition metal sulphides, selenides, tellurides, and nitrides. This approach greatly simplifies the synthesis of currently known materials, and provides a general framework for synthesising both predicted and unexpected new 2D compounds.

Novel PEG-Modified Hybrid PLGA-Vegetable Oils Nanostructured Carriers for Improving Performances of Indomethacin Delivery.

The purpose of this work was to more exhaustively study the influence of nanocarrier matrix composition and also the polyethylene glycol (PEG)-modified surface on the performances of formulations as lipophilic drug delivery systems. Poly (d,l-lactide-co-glycolide), two vegetable oils (Nigella sativa oil and Echium oil) and indomethacin were employed to prepare novel PEG-coated nanocarriers through emulsion solvent evaporation method. The surface modification was achieved by physical PEG adsorption (in the post-production step). Transmission electron microscopy (TEM) nanographs highlighted the core-shell structure of hybrid formulations while scanning electron microscopy (SEM) images showed no obvious morphological changes after PEG adsorption. Drug loading (DL) and entrapment efficiency (EE) varied from 4.6% to 16.4% and 28.7% to 61.4%, solely depending on the type of polymeric matrix. The oil dispersion within hybrid matrix determined a more amorphous structure, as was emphasized by differential scanning calorimetry (DSC) investigations. The release studies highlighted the oil effect upon the ability of nanocarrier to discharge in a more sustained manner the encapsulated drug. Among the kinetic models employed, the Weibull and Korsmeyer-Peppas models showed the better fit (R² = 0.999 and 0.981) with n < 0.43 indicating a Fickian type release pattern. According to cytotoxic assessment the PEG presence on the surface increased the cellular viability with ~1.5 times as compared to uncoated formulations.

Hybrid networks based on epoxidized camelina oil.

Lately, renewable resources received great attention in the macromolecular compounds area, regarding the design of the monomers and polymers with different applications. In this study the capacity of several modified vegetable oil-based monomers to build competitive hybrid networks was investigate, taking into account thermal and mechanical behavior of the designed materials. In order to synthesize such competitive nanocomposites, the selected renewable raw material, camelina oil, was employed due to the non-toxicity and biodegradability behavior. General properties of epoxidized camelina oil-based materials were improved by loading of different types of organic-inorganic hybrid compounds - polyhedral oligomeric silsesquioxane (POSS) bearing one (POSS1Ep) or eight (POSS8Ep) epoxy rings on the cages. In order to identify the chemical changes occurring after the thermal curing reactions, FT-IR spectrometry was employed. The new synthesized nanocomposites based on epoxidized camelina oil (ECO) were characterized by dynamic mechanical analyze and thermogravimetric analyze. The morphology of the ECO-based materials was investigate by scanning electron microscopy and supplementary information regarding the presence of the POSS compounds were establish by energy dispersive X-ray analysis and X-ray photoelectron spectroscopy. The smooth materials without any separation phase indicates a well dispersion of the Si-O-Si cages within the organic matrix and the incorporation of this hybrid compounds into the ECO network demonstrates to be a well strategy to improve the thermal and mechanical properties, simultaneously.

Indolizines and pyrrolo[1,2-c]pyrimidines decorated with a pyrimidine and a pyridine unit respectively.

The three possible structural isomers of 4-(pyridyl)pyrimidine were employed for the synthesis of new pyrrolo[1,2-c]pyrimidines and new indolizines, by 1,3-dipolar cycloaddition reaction of their corresponding N-ylides generated in situ from their corresponding cycloimmonium bromides. In the case of 4-(3-pyridyl)pyrimidine and 4-(4-pyridyl)pyrimidine the quaternization reactions occur as expected at the pyridine nitrogen atom leading to pyridinium bromides and consequently to new indolizines via the corresponding pyridinium N-ylides. However, in the case of 4-(2-pyridyl)pyrimidine the steric hindrance directs the reaction to the pyrimidinium N-ylides and, subsequently, to the formation of the pyrrolo[1,2-c]pyrimidines. The new pyrrolo[1,2-c]pyrimidines and the new indolizines were structurally characterized through NMR spectroscopy. The X-ray structures of two of the starting materials, 4-(2-pyridyl)pyrimidine and 4-(4-pyridyl)pyrimidine, are also reported.

Rice bran and raspberry seed oil-based nanocarriers with self-antioxidative properties as safe photoprotective formulations.

The aim of this research was to develop advanced lipid nanocarriers based on renewable vegetable resources (rice bran oil and raspberry seed oil) that possess self-antioxidative properties, having advantages in terms of minimal side effects and exhibiting the ability to simultaneously co-encapsulate and co-release two active compounds. The focus has been oriented towards developing safe cosmetic formulations with broad-spectrum photoprotection based on these new lipid nanocarriers that contain large amounts of vegetable oils and low concentrations of synthetic UVA and UVB filters (butyl-methoxydibenzoylmethane - BMDBM and octocrylene - OCT). The lipid nanocarriers have a spherical shape and show good physical stability, with a zeta potential in the range of -25.5 to -32.4 mV. Both vegetable oils play a key role in the preparation of efficient nanocarriers, leading to a less ordered arrangement of the lipid core that offers many spaces for the entrapment of large amounts of BMDBM (79%) and OCT (90%), as wells as improved antioxidant activity and UV absorption properties, particularly for the lipid nanocarriers prepared from rice bran oil. By formulating the lipid nanocarriers into creams containing only 3.5% of the UV filters and 10.5% of the vegetable oils, the resulting sunscreens exhibited improved photoprotection, reflecting up to 91% and 93% of UVA and UVB rays, respectively. A new direction of research achieved by this study is the multiple release strategy of both UV filters from the same lipid nanocarrier. After 24 hours, a slow release of BMDBM (less than 4%) and OCT (17.5%) was obtained through a Fick diffusion process. This study demonstrates a significant advance in the areas of both nanotechnology and cosmetics, developing safer cosmetic formulations that possess broad antioxidant, photoprotective and co-release effectiveness due to the existence of a high content of nanostructured vegetable oils combined with a low amount of synthetic UV filters in the same carrier system.