Isobornyl and Isocamphyl Photostabilizers in Poly(lactic acid)-Based Electrospun Fibers.

In this work, electrospun polylactide fibers with new photostabilizing additives, 4-methyl-2,6-diisobornylphenol (DIBP) and N-isocamphylaniline (NICA), have been tested under the influence of UV-C radiation (254 nm). The changes in the polymers' chemical structure under UV-C radiation were revealed through the increase in absorption in the 3600-3100 cm-1 region in regard to the FTIR spectra. In the samples that were irradiated for 1 h, the stabilizing effect of the photoprotectors became most noticeable as the difference in the content of the hydroxyl groups in stabilized and the pure PLA reached a maximum. The TG-DSC method revealed that the most sensitive indicator of the irradiation effect was the glass transition temperature (Tg), which persisted after 2 h of irradiation when using photostabilizers and their combinations. The PLA/DIBP(1) and PLA/NICA(1) samples showed the best results in protecting PLA from UV-C radiation based on the Tg values; although, the mixture of DIBP and NICA was not as effective. The chemical structure of the photostabilized PLA samples was studied using NMR, GPC, and Py-GC/MS analysis. The electrospun polylactide fibers were mechanically tested and the effects of the electrospun samples on cell viability were studied.

Giant dilatation of pancreatic duct associated with congenital anomaly of the pancreatic ductal system and small neuroendocrine tumor.

Dilatation of the main pancreatic duct (MPD) ˃50 mm is a rare phenomenon. We present the case of successful surgical treatment a 63-year-old female patient who presented epigastric pain and weight loss of 10 kg in 6 months. Based on preoperative examination, the dilatation of MPD was 75 mm. The preliminary diagnosis was main duct intraductal papillary mucinous neoplasm. Extended pylorus-preserving pancreatoduodenectomy with resection of the body of the pancreas was performed. According to the results of pathological and immunohistochemical studies, performed by independent experts, the final diagnosis of congenital anomaly of the ductal system and neuroendocrine tumor of the accessory pancreatic duct was made.

Effect of TiO2 on Pd/La2O3-CeO2-Al2O3 Systems during Catalytic Oxidation of Methane in the Presence of H2O and SO2.

New results on the effect of TiO2 on Pd/La2O3-CeO2-Al2O3 systems for catalytic oxidation of methane in the presence of H2O and SO2 have been received. Low-temperature N2-adsorption, XRD, SEM, HRTEM, XPS, EPR and FTIR techniques were used to characterize the catalyst. The presence of Ce3+ on the catalytic surface and in the volume near the lantana was revealed by EPR and XPS. After aging, the following changes are observed: (i) agglomeration of the Pd-clusters (from 8 nm to 12 nm); (ii) transformation of part of the TiO2 from anatase to larger particles of rutile; and (iii)-the increase in PdO/Pd-ratio above its optimum. The modification by Ti of the La2O3-CeO2-Al2O3 system leads to higher resistance towards the presence of SO2 most likely due to the prevailing formation of unstable surface sulfites instead of thermally stable sulfates. Based on kinetic model calculations, the reaction pathway over the Pd/La2O3-CeO2-TiO2-Al2O3 catalyst follows the Mars-van Krevelen mechanism. For evaluation of the possible practical application of the obtained material, a sample of Pd/La2O3-CeO2-TiO2-Al2O3, supported on rolled aluminum-containing stainless steel (Aluchrom VDM®), was prepared and tested. Methane oxidation in an industrial-scale monolithic reactor was simulated using a two-dimensional heterogeneous reactor model.

Hydrogen Storage Properties of Ball Milled MgH2 with Additives- Ni, V and Activated Carbons Obtained from Different By-Products.

The hydrogen sorption of materials based on 80 wt.% MgH2 with the addition of 15 wt.% Ni or V and 5 wt.% activated carbons synthesized from polyolefin wax, a waste product from polyethylene production (POW), walnut shells (CAN), and peach stones (CPS) prepared by milling under an inert Ar atmosphere for a period of 1 h, is investigated. All precursors are submitted to pyrolysis followed by steam activation in order to obtain the activated carbons. The hydrogen sorption evaluations are carried out for absorption at 473 and 573 K with pressure of 1 MPa and for desorption at 623 and 573 K with pressure of 0.15 MPa. The composition of the samples after milling and hydrogenation is monitored by X-ray diffraction analyses. The 80 wt.% MgH2-15 wt. %Ni-5 wt.% POW or CAN after absorption-desorption cycling and in a hydrogenated state at 573 K and 1 MPa are analyzed by TEM.

Effect of Chitosan on Rheological, Mechanical, and Adhesive Properties of Pectin-Calcium Gel.

In the present study, chitosan was included in the pectin ionotropic gel to improve its mechanical and bioadhesive properties. Pectin-chitosan gels P-Ch0, P-Ch1, P-Ch2, and P-Ch3 of chitosan weight fractions of 0.00, 0.25, 0.50, and 0.75 were prepared and characterized by dynamic rheological tests, penetration tests, and serosal adhesion ex vivo assays. The storage modulus (G') and loss modulus (G″) values, gel hardness, and elasticity of P-Ch1 were significantly higher than those of P-Ch0 gel. However, a further increase in the content of chitosan in the gel significantly reduced these parameters. The inclusion of chitosan into the pectin gel led to a decrease in weight and an increase in hardness during incubation in Hanks' solution at pH 5.0, 7.4, and 8.0. The adhesion of P-Ch1 and P-Ch2 to rat intestinal serosa ex vivo was 1.3 and 1.7 times stronger, whereas that of P-Ch3 was similar to that of a P-Ch0 gel. Pre-incubation in Hanks' solution at pH 5.0 and 7.4 reduced the adhesivity of gels; however, the adhesivity of P-Ch1 and P-Ch2 exceeded that of P-Ch0 and P-Ch3. Thus, serosal adhesion combined with higher mechanical stability in a wide pH range appeared to be advantages of the inclusion of chitosan into pectin gel.

Effect of Cross-Linking Cations on In Vitro Biocompatibility of Apple Pectin Gel Beads.

The study aimed to compare the in vitro biocompatibility of pectin gels formed by different cross-linking cations. Hydrogel beads named CaPG, ZnPG, FePG, and AlPG were prepared from 4% solutions of apple pectin using ionotropic gelling with CaCl2, ZnCl2, FeCl3, and AlCl3, respectively. Cations influenced the gel strength of the wet gel beads in the following order (least strong) Ca2+ < Zn2+ < Fe3+~Al3+ (most strong). The swelling degree of the CaPG beads after 24 h of incubation in the RPMI-1640 medium was 104%, whereas the ZnPG, FePG, and AlPG beads swelled by 76, 108, and 134%, respectively. The strength of the pectin gel decreased significantly after incubation in the RPMI-1640 medium for 24 h, regardless of the cross-linking cation, although the FePG beads remained the strongest. All the pectin beads adsorbed serum proteins to a low degree, however the serum protein adsorption by the ZnPG and FePG beads (1.46 ± 0.87 and 1.35 ± 0.19 µg/mm2) was more than the CaPG and AlPG beads (0.31 ± 0.36 and 0.44 ± 0.25 µg/mm2). All the pectin beads reduced the production of TNF-α and IL-10 by hPBMCs in response to LPS stimulation. The IL-1ß response of cells to LPS was significantly reduced by the CaPG, ZnPG, and FePG beads, whereas the AlPG beads enhanced it twofold. The CaPG, FePG, and AlPG beads had no cytotoxicity. The viability of hPBMCs and human fibroblasts incubated with ZnPG beads was 5.3 and 7.2%, respectively. Thus, the use of different cross-linking cations changed the properties of the pectin gel, which is important for biocompatibility.

Design, Synthesis, and Antiviral Activity of the Thiazole Positional Isomers of a Potent HIV-1 Entry Inhibitor NBD-14270.

The envelope glycoprotein gp120 of human immunodeficiency virus type 1 (HIV-1) plays a critical role in virus entry to the cells by binding to the host cellular protein CD4. Earlier, we reported the design and discovery of a series of highly potent small-molecule entry antagonists containing a thiazole ring (Scaffold A). Since this thiazole ring connected with an ethyl amide linkage represents the molecule's flexible part, we decided to explore substituting Scaffold A with two other positional isomers of the thiazole ring (Scaffold B and C) to evaluate their effect on the antiviral potency and cellular toxicity. Here we report the novel synthesis of two sets of positional thiazole isomers of the NBD-14270 by retrosynthetic analysis approach, their anti-HIV-1 activity, cellular toxicity, and structure-activity relationships. The study revealed that Scaffold A provided the best HIV-1 inhibitors with higher potency and better selectivity index (SI).

Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd1Ag3/Al2O3 Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism.

This research was focused on studying the performance of the Pd1Ag3/Al2O3 single-atom alloy (SAA) in the liquid-phase hydrogenation of di-substituted alkyne (1-phenyl-1-propyne), and development of a kinetic model adequately describing the reaction kinetic being also consistent with the reaction mechanism suggested for alkyne hydrogenation on SAA catalysts. Formation of the SAA structure on the surface of PdAg3 nanoparticles was confirmed by DRIFTS-CO, revealing the presence of single-atom Pd1 sites surrounded by Ag atoms (characteristic symmetrical band at 2046 cm-1) and almost complete absence of multiatomic Pdn surface sites (<0.2%). The catalyst demonstrated excellent selectivity in alkyne formation (95-97%), which is essentially independent of P(H2) and alkyne concentration. It is remarkable that selectivity remains almost constant upon variation of 1-phenyl-1-propyne (1-Ph-1-Pr) conversion from 5 to 95-98%, which indicates that a direct alkyne to alkane hydrogenation is negligible over Pd1Ag3 catalyst. The kinetics of 1-phenyl-1-propyne hydrogenation on Pd1Ag3/Al2O3 was adequately described by the Langmuir-Hinshelwood type of model developed on the basis of the reaction mechanism, which suggests competitive H2 and alkyne/alkene adsorption on single atom Pd1 centers surrounded by inactive Ag atoms. The model is capable to describe kinetic characteristics of 1-phenyl-1-propyne hydrogenation on SAA Pd1Ag3/Al2O3 catalyst with the excellent explanation degree (98.9%).

Iron oxidation to amplify the Na and Li storage capacities of nano-sized maricite NaFePO4.

This study reports an effective approach to improve dramatically the electrochemical performance of nanosized NaFePO4 with a maricite structure, which is commonly considered as electrochemically inactive due to the absence of structural channels for alkaline ion mobility. The approach is based on the complete oxidation under mild conditions (i.e. at low temperatures around 280 °C and traces of oxygen) of the nanosized maricite phase. It is prepared by the phosphate-formate precursor method and is additionally ball-milled with a carbon additive. The oxidation of Fe2+ proceeds at the nanoscale level within the maricite nanoparticles and causes a massive structural transformation of the maricite phase into a monoclinic NASICON phase Na3Fe2(PO4)3 with the preservation of the crystallinity. The oxidized maricite phase exhibits high specific capacities, cycling stability and rate capability when it is used as an electrode in both Na and Li half-cells. The effect of different sodium and lithium electrolytes on the storage performance is investigated as well. It is found that the highest specific capacity (of about 150 mA h g-1) is achieved in Li half-cells using the LiPF6 electrolyte, while in Na half-cells the electrolyte NaFSI/EC:DMC achieves a specific capacity of around 100 mA h g-1. The rate capability is better in Na half-cells than that in Li half-cells. The mechanism of the reversible intercalation/deintercalation of Na+ and Li+ ions is studied by ex situ XRD and TEM analyses. The results show that the maricite is an electrochemically inactive phase, but through manipulation including oxidation or amorphization it becomes an active electrode material.

Design of gp120 HIV-1 entry inhibitors by scaffold hopping via isosteric replacements.

We present the development of alternative scaffolds and validation of their synthetic pathways as a tool for the exploration of new HIV gp120 inhibitors based on the recently discovered inhibitor of this class, NBD-14136. The new synthetic routes were based on isosteric replacements of the amine and acid precursors required for the synthesis of NBD-14136, guided by molecular modeling and chemical feasibility analysis. To ensure that these synthetic tools and new scaffolds had the potential for further exploration, we eventually tested few representative compounds from each newly designed scaffold against the gp120 inhibition assay and cell viability assays.

Facilitated Synthesis of Mg2Ni Based Composites with Attractive Hydrogen Sorption Properties.

Composites based on Mg2Ni with 5% activated carbon from apricot stones (ACAP) have been prepared by ball milling and subsequent annealing in hydrogen atmosphere. The purpose of the primary metal (Mg, Ni, and V) milling was to reduce the particle size and achieve a good contact between them, without forming intermetallic compounds. During hydriding/dehydriding at 300 °C the amount of the Mg2Ni phase progressively increased, and after 10 cycles about 50% Mg2(Ni,V) was achieved. The hydrogenation produced mainly Mg2NiH4, but small amounts of MgH2 and VHx were also detected in the powder mixture. Relatively high hydrogen storage capacity and fast hydriding/dehydriding kinetics of the Mg2.1Ni0.7V0.3-5 wt.% ACAP composite were determined both from hydrogen gas phase and electrochemically.

Pectin-glycerol gel beads: Preparation, characterization and swelling behaviour.

Low methyl-esterified pectin (AU701) was found to form gel beads with glycerol. Wet AU701-glycerol gel beads exhibited similar diameter and hardness compared to the AU701-Ca gel beads, prepared by ionotropic gelation with Ca2+ and used for comparison. The morphology of dry pectin gel beads determined by scanning electron microscopy revealed that the beads exhibited rough and grooved surface. The AU701-glycerol gel beads absorbed more grams of water than AU701-Ca gel beads (12.2 g vs 3.9 g per 1 g of the beads). Rheological properties and hardness of the AU701-glycerol gel beads improved with the increase of the pectin/glycerol ratio. Swelling behavior of the AU701-glycerol gel beads was determined after sequential incubation in simulated gastric (SGF) and intestinal (SIF) fluids. The AU701-glycerol gel beads swelled in SGF to a greater extent and revealed higher stability in SIF than the gel beads cross-linked by Ca2+.

Preclinical Optimization of gp120 Entry Antagonists as anti-HIV-1 Agents with Improved Cytotoxicity and ADME Properties through Rational Design, Synthesis, and Antiviral Evaluation.

We previously reported a milestone in the optimization of NBD-11021, an HIV-1 gp120 antagonist, by developing a new and novel analogue, NBD-14189 (Ref1), which showed antiviral activity against HIV-1HXB2, with a half maximal inhibitory concentration of 89 nM. However, cytotoxicity remained high, and the absorption, distribution, metabolism, and excretion (ADME) data showed relatively poor aqueous solubility. To optimize these properties, we replaced the phenyl ring in the compound with a pyridine ring and synthesized a set of 48 novel compounds. One of the new analogues, NBD-14270 (8), showed a marked improvement in cytotoxicity, with 3-fold and 58-fold improvements in selectivity index value compared with that of Ref1 and NBD-11021, respectively. Furthermore, the in vitro ADME data clearly showed improvements in aqueous solubility and other properties compared with those for Ref1. The data for 8 indicated that the pyridine scaffold is a good bioisostere for phenyl, allowing the further optimization of this molecule.

Mechanical properties of the pectin hydrogels and inflammation response to their subcutaneous implantation.

We studied the influence of the mechanical properties of pectin hydrogels on acute inflammation and tissue repair after subcutaneous implantation. We used hard and soft pectin hydrogels. The results of histology and the analysis of serum-level cytokines demonstrated that the intensity of acute inflammation increased with increasing hardness of the pectin hydrogels. We also showed that the pectin hydrogels did not inhibit tissue repair. The results of the morphometric and texture analysis of the pectin hydrogels showed that the in vivo biodegradation kinetics of hard hydrogels were greater than those of soft pectin hydrogels. We also observed that on the surface of the hard and soft pectin hydrogels, a network of collagen fibers was formed. The surface of the pectin hydrogel was shown to prevent the adhesion of infiltrating inflammatory cells. The results of the in vitro experiments demonstrated that pectin hydrogels inhibited the functional activity of macrophages and minimally activated the complement system. Therefore, we showed that soft pectin hydrogels have low proinflammatory potential and can be used in surgery as a barrier material as prevention of adhesions in the abdominal cavity. The hard pectin hydrogel can be used in tissue engineering. The hard pectin hydrogels can be used in the reconstruction of skin because are overpopulated with collagen fibers and contribute to the formation of new connective tissue, their elasticity is comparable to the skin and can be adjusted. They are biodegradable, and no additional manipulation is required to remove them.

Swelling behavior and satiating effect of the gel microparticles obtained from callus cultures pectins.

Gel microparticles were prepared from pectins of campion (SVCgel) and duckweed (LMCgel) callus cultures, as well as from commercial apple pectin (APgel) by emulsion dehydration techniques with successive ionotropic gelation. The morphology and swelling behavior of the microparticles were determined after successive incubation in simulated gastric (SGF), intestinal (SIF), and colonic (SCF) fluids. Both SVCgel and LMCgel microparticles were found to swell in SGF and SIF gradually, and at oral administration decreased food intake by laboratory mice during the first 5 h of free-feeding. The SVCgel microparticles demonstrated the higher stability in SCF within 24 h than LMCgel ones. Only the SVCgel microparticles were shown to decrease food intake by 24% during the 21 h of free-feeding and decreased body weight of mice by 4% during 24 h after oral administration. The APgel microparticles lost their shape in SIF, then fully disintegrated after 0.5 h of incubation in SCF, and failed to affect food intake or mice body weight. The data obtained indicated that sustainability and swelling of the gel microparticles from the SVC pectin in the colonic fluid may provide the stronger satiating effect compared to that of the LMCgel microparticles.

Highly-Ordered PdIn Intermetallic Nanostructures Obtained from Heterobimetallic Acetate Complex: Formation and Catalytic Properties in Diphenylacetylene Hydrogenation.

Formation of PdIn intermetallic nanoparticles supported on α-Al2O3 was investigated by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and hydrogen temperature-programmed desorption (H2-TPD) methods. The metals were loaded as heterobimetallic Pd(µ-O2CMe)4In(O2CMe) complex to ensure intimate contact between Pd and In. Reduction in H2 at 200 °C resulted in Pd-rich PdIn alloy as evidenced by XRD and the disappearance of Pd hydride. A minor amount of Pd1In1 intermetallic phase appeared after reduction at 200 °C and its formation was accomplished at 400 °C. Neither monometallic Pd or in nor other intermetallic structures were found after reduction at 400⁻600 °C. Catalytic performance of Pd1In1/α-Al2O3 was studied in the selective liquid-phase diphenylacetylene (DPA) hydrogenation. It was found that the reaction rate of undesired alkene hydrogenation is strongly reduced on Pd1In1 nanoparticles enabling effective kinetic control of the hydrogenation, and the catalyst demonstrated excellent selectivity to alkene.

Preparation and release characteristics of mesalazine loaded calcium pectin-silica gel beads based on callus cultures pectins for colon-targeted drug delivery.

The aim of this work is to produce calcium pectin-silica gel beads containing mesalazine as a drug model in order to control the drug release in the colon. The mesalazine loaded calcium pectin-silica gel beads were prepared using the ionotropic gelation method. Energy-dispersive X-ray analysis revealed that increasing the Na2SiO3 concentration led to an increase of the silicon content on the surface and in the cross-sections of the beads. The addition of Na2SiO3 to the gel formulations made from the duckweed callus culture pectin led to a decrease in the swelling degree that appeared to be related to the higher gel strength of these beads. The beads made from pectins of campion and duckweed callus cultures with adding of 22.2 mg/ml of Na2SiO3 showed the lowest release of mesalazine in simulated gastric and intestinal fluids. An increase in the reaction time up to 60 min during incubation in the cross-linking solution of CaCl2 led to a slower release of drug from the beads. An elevated release of mesalazine was achieved in the simulated colonic fluid. Prepared calcium pectin-silica gel beads containing mesalazine as a drug model can be proposed for controlled drug release in the colon.

Mechanical properties, structure, bioadhesion, and biocompatibility of pectin hydrogels.

The surface structure, biocompatibility, textural, and adhesive properties of calcium hydrogels derived from 1, 2, and 4% solutions of apple pectin were examined in this study. An increase in the pectin concentration in hydrogels was shown to improve their stability toward elastic and plastic deformation. The elasticity of pectin hydrogels, measured as Young's modulus, ranged from 6 to 100 kPa. The mechanical properties of the pectin hydrogels were shown to correspond to those of soft tissues. The characterization of surface roughness in terms of the roughness profile (Ra) and the root-mean-square deviation of the roughness profile (Rq) indicated an increased roughness profile for hydrogels depending on their pectin concentration. The adhesion of AU2% and AU4% hydrogels to the serosa abdominal wall, liver, and colon was higher than that of the AU1% hydrogel. The adhesion of macrophages and the non-specific adsorption of blood plasma proteins were found to increase as the pectin concentration in the hydrogels increased. The rate of degradation of all hydrogels was higher in phosphate buffered saline (PBS) than that in DMEM and a fibroblast cell monolayer. The pectin hydrogel was also found to have a low cytotoxicity. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 2572-2581, 2017.

In vitro gastrointestinal-resistant pectin hydrogel particles for ß-glucuronidase adsorption.

Pectin hydrogel particles (PHPs) were prepared by ionotropic gelation of low methylesterified pectin of Tanacetum vulgare L. with calcium ions. Wet PHPs prepared from TVF exhibited a smaller diameter and the lower weight as well as exhibited the best textural properties in terms of hardness and elasticity compared to the PHPs prepared from commercial low methylesterified pectin (CU701) used for comparison. Upon air drying, PHPs prepared from CU701 became small and dense microspheres whereas the dry PHPs prepared from TVF exhibited a drop-like shape. The morphology of dry PHPs determined by scanning electron microscopy revealed that the surface of the TVF beads exhibited fibred structures, whereas the PHPs prepared from CU701 exhibited a smooth surface. The characterization of surface roughness using atomic force microscopy indicated less roughness profile of the PHPs prepared from TVF than CU701. PHPs prepared from TVF were found to possess in vitro resistance to successive incubations in simulated gastric (SGF), intestinal (SIF), and colonic fluid (SCF) at 37 °C for 2, 4 and 18 h, respectively. The PHPs prepared from CU701 swelled in SGF and then lost their spherical shape and were fully disintegrated after 4 h of incubation in SIF. The PHPs from TVF, which were subjected to treatment with SGF, SIF and SCF, were found to adsorb microbial ß-glucuronidase (ßG) in vitro. The data obtained offered the prospect for the development of the PHPs from TVF as sorbents of colonic ßG for the inhibition of re-absorption of estrogens.

Preparation and biocompatibility evaluation of pectin and chitosan cryogels for biomedical application.

Today, there is a need for the development of biomaterials with novel properties for biomedical purposes. The biocompatibility of materials is a key factor in determining its possible use in biomedicine. In this study, composite cryogels were obtained based on pectin and chitosan using ionic cryotropic gelation. For cryogel preparation, apple pectin (AP), Heracleum L. pectin (HP), and chitosan samples with different physical and chemical characteristics were used. The properties of pectin-chitosan cryogels were found to depend on the structural features and physicochemical characteristics of the pectin and chitosan within them. The addition of chitosan to cryogels can increase their mechanical strength, cause change in surface morphology, increase the degradation time, and enhance adhesion to biological tissues. Cryogels based on AP were less immunogenic when compared with cryogels from HP. Cryogels based on AP and HP were hemocompatible and the percentage of red blood cells hemolysis was less than 5%. Unlike cryogels based on HP, which exhibited moderate cytotoxicity, cryogels based on AP exhibited light cytotoxicity. Based on the results of low immunogenicity, light cytotoxicity data as well as a low level of hemolysis of composite cryogels based on AP and chitosan are biocompatible and can potentially be used in biomedicine. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 547-556, 2017.