Nanoparticles coated by chloramphenicol in hydrogels as a useful tool to increase the antibiotic release and antibacterial activity in dermal drug delivery

Abstract Background Nanocarriers for antibacterial drugs became hopeful tools against the increasing resistance of bacteria to antibiotics. This work focuses on a comprehensive study of the applicability and therapeutic suitability of dermal carbopol-based hydrogels containing chloramphenicol carried by various nanoparticles (AuNPs and SiNPs). Methods The different forms of carbopol-based drugs for dermal use were obtained. Five different concentrations of chloramphenicol and two types of nanoparticles (silica and gold) in carbopol-based ointments were tested. The influence of different carbopol formulations with nanocarriers on the rheological properties as well as the release profile of a…

Copolymerization of ethylene with norbornene or 1-octene using supported ionic liquid systems

Copolymerization of ethylene with norbornene (E/NB) and ethylene with 1-octene (E/Oct) is performed using supported ionic liquid (SIL) systems, in which metallocene (Cp2VCl2) or post-metallocene [VCl2(salenCl2)] vanadium catalysts are immobilized in pyridinium chloroaluminate ionic liquid supported on silica. The studied SIL catalysts show higher activities as well as stability than their non-supported analogues. In addition, higher activities and better comonomer incorporation are observed for norbornene (above 30 mol%). The comonomer incorporation has considerable influence on copolymer molecular weight (M w), melting temperature, crystallinity degree, and microstructure of the copolymers…

Nickel‐Catalyzed C(sp2)−C(sp3) Kumada Cross‐Coupling of Aryl Tosylates with Alkyl Grignard Reagents

Aryl tosylates are an attractive class of electrophiles for cross‐coupling reactions due to ease of synthesis, low price, and the employment of C−O electrophiles, however, the reactivity of aryl tosylates is low. Herein, we report the Ni‐catalyzed C(sp2)−C(sp3) Kumada cross‐coupling of aryl tosylates with primary and secondary alkyl Grignard reagents. The method delivers valuable alkyl arenes by cross‐coupling with challenging alkyl organometallics possessing β‐hydrogens that are prone to β‐hydride elimination and homo‐coupling. The reaction is catalyzed by an air‐ and moisture stable‐Ni(II) precatalyst. A broad range of electronically‐varied aryl tosylates, including bis‐tosylates, underwe…

A New Supported Zirconocene Catalyst for Ethylene Polymerization

Metallocene catalysts enable the structure of polymers to be tailored in a way which has not been reached before. However, they are more active than the conventional Ziegler — Natta catalysts only as homogeneous metalocene systems, a fact that has essentially restricted their use to industrial processes producing polymers in solution. Modern polymerization processes are solvent free slurry (with liquid monomer) or gas phase processes. To use metallocene catalysts in these modern processes, it is necessary to convert them to heterogeneous catalysts [1, 2]. However, problems have appeared chiefly concerning the activity of the supported catalysts, because heterogeneous metallocene catalysts a…

Cobalt−NHC Catalyzed C(sp 2 )−C(sp 3 ) and C(sp 2 )−C(sp 2 ) Kumada Cross‐Coupling of Aryl Tosylates with Alkyl and Aryl Grignard Reagents

Role of calcium carbonate in the process of heavy metal biosorption from solutions: synergy of metal removal mechanisms.

AbstractThe effect of calcium carbonate on the removal efficiency of cations of the selected heavy metals Cu, Zn and Pb from aqueous solutions using various biosorbents (BS) was investigated under laboratory static conditions. The main mechanism of biosorption of heavy metal cations is ion exchange, whereas the reaction with calcium carbonate results in precipitation of poorly soluble carbonates and hydroxides of the examined heavy metals. Studies conducted under static conditions have shown that the effect of Cu and Zn cations removal from solutions is better when using a mixture of BS and CaCO3 as compared to the effect of process, in which these two components were used separately. Remov…

On the impact of side methyl groups on the structure and vibrational properties of β-carotenoids. The case of butadiene and isoprene

Abstract Theoretical consideration about the impact of methyl groups on the structure and vibrational properties of β-carotenoids, using medium size molecules of trans-butadiene and trans-isoprene, are reported. Density functional theory (DFT) calculations with correlation-consistent and polarization-consistent basis sets were applied to trans-1,3-butadiene and trans-isoprene as the smallest building bricks of β-carotenoids. Their structure and harmonic vibrations were estimated in the complete basis set limit (CBS) using the non-linear least square fit. Optimized geometries and harmonic frequencies, obtained with B3LYP and BLYP density functionals and large basis sets, were favorably repro…

Ionic Liquids in Biphasic Ethylene Polymerisation

Over the past several years there has been a considerable increase in the interest of ionic liquids as versatile reaction media for a wide variety of synthetic processes. The popularity of ionic liquids has been related primarily to their unique physical and chemical properties, which can be tailored by the judicious selection of cations and anions. These properties make it possible to use ionic liquids as solvents for many organic, inorganic, and organometallic compounds, including catalysts and co-catalysts, for various types of reactions. In particular, the polar but weakly coordinating character of ionic liquids enables them to be applied as mediums in catalysis, to immobilize various k…

Pyrazole amino acids: hydrogen bonding directed conformations of 3-amino-1H-pyrazole-5-carboxylic acid residue

A series of model compounds containing 3-amino-1H-pyrazole-5-carboxylic acid residue with N-terminal amide/urethane and C-terminal amide/hydrazide/ester groups were investigated by using NMR, Fourier transform infrared, and single-crystal X-ray diffraction methods, additionally supported by theoretical calculations. The studies demonstrate that the most preferred is the extended conformation with torsion angles ϕ and ψ close to ±180°. The studied 1H-pyrazole with N-terminal amide/urethane and C-terminal amide/hydrazide groups solely adopts this energetically favored conformation confirming rigidity of that structural motif. However, when the C-terminal ester group is present, the second con…

High crystallinity polyethylene obtained in biphasic polymerization using pyridinium chloroaluminate ionic liquid

A series of N-n-alkylpyridinium chloroaluminate ionic liquids [C n -py][AlCl4] (where n-alkyl = n-butyl, n-hexyl, and n-octyl) was applied as a medium of the Cp2TiCl2 catalyst, activated by AlEtCl2 or AlEt2Cl, to evaluate the influence of the studied ionic liquids on the performance of the biphasic ionic liquid/hexane ethylene polymerization and the properties of the produced polyethylene (PE). The best results were obtained using N-n-butylpyridinium chloroaluminate. The polyethylene obtained in the biphasic polymerization have the high crystallinity, which was confirmed by DSC, WAXS and PALS methods, as well as the bulk density comparable to commercial HDPE. These unique properties results…

Vanadium catalysts for ethylene-norbornene copolymerization

Cyclic olefin copolymers (COCs) are a promising group of materials with specific, projectable properties. In this group, copolymers of ethylene and norbornene are of particular interest. A variety of transition metal complexes are used for their synthesis, mostly elements from group 4. This review presents the application of vanadium catalysts with various types of ligands in the synthesis of ethylene-norbornene copolymers. The influence of ligands and reaction conditions on the activity of catalyst and selected properties of copolymers are described in this paper.

Effect of sample preparation on gel permeation chromatography results of determination of molecular weight of polyethylene obtained with using of zirconocene catalyst actiyated with methyl aluminoxane

Molecular weights of polyethylene (PE) obtained with using of zirconocene catalyst activated with large excess of methylaluminoxane (MAO) were determined by gel permeation chromatography (GPC) method. It was found that repeatability of the measurements is strongly influenced by MAO remained in PE samples as well as time of sample keeping in the apparatus (dissolution + measurement time) at temp. 142 °C. A method of MAO removing from PE samples, before GPC measurement, based on additional washing of the sample with HF in methanol solution has been proposed. This modification leads to better both authenticity and repeatability of the results. Studies on the influence of time of sample keeping…

Magnesium chloride modified with organoaluminium compounds as a support of the zirconocene catalyst for ethylene polymerisation

Abstract This work describes the influence of the modification of the MgCl2(THF)2 and MgCl2 magnesium supports with the AlEt2Cl, MAO, AlEt3, AlMe3, and AlEt2Cl alkylaluminium compounds on heterogenisation of the bis(cyclopentadienyl) zirconium(IV) dichloride Cp2ZrCl2 catalyst. It was found that only the MgCl2(THF)2 support modified with AlEt2Cl gave the heterogeneous catalyst. On the contrary, application of a magnesium carrier modified by AlEt3, AlMe3, and MAO compounds only results in a homogeneous zirconocene catalyst.

Effect of immobilization of titanocene catalyst in aralkyl imidazolium chloroaluminate media on performance of biphasic ethylene polymerization and polyethylene properties

1-(2-Phenylethyl)-3-methylimidazolium and 1-benzyl-3-methylimidazolium chloroaluminates, [Ph-C2mim][AlCl4] and [Bzlmim][AlCl4], were applied as media of the Cp2TiCl2 catalyst for biphasic ethylene polymerization. The studied aralkyl ionic liquids ensure greater stability of the catalyst at higher temperatures and more regular morphology of the produced polyethylene than analogous 1-n-alkyl-3-methylimidazolium chloroaluminates. The alkylaluminium compound participates in the termination reaction of the polymer chain. The catalyst is stable and enables recycling of the ionic liquid phase in the consecutive polymerization reactions. The [Ph-C2mim][AlCl4] ionic liquid and AlEt2Cl alkylaluminium…

Titanium and Vanadium Catalysts with 2-Hydroxyphenyloxazoline and Oxazine Ligands for Ethylene-Norbornene (co)Polymerization

A series of titanium and vanadium complexes with oxazoline 2-(4,5-dihydro-1,3-oxazol-2-yl)phenol (L1), 2-(4-methyl-4,5-dihydro-1,3-oxazol-2-yl)phenol (L2), and oxazine 2-(5,6-dihydro-4H-1,3-oxazin-2-yl)phenol (L3) ligands were synthesized, and their structures were determined by NMR and MS methods as (L)2MtCl2. The vanadium complexes were found to be highly active in ethylene (7300 kgPE/(molV&middot

Biphasic ethylene polymerisation using ionic liquid over a titanocene catalyst activated by an alkyl aluminium compound

Abstract 1-n-Butyl-3-methylimidazolium tetrachloroaluminate ([BMIM]+[AlCl4]−) was applied to biphasic ionic liquid/hexane ethylene polymerisation as a medium of the Cp2TiCl2 titanocene catalyst activated by alkylaluminium compounds (MAO, AlEt2Cl, AlEt3). The best results were obtained using AlEt2Cl. The results show that catalyst recycling, higher ethylene pressure, and greater Al/Ti molar ratio along with a greater volume of the ionic liquid phase enhance catalyst activity. The polyethylene gathered from the hexane phase is characterised primarily by its high purity. Its physical properties remain polyethylene obtained over a heterogeneous metallocene catalyst. Thus, biphasic ionic liquid …

Direct synthesis of fibrous high molecular weight polyethylene using vanadium catalysts supported on an SiO2ionic liquid system

Polyethylene of fibrous morphology was obtained using Cp2VCl2 and VCl2(salenCl2) catalysts activated by AlEt2Cl and AlEtCl2 and heterogenized on a supported ionic liquid system prepared with SiO2 and 1-(3-triethoxysilyl)propyl-3-methylimidazolium chloroaluminate. The fibre length ranges from 15 to 60 µm, depending on the reaction conditions. The polyethylene is characterized by a high molecular weight ((1.1–2.4) × 106 g mol−1) and a narrow molecular weight distribution (1.4–2.5). It is a linear polymer, properly without branching. The DSC method reveals characteristic changes in melting temperature and crystallinity degree between the first and second scan heating cycles (141 °C and 136 °C,…

Titanium and vanadium catalysts with oxazoline ligands for ethylene-norbornene (co)polymerization

A series of catalysts, (Py-ox)TiCl4, (Py-box)TiCl4, (Py-ox)VCl3, (Py-box)VCl3, SIL/(Py-ox)VCl3, SIL/(Py-box)VCl3, with 2-(1,3-oxazolin-2-yl)pyridine (Py-ox) and 2,6-bis(1,3-oxazolin-2-yl)pyridine (Py-box) ligands, silica support modified by 1-[3-(triethoxysilyl)propyl]pyridinium ethylchloroaluminate ionic liquid (SIL), activated by AlEt2Cl, AlEtCl2, and methylaluminoxane (MMAO) were studied in ethylene polymerization and ethylene-norbornene copolymerization. Single-crystal X-ray diffraction is given for both Py-ox and Py-box. The complexation was confirmed by NMR and ESI-MS methods. All complexes were found to be active in ethylene polymerization with better performance of the vanadium cata…

Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts

The series of ethylene-norbornene (E-NB) copolymers was obtained using different vanadium homogeneous and supported ionic liquid (SIL) catalyst systems. The 13C and 1H NMR (carbon and proton nuclear magnetic resonance spectroscopy) together with differential scanning calorimetry (DSC) were applied to determine the composition of copolymers such as comonomer incorporation (CNB), monomer dispersity (MD), monomer reactivity ratio (re), sequence length of ethylene (le) and tetrad microblock distributions. The relation between the type of catalyst, reaction conditions and on the other hand, the copolymer microstructure, chain termination reaction analyzed by the type of unsaturation are discusse…

Metallocenes and post-metallocenes immobilized on ionic liquid-modified silica as catalysts for polymerization of ethylene

Abstract The supported ionic liquid (SIL) strategy was used for the first time to metallocene and post-metallocene heterogeneous catalysts for olefin polymerization. The metal complexes: Cp2TiCl2, Cp2ZrCl2, FI–Ti, and Sal–Ti were immobilized in the 1-(3-triethoxysilyl)propyl-3-methylimidazolium alkylchloroaluminate ionic liquid, anchored on the surface of the mesoporous amorphous silica. The SIL systems were characterized by FTIR, 29Si NMR, N2 adsorption, EA, AAS, TG, and SEM techniques. The developed supported catalytic systems were found to be active in the ethylene polymerization and produce the polyethylene of various properties.

2-(1,3-Oxazolin-2-yl)pyridine and 2,6-bis(1,3-oxazolin-2-yl) pyridine

The data presented in this article are related to research articles “Titanium and vanadium catalysts with oxazoline ligands for ethylene-norbornene (co)polymerization (Ochędzan-Siodłak et al., 2018). For the title compounds, 2-(1,3-oxazolin-2-yl)pyridine (Py-ox) and 2,6-bis(1,3-oxazolin-2-yl)pyridine (Py-box), the single-crystal X-ray diffraction measurement together with NMR, GC, MS, DSC analysis, like also the method of crystallization are presented. Keywords: Ligands, Oxazoline, Pyridine, Conformation, Association

Improvement of biphasic polymerization by application of binary ionic liquid mixture

Abstract The mixture of two ionic liquids, 1- n -butyl-3-methylimidazolium and 1-(2-phenylethyl)-3-methylimidazolium chloroaluminates, [C 4 -mim][AlCl 4 ] and [PhC 2 -mim][AlCl 4 ], were applied as a medium to immobilize the Cp 2 TiCl 2 titanocene catalyst for biphasic ionic liquid/hexane ethylene polymerization. The system makes possible to perform the reaction at lower temperatures, below the melting temperature of the aralkyl ionic liquid. A better separation of the ionic liquid phase was observed and an easier mass transfer of the polymer product from the ionic liquid to the hexane phase was obtained. The polyethylene reveals bimodal distribution of molecular weight. It is characterized…

CCDC 1534810: Experimental Crystal Structure Determination

Related Article: Anna Kusakiewicz-Dawid, Monika Porada, Wioletta Ochędzan-Siodłak, Małgorzata A. Broda, Maciej Bujak, Dawid Siodłak|2017|J.Pept.Sci.|23|716|doi:10.1002/psc.3018

CCDC 1815355: Experimental Crystal Structure Determination

Related Article: Wioletta Ochędzan-Siodłak, Anna Bihun-Kisiel, Dawid Siodłak, Anna Poliwoda, Błażej Dziuk|2018|Data in Brief|21|449|doi:10.1016/j.dib.2018.09.129

CCDC 1580983: Experimental Crystal Structure Determination

Related Article: Wioletta Ochędzan-Siodłak, Anna Bihun-Kisiel, Dawid Siodłak, Anna Poliwoda, Błażej Dziuk|2018|Data in Brief|21|449|doi:10.1016/j.dib.2018.09.129