Structure and Mechanical Properties of iPP-Based Nanocomposites Crystallized under High Pressure.

The unique nonparallel chain arrangement in the orthorhombic γ-form lamellae of isotactic polypropylene (iPP) results in the enhancement of the mechanical properties of γ-iPP. Our study aimed at the investigation of the mechanical properties of γ-iPP nanocomposites with 1-5 wt.% multiwall carbon nanotubes (MWCNT) and 5 wt.% organo-modified montmorillonite prepared by melt-mixing and high-pressure crystallization. Neat iPP and the nanocomposites were crystallized under high pressures of 200 MPa and 300 MPa, and for comparison under 1.4 MPa, in a custom-built high-pressure cell. The structure of the materials was studied using WAXS, SAXS, DSC, and SEM, whereas their mechanical properties were tested in plane-strain compression. Under a small pressure of 1.4 MPa, polymer matrix in all materials crystallized predominantly in the α-form, the most common monoclinic form of iPP, whereas under high pressure it crystallized in the γ-form. This caused a significant increase in the elastic modulus, yield stress, and stress at break. Moreover, due to the presence of MWCNT, these parameters of the nanocomposites exceeded those of the neat polymer. As a result, a 60-70% increase in the elastic modulus, yield stress, and stress at break was achieved by filling of iPP with MWCNT and high-pressure crystallization.

Synthesis and biophysical evaluation of carbosilane dendrimers as therapeutic siRNA carriers.

Gene therapy presents an innovative approach to the treatment of previously incurable diseases. The advancement of research in the field of nanotechnology has the potential to overcome the current limitations and challenges of conventional therapy methods, and therefore to unlocking the full potential of dendrimers for use in the gene therapy of neurodegenerative disorders. The blood-brain barrier (BBB) poses a significant challenge when delivering therapeutic agents to the central nervous system. In this study, we investigated the biophysical properties of dendrimers and their complexes with siRNA directed against the apolipoprotein E (APOE) gene to identify an appropriate nanocarrier capable of safely delivering the cargo across the BBB. Our study yielded valuable insights into the complexation process, stability over time, the mechanisms of interaction, the influence of dendrimers on the oligonucleotide's spatial structure, and the potential cytotoxic effects on human cerebral microvascular endothelium cells. Based on our findings, we identified that the dendrimer G3Si PEG6000 was an optimal candidate for further research, potentially serving as a nanocarrier capable of safely delivering therapeutic agents across the BBB for the treatment of neurodegenerative disorders.

3D printing of dolutegravir-loaded polylactide filaments as a long-acting implantable system for HIV treatment.

3D printing was used to prepare implantable systems or tablets loaded with dolutegravir to explore their potential as long-acting implantables (LAIs). Our strategy relies on preparing a polylactide (PLA) filament loaded with the anti-HIV drug. Subsequently, 3D printing was performed under conditions that allowed the PLA to be simultaneously melted and the drug encapsulated within the printed strand. The dolutegravir release profiles indicated its sustained release for 47 days. Furthermore, neat and drug-loaded tablets were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA), while their morphology was assessed by scanning electron microscopy (SEM). Finally, their biocompatibility was proved by MTT assay against ISO standards recommended L929 mouse and human Hs68 skin fibroblast cells. All the results indicated that the 3D printing of PLA-based tablets could produce customized medications with potential applications against HIV.

A New Look at the Mechanism of Cocrystal Formation and Coformers Exchange in Processes Forced by Mechanical and/or Thermal Stimuli - ex situ and in†situ Studies of Low-Melting Eutectic Mixtures.

Three different devices: ball mill, hot stage melting, and magic angle spinning (MAS) NMR rotor were used for the preparation of ethenzamide (ET) cocrystals with glutaric acid (GLU), ethylmalonic acid (EMA) and maleic acid (MAL) as coformers. In each case, well-defined binary systems (ET:EMA, ET:GLU, ET:MAL) were obtained. The common features of the two solvent free methods of cocrystal formation (grinding, melting) are presented on the basis of arguments obtained by solid state NMR spectroscopy. Thermal analysis (Differential Scanning Calorimetry) proved that the eutectic phase arises over a wide range of molar ratios of components for each of the binary systems. NMR techniques, supported by theoretical calculations, allowed to provide details about the pathway of the reaction mechanism with atomic accuracy. It was found that the formation of ET cocrystals is a complex process that requires five steps. Each step has been recognized and described. Variable temperature 1D and 2D MAS NMR experiments allowed to track physicochemical processes taking place in a molten state. Moreover, it was found that in a multicomponent mixture consisting of all four components, ET, EMA, GLU, and MAL, ET in the molten phase behaves as a specific selector choosing only one partner to form binary cocrystals according to energy preferences. The process of exchange of coformers in binary systems during grinding, melting, and NMR measurements is described. The stabilization energies (Estab ) and molecular electrostatic potential (MEP) maps computed for the cocrystals under discussion and their individual components rationalize the selection rules and explain the relationships between individual species.

Influence of hydrophilic block length on the aggregation properties of polyglycidol-polystyrene-polyglycidol copolymers.

Amphiphilic triblock copolymers, polyglycidol-polystyrene-polyglycidol (PGL-PS-PGL), were synthesised via anionic polymerization starting from the synthesis of a polystyrene macroinitiator with 60 styrene units in the block terminated by ethylene oxide. Poly(ethoxyethyl glycidyl ether) blocks of different lengths were created on both sides of the macroinitiator. By removing the ethoxyethyl blocking groups, PGL-PS-PGL copolymers containing polyglycidol blocks with DP 11, 23, 44 and 63 were received. Their structures were determined by NMR and FTIR. The hydrophilicity of PLG-PS-PGL films was studied upon exposure to water vapour. To perform the copolymers' aggregation in water, the samples were dialysed from DMF into water. The critical concentration of their micellisation (CMC) was determined by measuring the absorbance of the 1,6-diphenylhexa-1,3,5-triene (DPH) probe and the intensity of light scattered by the copolymers' solution as a function of concentration. CMC values increased with increasing the number of hydrophilic glycidol units in the copolymer chain. The sizes of aggregates formed slightly above the critical concentration were measured by dynamic light scattering (DLS), and particles were imaged by cryo-TEM. Cryo-TEM pictures showed the presence of regular micelles in copolymer dispersions. For copolymers with shorter PGL chains aggregated partices were detected. Moreover, cryo-TEM demonstrated that the copolymers with a polyglycidol block of DP = 63 formed regular spherical micelles that formed 2D ordered organisation on the surface. X-ray measurements showed the formation of a partially crystallised PS core in the micelle's interior. The aggregates of all copolymers were stable. Their sizes did not change after one year of storage. The particles did not disassociate even after diluting their dispersions to a concentration 10 times lower than the critical concentration.

Electrical Conductivity and Antibacterial Activity of Woven Fabrics through Quercetin-Assisted Thermal Reduction of a Graphene Oxide Coating.

Cotton and poly(ethylene terephthalate) (PET) woven fabrics were coated with graphene oxide (GO) using a padding method and the GO deposited on the fiber surfaces was thermally reduced to impart electrical conductivity to the fabrics. To assist the thermal reduction of GO, quercetin (Q)-a natural flavonoid-was used. To this end, before the reduction, the GO-padded fabrics were immersed in Q solutions in ethanol with different Q concentrations. Q enhanced the thermal reduction of GO. Depending on the Q concentration in the solutions, electrical surface resistivities of the cotton fabric of 750 kΩ/sq to 3.3 MΩ/sq and of the PET fabric of 240 kΩ/sq to 730 kΩ/sq were achieved. The cotton and PET fabrics also became hydrophobic, with water contact angles of 163° and 147°, respectively. In addition to the electrical conductivity, the presence of Q resulted in antibacterial activity of the fabrics against Escherichia coli and Staphylococcus aureus.

Nanohybrids Composed of Tannic Acid Cross-Linked by Metal Ions Obtained by a Microfluidic Technique.

Naturally occurring compounds, such as tannic acid (TA), are perfect for constructing nanohybrids (NHs) with metal ions due to their anticarcinogenic, antimicrobial, and antioxidant properties. To date, the batch methods are the ones in which such NHs were constructed; however, those methods possess many drawbacks, such as low reproducibility or size variations. To overcome this limitation, microfluidic preparation is proposed for NHs construction composed of TA and iron (III). The spherical particles with a size between 70 and 150 nm and antimicrobial properties can be easily fabricated in a controlled manner.

Electrically conductive crystalline polylactide nonwovens obtained by electrospinning and modification with multiwall carbon nanotubes.

Polylactide nonwovens were electrospun from solutions and then crystallized, one in α-form, and another, S-PLA, made of poly(l-lactide) and poly(d-lactide) 1:1 blend, in scPLA crystals with high melting temperature, close to 220 °C. To make the nonwovens electrically conductive, they were coated with multiwall carbon nanotubes (MWCNT) by padding and dip-coating with an aqueous dispersion of MWCNT. The electrical conductivity evidenced the formation of the electrically conductive MWCNT network on the fiber surfaces. Depending on the coating method, the surface resistivity (Rs) of S-PLA nonwoven of 1.0 kΩ/sq and 0.09 kΩ/sq was reached. To study the effect of surface roughness, before the modification the nonwovens were etched with sodium hydroxide, which additionally made them hydrophilic. The effect of etching depended on the coating method and led to an increase or decrease of Rs, in the case of padding or dip-coating, respectively. All MWCNT-modified nonwovens, unetched and etched, were hydrophobic with water contact angles of 138-144°. Scanning electron microscopy corroborated the presence of MWCNT on the fiber surfaces. Impedance spectroscopy confirmed the dominant role of the network of MWCNT direct contacts on the electrical properties of MWCNT-modified nonwovens in a broad frequency range.

New Class of Polymer Materials-Quasi-Nematic Colloidal Particle Self-Assemblies: The Case of Assemblies of Prolate Spheroidal Poly(Styrene/Polyglycidol) Particles.

Assemblies of colloidal polymer particles find various applications in many advanced technologies. However, for every type of application, assemblies with properly tailored properties are needed. Until now, attention has been concentrated on the assemblies composed of spherical particles arranged into so-called perfect colloidal crystals and on complex materials containing mixtures of crystal and disordered phases. However, new opportunities are opened by using assemblies of spheroidal particles. In such assemblies, the particles, in addition to the three positional have three angular degrees of freedom. Here, the preparation of 3D assemblies of reference microspheres and prolate spheroidal poly(styrene/polyglycidol) microparticles by deposition from water and water/ethanol media on silicon substrates is reported. The particles have the same polystyrene/polyglycidol composition and the same volumes but differ with respect to their aspect ratio (AR) ranged from 1 to 8.5. SEM microphotographs reveal that particles in the assembly top layers are arranged into the quasi-nematic structures and that the quality of their orientation in the same direction increase with increasing AR. Nano- and microindentation studies demonstrate that interactions of sharp and flat tips with arrays of spheroidal particles lead to different types of particle deformations.

Microbiologically Pure Cotton Fabrics Treated with Tetrabutylammonium OXONE as Mild Disinfection Agent.

The microbiological purity of textiles plays a pivotal role in the use of textiles, especially in hospitals and other medical facilities. Microbiological purity of cotton fabric was achieved by a new disinfection method using tetrabutyloammonium OXONE (TBA-OXONE) before washing. As a result of the disinfection, the cotton fabric became microbiologically pure, despite the markedly decreased washing time with respect to the widely used standard procedure. Shortening of the washing time allowed for significant energy savings. In addition, the effect of the number of disinfection and washing cycles on the tensile properties and tearing force of the fabric was examined. After 120 disinfection and washing cycles the mechanical properties of cotton fabric were only slightly worsened.

Antibacterial Electroconductive Composite Coating of Cotton Fabric.

Graphene oxide (GO) was deposited on a cotton fabric and then thermally reduced to reduced graphene oxide (rGO) with the assistance of L-ascorbic acid. The GO reduction imparted electrical conductivity to the fabric and allowed for electrochemical deposition of Ag° particles using cyclic voltammetry. Only the Ag°/rGO composite coating imparted antibacterial properties to the fabric against Escherichia coli and Staphylococcus aureus. Ag°/rGO-modified fibers were free of bacterial film, and bacterial growth inhibition zones around the material specimens were found. Moreover, Ag°/rGO-modified fabric became superhydrophobic with WCA of 161°.

Synthesis, Hydrophilicity and Micellization of Coil-Brush Polystyrene-b-(polyglycidol-g-polyglycidol) Copolymer-Comparison with Linear Polystyrene-b-polyglycidol.

In this paper, an original method of synthesis of Coil-Brush amphiphilic polystyrene-b-(polyglycidol-g-polyglycidol) (PS-b-(PGL-g-PGL)) block copolymers was developed. The hypothesis that their hydrophilicity and micellization can be controlled by polyglycidol blocks architecture was verified. The research enabled comparison of behavior in water of PS-b-PGL copolymers and block-brush copolymers PS-b-(PGL-g-PGL) with similar composition. The Coil-Brush copolymers were composed of PS-b-PGL linear core with average DPn of polystyrene 29 and 13 of polyglycidol blocks. The DPn of polyglycidol side blocks of coil-b-brush copolymers were 2, 7, and 11, respectively. The copolymers were characterized by 1H and 13C NMR, GPC, and FTIR methods. The hydrophilicity of films from the linear and Coil-Brush copolymers was determined by water contact angle measurements in static conditions. The behavior of Coil-Brush copolymers in water and their critical micellization concentration (CMC) were determined by UV-VIS using 1,6-diphenylhexa-1,3,5-trien (DPH) as marker and by DLS. The CMC values for brush copolymers were much higher than for linear species with similar PGL content. The results of the copolymer film wettability and the copolymer self-assembly studies were related to fraction of hydrophilic polyglycidol. The CMC for both types of polymers increased exponentially with increasing content of polyglycidol.

Modification of Polylactide Nonwovens with Carbon Nanotubes and Ladder Poly(silsesquioxane).

Electrospun nonwovens of poly(L-lactide) (PLLA) modified with multiwall carbon nanotubes (MWCNT) and linear ladder-like poly(silsesquioxane) with methoxycarbonyl side groups (LPSQ-COOMe) were obtained. MWCNT and LPSQ-COOMe were added to the polymer solution before the electrospinning. In addition, nonwovens of PLLA grafted to modified MWCNT were electrospun. All modified nonwovens exhibited higher tensile strength than the neat PLA nonwoven. The addition of 10 wt.% of LPSQ-COOMe and 0.1 wt.% of MWCNT to PLLA increased the tensile strength of the nonwovens 2.4 times, improving also the elongation at the maximum stress.

Microfluidic-assisted nanoprecipitation of biodegradable nanoparticles composed of PTMC/PCL (co)polymers, tannic acid and doxorubicin for cancer treatment.

This study was aimed towards the development of a novel microfluidic approach for the preparation of (co)polymeric and hybrid nanoparticles (NPs) composed of (co)polymers/tannic acid (TA) in the microfluidic flow-focusing glass-capillary device. The MiliQ water was used as water phase, whereas the organic phase was composed of poly(ε-caprolactone) (PCL) and poly(trimethylene carbonate) (PTMC) homopolymers and (co)polymers with different proportion of comonomers which were prepared via enzymatic polymerization that allows avoiding the usage of potentially toxic catalyst. To prepare hybrid NPs, TA was additionally added to the organic phase. Subsequently, as a result of mixing between these distinct phases in microfluidic channels, the nanoprecipitation in the form of spherical NPs occurs. The size of NPs was tuned over the range of 140-230 nm by controlling phase flow rates and the composition of NPs. Moreover, the release studies of the encapsulated anticancer drug doxorubicin (DOX) demonstrated that the drug release is greatly influenced by the (co)polymers composition, their molecular weight, NPs size, and the presence of TA. The antitumor activities of the (co)polymeric and hybrid NPs toward breast cancer cells (MCF-7) were tested in vitro. Among all tested formulation, the NPs composed of PCL/TA most efficiently inhibit the cell proliferation of MCF-7 cells, most importantly, their efficiency was higher than free DOX. The proposed strategy may provide an efficient alternative for the construction of nanocarriers with great potential in anticancer therapy.

Hybrid Fluorescent Poly(silsesquioxanes) with Amide- and Triazole-Containing Side Groups for Light Harvesting and Cation Sensing.

Hybrid polymers containing pyrene (Py) units bound to linear poly(silsesquioxane) (LPSQ) chains through flexible linkers containing heteroatoms (S, N, O) (LPSQ-triazole-Py and LPSQ-amide-Py) exhibit intense fluorescence emission, both in very diluted solutions (c = 10-8 mol/L) and in the solid state. The materials are thermally stable and exhibit good thin film forming abilities. Their optical and physicochemical properties were found to be strongly dependent on the structure of the side chains. Comparative studies with octahedral silsesquioxane (POSS) analogues (POSS-triazole-Py and POSS-amide-Py) emphasized the role of the specific double-strand architecture of the LPSQ backbone and distribution of side Py groups for their photo-luminescent properties. The new hybrid materials were tested as fluorescence energy donors to red-emitting dyes (Nile Red and Coumarine 6). All the silsesquioxanes studied were found to be able to transfer FL emission energy to Coumarin 6, irrespectively of their spatial structure. However, due to the differences in the wavelength range of FL emission, only LPSQ-triazole-Py were able to act as energy donors to Nile Red. The Py-grafted LPSQ may be also applied for development of soluble and highly emissive chemosensors. Their fluorescent nature was explored for the detection of Cu(II), Fe(III), Co(II), Ag(I), Hg(II), Mg(II), Ca(II), Pb(II) and Zn(II). The morphology of the side chains and hydrogen-bonding interactions influenced the sensing capacity of all the studied materials.

PLA/ß-CD-based fibres loaded with quercetin as potential antibacterial dressing materials.

Microbial infections lead to elevated inflammatory responses, which usually result in prolonged and incomplete wound healing. Therefore, there is an increasing demand for biodegradable fibres that are effective against a different range of microorganisms, especially those with antibiotic resistance. Herein, quercetin-(Q)-loaded polylactide-based fibres were developed using the electrospinning technique. Since Q exhibits low chemical stability, we used star-shaped polylactides (PLAs) with a ß-CD core to host Q by inclusion complexation. To enhance the stability of the fibres and additionally entrap the Q between polymeric chains, we adapted supramolecular cross-linking by the stereocomplexation of PLAs with opposite configurations. As a control, we prepared an additional formulation of star-shaped/commercial PLA/Q for the preparation of nonwovens in which the ß-CD moiety was not present. All developed fibres were smooth and continuous, with an average diameter of 37 µm. Although nonwovens did not possess diffusible activity, good antibacterial effects against Staphylococcus aureus (S. aureus), Escherichia coli (E.coli) and Klebsiella pneumoniae (K. pneumoniae) were observed. All these features validate the proposed approach, in which different supramolecular interactions were used to modify the properties of PLA-based fibres and, most importantly, show their great potential usefulness against microbial infections.

Adsorption and covalent binding of fibrinogen as a method for probing the chemical composition of poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) microsphere surfaces.

We investigated the distribution of polyglycidol and polystyrene on the surface of poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) microspheres (random distribution or segregated into hydrophilic and hydrophobic patches), using fibrinogen (Fb) as a macromolecular probe. The fibrinogen was adsorbed or covalently attached to the surface of the poly(styrene-co-α-tert-butoxy-ω-vinylbenzyl-polyglycidol) (P(S/PGLy)) microspheres. The P(S/PGLy) particles were prepared by emulsion copolymerization of styrene and α-tert-butoxy-ω-vinylbenzyl-polyglycidol (PGLy) macromonomer initiated with potassium persulfate. The polymerizations yielded P(S/PGLy) particles with various surface fractions of polyglycidol, depending on the amount of added macromonomer and the addition process. In some syntheses, the entire macromonomer amount was added once at the beginning of the polymerization, while in others, the macromonomer was added gradually after the formation of particle seeds from pure polystyrene. XPS studies revealed that the fraction of polyglycidol in the interfacial layer of the microspheres was larger when the entire amount of macromonomer was added at the beginning of the polymerization than when it was added after formation of the polystyrene seeds. Studies of fibrinogen adsorption provided the first evidence of segregation of the hydrophobic (polystyrene) and hydrophilic (polyglycidol) components at the surface of the composite P(S/PGLy) microspheres into patches. The hydrophobic patches are composed mainly of polystyrene. However, they also contain a small amount of polyglycidol chains, making the adsorption of fibrinogen weaker than the adsorption onto the pure polystyrene. Studies of covalent immobilization of fibrinogen on the microspheres via 1,3,5-trichlorotriazine confirmed these findings.

Supramolecular self-assembly of linear oligosilsesquioxanes on mica--AFM surface imaging and hydrophilicity studies.

Linear oligomeric [2-(carboxymethylthio)ethylsilsesquioxanes] (LPSQ-COOH) adsorb spontaneously on muscovite mica and form smooth, well-ordered lamellar structures at the liquid-solid interface. Side carboxylic groups, having donor-acceptor character with regard to hydrogen bonds, are engaged both in multipoint molecule-to-substrate interactions and intermolecular cross-linking. The unique arrangement of silsesquioxane macromolecules, with COOH groups situated at the interface with air, produces highly hydrophilic surfaces of good thermal and solvolytic stability. Supramolecular assemblies of LPSQ-COOH were studied using atomic force microscopy (AFM), angle-resolved X-ray photoelectron spectroscopy (ARXPS) and attenuated total reflectance (ATR) FTIR spectroscopy. Comparative height profile analysis combined with ATR-FTIR studies of the spectral regions characteristic of carboxylic groups and C1s core level envelope by XPS confirmed specific interactions between LPSQ-COOH and mica.

Nanostructured surfaces by supramolecular self-assembly of linear oligosilsesquioxanes with biocompatible side groups.

Linear oligomeric silsesquioxanes with polar side moieties (e.g., carboxylic groups and derivatives of N-acetylcysteine, cysteine hydrochloride or glutathione) can form specific, self-assembled nanostructures when deposited on mica by dip coating. The mechanism of adsorption is based on molecule-to-substrate interactions between carboxylic groups and mica. Intermolecular cross-linking by hydrogen bonds was also observed due to the donor-acceptor character of the functional groups. The texture of supramolecular nanostructures formed by the studied materials on mica was analysed with atomic force microscopy and their specific surface energy was estimated by contact angle measurements. Significant differences in the surface roughness, thickness and the arrangement of macromolecules were noted depending on the kind of functional groups on the side chains. Specific changes in the morphology of the surface layer were observed when mica was primed with a monolayer of small organic compounds (e.g., N-acetylcysteine, citric acid, thioglycolic or acid). The adsorption of both silsesquioxane oligomers and organic primers was confirmed with attenuated total reflectance infrared spectroscopy. The observed physiochemical and textural variations in the adsorbed materials correlate with the differences in the chemical structure of the applied oligomers and primers.

[Cardiovascular diseases risk factors knowledge among soldiers of the Polish army]. / Znajomosc czynników ryzyka chorób ukladu sercowo-naczyniowego wsród zolnierzy polskiej armii.

UNLABELLED: Cardiovascular diseases (CVDs) are the main cause of death and disability in Poland. There are many risk factors of CVD which are modifiable due to preventive strategies. Knowledge about these factors among population at risk of CVD is the most important condition for success of them. THE AIM OF THE STUDY: To evaluate the knowledge of CVD risk factors among soldiers of the Polish Army and try to identify a demographic factors influenced on them. MATERIAL AND METHODS: Authors investigated the level of knowledge about CVD risk factors among 644 soldiers (aged between 18 to 62 years) using the special questionnaire. Whole group was analyzed according to a place of origin: city, town and village and according to a function: professionals and conscripts. RESULTS: Soldiers achieved a total score of 58.4% correct answers. Commonly known risk factors of CVD (average 82% of correct answers) in studied group were: obesity, tobacco smoking, high level of cholesterol and hypertension. Knowledge about above risk factors was significantly higher (p < 0.01) than about other. Lesser known risk factors (average 54% of correct answers) were: male gender, abnormal diet, sedentary lifestyle, family history of CVDs, diabetes, family history of heart infarction below 55 yrs and peripheral atherosclerosis. residents achieved 64.5% correct answers, town--61.5%, and village--58%. Professionals achieved 65.1% vs. 58.8% for conscripts. The level of knowledge about CVD risk factors are significantly higher among professionals than in urban population. CONCLUSIONS: Our data confirm the need of continuation and developing new CVDs preventive strategies in Poland, especially among poor educated and village populations. There is a need to emphasize the role of lesser known, modifiable CVD risk factors (e.g., obesity, sedentary lifestyle) in existing and future health programs.