bluuebunny/crossref_metadata_2025 huggingface dataset:
Molecular Evidence for Flea-Borne Rickettsiosis in Febrile Patients from Madagascar
Authors: Keller Christian , Rakotozandrindrainy Raphaël , von Kalckreuth Vera , Heriniaina Jean Noël , Schwarz Norbert Georg , Pak Gi Deok , Im Justin , Espinoza Ligia Maria Cruz , Hagen Ralf Matthias , Frickmann Hagen , Rakotondrainiarivelo Jean Philibert , Razafindrabe Tsiry , Dekker Denise , May Jürgen , Poppert Sven , Marks Florian
Published: November 2021

Rickettsiae may cause febrile infections in humans in tropical and subtropical regions. From Madagascar, no molecular data on the role of rickettsioses in febrile patients are available. Blood samples from patients presenting with fever in the area of the capital Antananarivo were screened for the presence of rickettsial DNA. EDTA (ethylenediaminetetraacetic acid) blood from 1020 patients presenting with pyrexia > 38.5 °C was analyzed by gltA-specific qPCR. Positive samples were confirmed by ompB-specific qPCR. From confirmed samples, the gltA amplicons were sequenced and subjected to phylogenetic analysis. From five gltA-reactive samples, two were confirmed by ompB-specific qPCR. The gltA sequence in the sample taken from a 38-year-old female showed 100% homology with R. typhi. The other sample taken from a 1.5-year-old infant was 100% homologous to R. felis. Tick-borne rickettsiae were not identified. The overall rate of febrile patients with molecular evidence for a rickettsial infection from the Madagascan study site was 0.2% (2/1020 patients). Flea-borne rickettsiosis is a rare but neglected cause of infection in Madagascar. Accurate diagnosis may prompt adequate antimicrobial treatment.
Phage Therapy in the 21st Century: Is There Modern, Clinical Evidence of Phage-Mediated Efficacy?
Authors: Abedon Stephen , Danis-Wlodarczyk Katarzyna , Alves Diana
Published: November 2021

Many bacteriophages are obligate killers of bacteria. That this property could be medically useful was first recognized over one hundred years ago, with 2021 being the 100-year anniversary of the first clinical phage therapy publication. Here we consider modern use of phages in clinical settings. Our aim is to answer one question: do phages serve as effective anti-bacterial infection agents when used clinically? An important emphasis of our analyses is on whether phage therapy-associated anti-bacterial infection efficacy can be reasonably distinguished from that associated with often coadministered antibiotics. We find that about half of 70 human phage treatment reports—published in English thus far in the 2000s—are suggestive of phage-mediated anti-bacterial infection efficacy. Two of these are randomized, double-blinded, infection-treatment studies while 14 of those studies, in our opinion, provide superior evidence of a phage role in observed treatment successes. Roughly three-quarters of these potentially phage-mediated outcomes are based on microbiological as well as clinical results, with the rest based on clinical success. Since many of these phage treatments are of infections for which antibiotic therapy had not been successful, their collective effectiveness is suggestive of a valid utility in employing phages to treat otherwise difficult-to-cure bacterial infections.
Exploration of Benzenesulfonamide-Bearing Imidazole Derivatives Activity in Triple-Negative Breast Cancer and Melanoma 2D and 3D Cell Cultures
Authors: Balandis Benas , Mickevičius Vytautas , Petrikaitė Vilma
Published: November 2021

Heterocyclic compounds are one of the main groups of organic compounds possessing wide range of applications in various areas of science and their derivatives are present in many bioactive structures. They display a wide variety of biological activities. Recently, more and more attention has been focused to such heterocyclic compounds as azoles. In this work, we have synthesized a series of new imidazole derivatives incorporating a benzenesulfonamide moiety in their structure, which then were evaluated for their cytotoxicity against human triple-negative breast cancer MDA-MB-231 and human malignant melanoma IGR39 cell lines by MTT assay. Benzenesulfonamide-bearing imidazole derivatives containing 4-chloro and 3,4-dichlorosubstituents in benzene ring, and 2-ethylthio and 3-ethyl groups in imidazole ring have been determined as the most active compounds. Half-maximal effective concentration (EC50) of the most cytotoxic compound was 27.8 ± 2.8 µM against IGR39 cell line and 20.5 ± 3.6 µM against MDA-MB-231 cell line. Compounds reduced cell colony formation of both cell lines and inhibited the growth and viability of IGR39 cell spheroids more efficiently compared to triple-negative breast cancer spheroids.
Original Contributions to the Chemical Composition, Microbicidal, Virulence-Arresting and Antibiotic-Enhancing Activity of Essential Oils from Four Coniferous Species
Authors: Visan Diana-Carolina , Oprea Eliza , Radulescu Valeria , Voiculescu Ion , Biris Iovu-Adrian , Cotar Ani Ioana , Saviuc Crina , Chifiriuc Mariana Carmen , Marinas Ioana Cristina
Published: November 2021

This study aimed to establish the essential oil (EO) composition from young shoots of Picea abies, Larix decidua, Pseudotsuga menziesii, and Pinus nigra harvested from Romania and evaluate their antimicrobial and anti-virulence activity, as well as potential synergies with currently used antibiotics. The samples’ EO average content varied between 0.62% and 1.02% (mL/100 g plant). The mono- and sesquiterpene hydrocarbons were dominant in the composition of the studied EOs. The antimicrobial activity revealed that the minimum inhibitory concentration (MIC) values for the tested EOs and some pure compounds known for their antimicrobial activity ranged from 6.25 to 100 µL/mL. The most intensive antimicrobial effect was obtained for the Pinus nigra EO, which exhibited the best synergistic effect with some antibiotics against Staphylococcus aureus strains (i.e., oxacillin, tetracycline, erythromycin and gentamycin). The subinhibitory concentrations (sMIC) of the coniferous EOs inhibited the expression of soluble virulence factors (DN-ase, lipase, lecithinase, hemolysins, caseinase and siderophore-like), their efficiency being similar to that of the tested pure compounds, and inhibited the rhl gene expression in Pseudomonas aeruginosa, suggesting their virulence-arresting drug potential.
NanoUPLC-QTOF-MS/MS Determination of Major Rosuvastatin Degradation Products Generated by Gamma Radiation in Aqueous Solution
Authors: Dončević Lucija , Svetličić Ema , Hozić Amela , Mihaljević Branka , Jarmużek Dorota , Tartaro Bujak Ivana , Pluskota-Karwatka Donata , Ozdanovac Luka , Džeba Iva , Cindrić Mario
Published: November 2021

Rosuvastatin, a member of the statin family of drugs, is used to regulate high cholesterol levels in the human body. Moreover, rosuvastatin and other statins demonstrate a protective role against free radical-induced oxidative stress. Our research aimed to investigate the end-products of free radical-induced degradation of rosuvastatin. To induce the radical degradation, an aqueous solution of rosuvastatin was irradiated using different doses of gamma radiation (50–1000 Gy) under oxidative conditions. Rosuvastatin and related degradation products were separated on nanoC18 column under gradient elution, and identification was carried out on hyphenated nanoUPLC and nanoESI-QTOF mass spectrometer system. Elemental composition analysis using highly accurate mass measurements together with isotope fitting algorithm identified nine major degradation products. This is the first study of gamma radiation-induced degradation of rosuvastatin, where chemical structures, MS/MS fragmentation pathways and formation mechanisms of the resulting degradation products are detailly described. The presented results contribute to the understanding of the degradation pathway of rosuvastatin and possibly other statins under gamma radiation conditions.
BX795-Organic Acid Coevaporates: Evaluation of Solid-State Characteristics, In Vitro Cytocompatibility and In Vitro Activity against HSV-1 and HSV-2
Authors: Sutar Yogesh , Yadavalli Tejabhiram , Paul Sagar Kumar , Mallick Sudipta , Koganti Raghuram , Chauhan Harsh , Date Abhijit A. , Shukla Deepak
Published: November 2021

BX795 is a TANK binding kinase-1 inhibitor that has shown excellent therapeutic activity in murine models of genital and ocular herpes infections on topical delivery. Currently, only the BX795 free base and its hydrochloride salt are available commercially. Here, we evaluate the ability of various organic acids suitable for vaginal and/or ocular delivery to form BX795 salts/cocrystals/co-amorphous systems with the aim of facilitating pharmaceutical development of BX795. We characterized BX795-organic acid coevaporates using powder X-ray diffractometry, Fourier-transform infrared spectroscopy (FT-IR), Raman spectroscopy, 1H-nuclear magnetic resonance spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) to elucidate the interaction between BX795 and various organic acids such as taurine, maleic acid, fumaric acid, tartaric acid, and citric acid. Furthermore, using human corneal epithelial cells and HeLa cells, we evaluated BX795-organic acid coevaporates for in vitro cytocompatibility and in vitro antiviral activity against herpes simplex virus-type 1 (HSV-1) and type-2 (HSV-2). Our studies indicate that BX795 forms co-amorphous systems with tartaric acid and citric acid. Interestingly, the association of organic acids with BX795 improved its thermal stability. Our in vitro cytocompatibility and in vitro antiviral studies to screen suitable BX795-organic acid coevaporates for further development show that all BX795-organic acid systems, at a concentration equivalent to 10 µM BX795, retained antiviral activity against HSV-1 and HSV-2 but showed differential cytocompatibility. Further, dose-dependent in vitro cytocompatibility and antiviral activity studies on the BX795-fumaric acid system, BX795-tartaric acid co-amorphous system, and BX795-citric acid co-amorphous system show similar antiviral activity against HSV-1 and HSV-2 compared to BX795, whereas only the BX795-citric acid co-amorphous system showed higher in vitro cytocompatibility compared to BX795.
Towards the Development of a Female Animal Model of T1DM Using Hyaluronic Acid Nanocoated Cell Transplantation: Refinements and Considerations for Future Protocols
Authors: Zamboni Fernanda , Cengiz Ibrahim F. , Barbosa Ana M. , Castro Antonio G. , Reis Rui L. , Oliveira Joaquim M. , Collins Maurice N.
Published: November 2021

Female mice (Black 6 strain) (C57BL/6) aged 6 weeks were subject to low dose streptozotocin (STZ) treatment for five consecutive days to mimic type 1 diabetes mellitus (T1DM) with insulitis. At two weeks after STZ injections, evaluation of the elevated glucose levels was used to confirm diabetes. The diabetic mice were then subject to the transplantation of pancreatic β-cells (MIN-6 line). Four groups of mice were studied. The first group was injected with saline-only acting as the placebo surgery control, also known as SHAM group, the second and third groups were injected with MIN-6 single cells and polyethylene glycol-modified dipalmitoyl-glycerol-phosphatidyl ethanolamine (PEG-DPPE) modified MIN-6 single cells (500 µg per 1.106 cells), respectively, while the fourth group was injected with hyaluronic acid (HA)-coated MIN-6 single cells (5 bilayers). At seven- and fourteen-days following transplantation, the mice were euthanised. The renal and pancreatic tissues were then collected and histologically analysed. The induction of diabetes in female mice, through five-consecutive daily STZ injections resulted in inconsistent glycaemic levels. Interestingly, this shows an incomplete diabetes induction in female mice, of which we attribute to sex dimorphism and hormonal interferences. Transplantation failure of free-floating encapsulated cells was unable to decrease blood glucose hyperglycaemia to physiological ranges. The result is attributed to deprived cell–cell interactions, leading to decreased β-cells functionality. Overall, we highlight the necessity of refining T1DM disease models in female subjects when using multiple low-dose STZ injections together with transplantation protocols. Considerations need to be made regarding the different developmental stages of female mice and oestrogen load interfering with pancreatic β-cells susceptibility to STZ. The use of pseudo islets, cell aggregates and spheroids are sought to improve transplantation outcome in comparison to free-floating single cells.
Synthesis, Characterization, and Intrinsic Dissolution Studies of Drug–Drug Eutectic Solid Forms of Metformin Hydrochloride and Thiazide Diuretics
Authors: Coyote-Dotor Guadalupe , Páez-Franco José C. , Canseco-González Daniel , Núñez-Pineda Alejandra , Dorazco-González Alejandro , Fuentes-Noriega Inés , Vilchis-Néstor Alfredo R. , Rodríguez-Hernández Joelis , Morales-Morales David , Germán-Acacio Juan Manuel
Published: November 2021

The mechanochemical synthesis of drug–drug solid forms containing metformin hydrochloride (MET·HCl) and thiazide diuretics hydrochlorothiazide (HTZ) or chlorothiazide (CTZ) is reported. Characterization of these new systems indicates formation of binary eutectic conglomerates, i.e., drug–drug eutectic solids (DDESs). Further analysis by construction of binary diagrams (DSC screening) exhibited the characteristic V-shaped form indicating formation of DDESs in both cases. These new DDESs were further characterized by different techniques, including thermal analysis (DSC), solid state NMR spectroscopy (SSNMR), powder X-ray diffraction (PXRD) and scanning electron microscopy–energy dispersive X-ray spectroscopy analysis (SEM–EDS). In addition, intrinsic dissolution rate experiments and solubility assays were performed. In the case of MET·HCl-HTZ (χMET·HCl = 0.66), we observed a slight enhancement in the dissolution properties compared with pure HTZ (1.21-fold). The same analysis for the solid forms of MET·HCl-CTZ (χMET·HCl = 0.33 and 0.5) showed an enhancement in the dissolved amount of CTZ accompanied by a slight improvement in solubility. From these dissolution profiles and saturation solubility studies and by comparing the thermodynamic parameters (ΔHfus and ΔSfus) of the pure drugs with these new solid forms, it can be observed that there was a limited modification in these properties, not modifying the free energy of the solution (ΔG) and thus not allowing an improvement in the dissolution and solubility properties of these solid forms.
Magnetofection In Vivo by Nanomagnetic Carriers Systemically Administered into the Bloodstream
Authors: Sizikov Artem A. , Nikitin Petr I. , Nikitin Maxim P.
Published: November 2021

Nanoparticle-based technologies are rapidly expanding into many areas of biomedicine and molecular science. The unique ability of magnetic nanoparticles to respond to the magnetic field makes them especially attractive for a number of in vivo applications including magnetofection. The magnetofection principle consists of the accumulation and retention of magnetic nanoparticles carrying nucleic acids in the area of magnetic field application. The method is highly promising as a clinically efficient tool for gene delivery in vivo. However, the data on in vivo magnetofection are often only descriptive or poorly studied, insufficiently systematized, and sometimes even contradictory. Therefore, the aim of the review was to systematize and analyze the data that influence the in vivo magnetofection processes after the systemic injection of magnetic nanostructures. The main emphasis is placed on the structure and coating of the nanomagnetic vectors. The present problems and future trends of the method development are also considered.
Complementary Nucleobase Interactions Drive Co-Assembly of Drugs and Nanocarriers for Selective Cancer Chemotherapy
Authors: Ilhami Fasih Bintang , Bayle Enyew Alemayehu , Cheng Chih-Chia
Published: November 2021

A new concept in cooperative adenine–uracil (A–U) hydrogen bonding interactions between anticancer drugs and nanocarrier complexes was successfully demonstrated by invoking the co-assembly of water soluble, uracil end-capped polyethylene glycol polymer (BU-PEG) upon association with the hydrophobic drug adenine-modified rhodamine (A-R6G). This concept holds promise as a smart and versatile drug delivery system for the achievement of targeted, more efficient cancer chemotherapy. Due to A–U base pairing between BU-PEG and A-R6G, BU-PEG has high tendency to interact with A-R6G, which leads to the formation of self-assembled A-R6G/BU-PEG nanogels in aqueous solution. The resulting nanogels exhibit a number of unique physical properties, including extremely high A-R6G-loading capacity, well-controlled, pH-triggered A-R6G release behavior, and excellent structural stability in biological media. Importantly, a series of in vitro cellular experiments clearly demonstrated that A-R6G/BU-PEG nanogels improved the selective uptake of A-R6G by cancer cells via endocytosis and promoted the intracellular release of A-R6G to subsequently induce apoptotic cell death, while control rhodamine/BU-PEG nanogels did not exert selective toxicity in cancer or normal cell lines. Overall, these results indicate that cooperative A–U base pairing within nanogels is a critical factor that improves selective drug uptake and effectively promotes apoptotic programmed cell death in cancer cells.
Thinking Quantitatively of RNA-Based Information Transfer via Extracellular Vesicles: Lessons to Learn for the Design of RNA-Loaded EVs
Authors: Piffoux Max , Volatron Jeanne , Silva Amanda , Gazeau Florence
Published: November 2021

Extracellular vesicles (EVs) are 50–1000 nm vesicles secreted by virtually any cell type in the body. They are expected to transfer information from one cell or tissue to another in a short- or long-distance way. RNA-based transfer of information via EVs at long distances is an interesting well-worn hypothesis which is ~15 years old. We review from a quantitative point of view the different facets of this hypothesis, ranging from natural RNA loading in EVs, EV pharmacokinetic modeling, EV targeting, endosomal escape and RNA delivery efficiency. Despite the unique intracellular delivery properties endowed by EVs, we show that the transfer of RNA naturally present in EVs might be limited in a physiological context and discuss the lessons we can learn from this example to design efficient RNA-loaded engineered EVs for biotherapies. We also discuss other potential EV mediated information transfer mechanisms, among which are ligand–receptor mechanisms.
Poultry Feather Waste as Bio-Based Cross-Linking Additive for Ethylene Propylene Diene Rubber
Authors: Brenner Markus , Weichold Oliver
Published: November 2021

Most rubbers used today rely on sulphur as a cross-linking agent and carbon black from fossil resources to modify the mechanical properties. A very promising substitute can be found in natural keratins such as feathers. These are not only tough, but also contain a relevant amount of sulphur in the form of disulphide bridges. The present study shows that these can be activated under vulcanisation conditions and then bind covalently to EPDM rubber to form a cross-linked network. Feathers were cut into lengths of 0.08, 0.2, and 1 mm and incorporated at 38, 69, or 100 phr into EPDM mixtures containing either no carbon black or no carbon black nor sulphur. The presence of feather cuttings increases the tensile and compressive strength as well as the hardness, and reduces the rebound resilience. Due to their high (approximately 17%) nitrogen content, the feathers also improve the thermal stability of the composite, as the main degradation step is shifted from 400 °C to 470 °C and the decomposition is significantly slowed down. Since elastomers are a large market and feathers in particular are a high-volume waste, the combination of these two offers enormous ecological and economic prospects.
Synthesis of Functional Building Blocks for Type III-B Rotaxane Dendrimer
Authors: Kwan Chak-Shing , Ho Watson K.-W. , Chen Yanyan , Cai Zongwei , Leung Ken Cham-Fai
Published: November 2021

Second-generation type III-B rotaxane dendrons, equipped with succinimide and acetylene functional groups, were synthesized successfully and characterized by NMR spectroscopy and mass spectrometry. A cell viability study of a dendron with a normal cell line of L929 fibroblast cells revealed no obvious cytotoxicity at a range of 5 to 100 μM. The nontoxic properties of the sophisticated rotaxane dendron building blocks provided a choice of bio-compatible macromolecular machines that could be potentially developed into polymeric materials.
Ionotropic Gelation-Based Synthesis of Chitosan-Metal Hybrid Nanoparticles Showing Combined Antimicrobial and Tissue Regenerative Activities
Authors: Lozano Chamizo Laura , Luengo Morato Yurena , Ovejero Paredes Karina , Contreras Caceres Rafael , Filice Marco , Marciello Marzia
Published: November 2021

The treatment of skin wounds poses significant clinical challenges, including the risk of bacterial infection. In particular due to its antimicrobial and tissue regeneration abilities chitosan (a polymeric biomaterial obtained by the deacetylation of chitin) has received extensive attention for its effectiveness in promoting skin wound repair. On the other hand, due to their intrinsic characteristics, metal nanoparticles (e.g., silver (Ag), gold (Au) or iron oxide (Fe3O4)) have demonstrated therapeutic properties potentially useful in the field of skin care. Therefore, the combination of these two promising materials (chitosan plus metal oxide NPs) could permit the achievement of a promising nanohybrid with enhanced properties that could be applied in advanced skin treatment. In this work, we have optimized the synthesis protocol of chitosan/metal hybrid nanoparticles by means of a straightforward synthetic method, ionotropic gelation, which presents a wide set of advantages. The synthesized hybrid NPs have undergone to a full physicochemical characterization. After that, the in vitro antibacterial and tissue regenerative activities of the achieved hybrids have been assessed in comparison to their individual constituent. As result, we have demonstrated the synergistic antibacterial plus the tissue regeneration enhancement of these nanohybrids as a consequence of the fusion between chitosan and metallic nanoparticles, especially in the case of chitosan/Fe3O4 hybrid nanoparticles.
Exposure of Von Willebrand Factor Cleavage Site in A1A2A3-Fragment under Extreme Hydrodynamic Shear
Authors: Languin-Cattoën Olivier , Laborie Emeline , Yurkova Daria O. , Melchionna Simone , Derreumaux Philippe , Belyaev Aleksey V. , Sterpone Fabio
Published: November 2021

Von Willebrand Factor (vWf) is a giant multimeric extracellular blood plasma involved in hemostasis. In this work we present multi-scale simulations of its three-domains fragment A1A2A3. These three domains are essential for the functional regulation of vWf. Namely the A2 domain hosts the site where the protease ADAMTS13 cleavages the multimeric vWf allowing for its length control that prevents thrombotic conditions. The exposure of the cleavage site follows the elongation/unfolding of the domain that is caused by an increased shear stress in blood. By deploying Lattice Boltzmann molecular dynamics simulations based on the OPEP coarse-grained model for proteins, we investigated at molecular level the unfolding of the A2 domain under the action of a perturbing shear flow. We described the structural steps of this unfolding that mainly concerns the β-strand structures of the domain, and we compared the process occurring under shear with that produced by the action of a directional pulling force, a typical condition of single molecule experiments. We observe, that under the action of shear flow, the competition among the elongational and rotational components of the fluid field leads to a complex behaviour of the domain, where elongated structures can be followed by partially collapsed melted globule structures with a very different degree of exposure of the cleavage site. Our simulations pose the base for the development of a multi-scale in-silico description of vWf dynamics and functionality in physiological conditions, including high resolution details for molecular relevant events, e.g., the binding to platelets and collagen during coagulation or thrombosis.
Effect of Drawing Parameters on the Properties of Polypropylene/Inorganic Particles Composites by Solid-State Die Drawing
Authors: Cai Jianchen , Jiang Jinyun , Yang Qun , Cheng Peng , Chen Ke , Wang Suwei
Published: November 2021

Die drawing is an effective method for improving the properties of polymer. In this work, polypropylene (PP)/inorganic particle composites were fabricated by a solid-state die drawing process to investigate the effects of drawing parameters, such as inorganic particles types, drawing temperature, and drawing speed, on the thermal properties, microstructure, and mechanical behavior of the drawn composites. The mechanical properties of the material were significantly improved through this processing method. For the drawn PP/inorganic particle composites with 45 wt% CaCO3, when the drawing speed was 2.0 m/min and the drawing temperature was 110 °C, the density of the drawn composites reached the lowest at 1.00 g/cm3. At this time, the tensile strength, flexural strength, and impact strength of the drawn composites were 128.32 MPa, 77.12 MPa, and 170.42 KJ/m2, respectively. This work provides a new strategy for the preparation of lightweight and high-strength PP-based composites, which have broad application prospects in the field of engineering and structural materials.
Cross-Linking and Evaluation of the Thermo-Mechanical Behavior of Epoxy Based Poly(ionic Liquid) Thermosets
Authors: Wanghofer Florian , Wolfberger Archim , Wolfahrt Markus , Schlögl Sandra
Published: November 2021

Poly(ionic liquids) (PILs) and ionenes are polymers containing ionic groups in their repeating units. The unique properties of these polymers render them as interesting candidates for a variety of applications, such as gas separation membranes and polyelectrolytes. Due to the vast number of possible structures, numerous synthesis protocols to produce monomers with different functional groups for task-specific PILs are reported in literature. A difunctional epoxy-IL resin was synthesized and cured with multifunctional amine and anhydride hardeners and the thermal and thermomechanical properties of the networks were assessed via differential scanning calorimetry and dynamic mechanical analysis. By the selection of suitable hardeners, the glass transition onset temperature (Tg,onset) of the resulting networks was varied between 18 °C and 99 °C. Copolymerization of epoxy-IL with diglycidyl ether of bisphenol A (DGEBA) led to a further increase of the Tg,onset. The results demonstrate the potential of epoxy chemistry for tailorable PIL networks, where the hardener takes the place of the ligands without requiring an additional synthesis step and can be chosen from a broad range of commercially available compounds.
Membranes for Cation Transport Based on Dendronized Poly(Epichlorohydrin-Co-Ethylene Oxide). Part 2: Membrane Characterization and Transport Properties
Authors: Zare Alireza , Montané Xavier , Reina José Antonio , Giamberini Marta
Published: November 2021

In this paper, we report on the preparation and characterization of membranes out of two side-chain liquid crystalline copolymers, dendronized at two different extents (20 and 40%, CP20 and CP40, respectively). The membranes were characterized by atomic force microscopy (AFM), field-emission scanning electron microscopy (FESEM), contact angle (CA) analysis, and water uptake. Moreover, transport properties were studied by methanol and proton conductivity experiment and by linear sweep voltammetry (LSV). For the sake of comparison, the behavior of the grafted copolymers was compared with the unmodified copolyether CP0 and with Nafion 117. Results demonstrated that in CP20 and CP40, cation transport depends on the presence of defined cationic channels, not affected by water presence; the comparison between LSV experiments performed with different alkaline cations suggests that CP40 possesses channels with larger diameters and better-defined inner structures.
Characterisation and Modelling of an Artificial Lens Capsule Mimicking Accommodation of Human Eyes
Authors: Wei Huidong , Wolffsohn James S. , Gomes de Oliveira Otavio , Davies Leon N.
Published: November 2021

A synthetic material of silicone rubber was used to construct an artificial lens capsule (ALC) in order to replicate the biomechanical behaviour of human lens capsule. The silicone rubber was characterised by monotonic and cyclic mechanical tests to reveal its hyper-elastic behaviour under uniaxial tension and simple shear as well as the rate independence. A hyper-elastic constitutive model was calibrated by the testing data and incorporated into finite element analysis (FEA). An experimental setup to simulate eye focusing (accommodation) of ALC was performed to validate the FEA model by evaluating the shape change and reaction force. The characterisation and modelling approach provided an insight into the intrinsic behaviour of materials, addressing the inflating pressure and effective stretch of ALC under the focusing process. The proposed methodology offers a virtual testing environment mimicking human capsules for the variability of dimension and stiffness, which will facilitate the verification of new ophthalmic prototype such as accommodating intraocular lenses (AIOLs).
Syngas Fermentation for the Production of Bio-Based Polymers: A Review
Authors: Dhakal Nirpesh , Acharya Bishnu
Published: November 2021

Increasing environmental awareness among the general public and legislators has driven this modern era to seek alternatives to fossil-derived products such as fuel and plastics. Addressing environmental issues through bio-based products driven from microbial fermentation of synthetic gas (syngas) could be a future endeavor, as this could result in both fuel and plastic in the form of bioethanol and polyhydroxyalkanoates (PHA). Abundant availability in the form of cellulosic, lignocellulosic, and other organic and inorganic wastes presents syngas catalysis as an interesting topic for commercialization. Fascination with syngas fermentation is trending, as it addresses the limitations of conventional technologies like direct biochemical conversion and Fischer–Tropsch’s method for the utilization of lignocellulosic biomass. A plethora of microbial strains is available for syngas fermentation and PHA production, which could be exploited either in an axenic form or in a mixed culture. These microbes constitute diverse biochemical pathways supported by the activity of hydrogenase and carbon monoxide dehydrogenase (CODH), thus resulting in product diversity. There are always possibilities of enzymatic regulation and/or gene tailoring to enhance the process’s effectiveness. PHA productivity drags the techno-economical perspective of syngas fermentation, and this is further influenced by syngas impurities, gas–liquid mass transfer (GLMT), substrate or product inhibition, downstream processing, etc. Product variation and valorization could improve the economical perspective and positively impact commercial sustainability. Moreover, choices of single-stage or multi-stage fermentation processes upon product specification followed by microbial selection could be perceptively optimized.
Synthesis and Characterization of Activated Carbon Fibers Derived from Linear Low-Density Polyethylene Fibers Stabilized at a Low Temperature
Authors: Kim Kwan-Woo , Lee Hye-Min , Kang Seong-Hyun , Kim Byung-Joo
Published: November 2021

In this study, activated carbon fibers (ACFs) were prepared using a new method from polyethylene (PE) fibers. The stabilizing (or crosslinking) process of PE, an essential step, was achieved through a hybrid treatment using electron-beam/sulfuric acid at 110 °C that was more effective than the traditional method of using sulfuric acid at 180 °C for polyolefin. The stabilized precursor was then carbonized at 700 °C and activated at 900 °C with different activation times. The structural characteristics and morphologies of these ACFs were observed using an X-ray diffractometer and a field-emission scanning electron microscope, respectively. In addition, the N2/77K adsorption isotherm was used to discern textural properties. The total pore volume and specific surface area of these ACFs were found to be increased with a longer activation time, reaching final values of 0.99 cm3/g and 1750 m2/g, respectively. These ACFs also exhibited a high mesopore volume ratio (39%) according to crosslinking and crystallite formation conditions.
Carbon-Doping as Efficient Strategy for Improving Photocatalytic Activity of Polysilicon Supported Pd in Hydrogen Evolution from Formic Acid
Authors: Al-Azmi Amal , Keshipour Sajjad
Published: November 2021

Interest in cost-effective materials pushes researchers to the inexpensive and abundant semiconductors to use photons’ energy for generating electrons and holes required for photocatalytic transformations. At the same time, polysilicon is one of the economic semiconductors with a disadvantage of high bandgap which could be solved by carbon-doping. We employed this strategy to the synthesis of carbon-doped polysilicon by a new approach starting from citric acid and methyltrimethoxysilane. The nanocomposite obtained was utterly characterized, and compared with bare polysilicon; increased UV–Vis absorbance and shift to higher wavelengths were the most notable characteristics of the synthesized catalyst. The carbon-doped polysilicon was modified with Pd nanoparticles to obtain a new heterogeneous photocatalyst for the formic acid degradation. The decomposition of formic acid was photocatalyzed by the obtained nanocomposite with a hydrogen production turnover frequency of up to 690 h−1. Moreover, it was demonstrated that the catalyst is stable and recyclable.
Polymeric Micro/Nanocarriers and Motors for Cargo Transport and Phototriggered Delivery
Authors: Mena-Giraldo Pedro , Orozco Jahir
Published: November 2021

Smart polymer-based micro/nanoassemblies have emerged as a promising alternative for transporting and delivering a myriad of cargo. Cargo encapsulation into (or linked to) polymeric micro/nanocarrier (PC) strategies may help to conserve cargo activity and functionality when interacting with its surroundings in its journey to the target. PCs for cargo phototriggering allow for excellent spatiotemporal control via irradiation as an external stimulus, thus regulating the delivery kinetics of cargo and potentially increasing its therapeutic effect. Micromotors based on PCs offer an accelerated cargo–medium interaction for biomedical, environmental, and many other applications. This review collects the recent achievements in PC development based on nanomicelles, nanospheres, and nanopolymersomes, among others, with enhanced properties to increase cargo protection and cargo release efficiency triggered by ultraviolet (UV) and near-infrared (NIR) irradiation, including light-stimulated polymeric micromotors for propulsion, cargo transport, biosensing, and photo-thermal therapy. We emphasize the challenges of positioning PCs as drug delivery systems, as well as the outstanding opportunities of light-stimulated polymeric micromotors for practical applications.
Concentration Effect over Thermoresponse Derived from Organometallic Compounds of Functionalized Poly(N-isopropylacrylamide-co-dopamine Methacrylamide)
Authors: Moral-Zamorano María , Quijada-Garrido Isabel , San-Miguel Verónica , Serrano Berna , Baselga Juan , Hashmi Saud , Stadler Florian J. , García-Peñas Alberto
Published: November 2021

The functionalization of smart polymers is opening a new perspective in catalysis, drug carriers and biosensors, due to the fact that they can modulate the response regarding conventional devices. This smart response could be affected by the presence of organometallic complexes in terms of interactions which could affect the physical chemical properties. In this sense, the thermoresponsive behavior of copolymers based on N-isopropylacrylamide (NIPAM) could be affected due to the presence of hydrophobic groups and concentration effect. In this work, the functionalization of a copolymer based on NIPAM and dopamine methacrylamide with different amounts of bis(cyclopentadienyl)titanium (IV) dichloride was carried out. The resulting materials were characterized, showing a clear idea about the mechanism of functionalization through FTIR spectroscopy. The thermoresponsive behavior was also studied for various polymeric solutions in water by UV–vis spectroscopy and calorimetry. The hydrophobic interactions promoted by the organometallic complex could affect the transition associated with the lower critical solution temperature (LCST), specifically, the segments composed by pure NIPAM. That fact would explain the reduction of the width of the LCST-transition, contrary to what could be expected. In addition, the hydrophobicity was tested by the contact angle and also DNA interactions.
Reinforcement Mechanism of Carbon Black-Filled Rubber Nanocomposite as Revealed by Atomic Force Microscopy Nanomechanics
Authors: Liang Xiaobin , Ito Makiko , Nakajima Ken
Published: November 2021

In this study, atomic force microscopy (AFM) nanomechanics were used to visualize the nanoscale stress distribution in carbon black (CB)-reinforced isoprene rubber (IR) vulcanizates at different elongations and quantitatively evaluate their volume fractions for the first time. The stress concentrations in the protofibrous structure (stress chains) that formed around the CB filler in CB-reinforced IR vulcanizates were directly observed at the nanoscale. The relationship between the local nanoscale stress distribution and macroscopic tensile properties was revealed based on the microscopic stress distribution and microscopic spatial structure. This study can help us gain insight into the microscopic reinforcement mechanism of carbon black-containing rubber composites.
Development and Characterization of Silver Containing Free Standing Polymer FILMS for Dosimetry Applications
Authors: Merkis Mantvydas , Puišo Judita , Adliene Diana , Laurikaitiene Jurgita
Published: November 2021

Polymer gels and films, due to their near equivalence to biological tissue, are amongst the most promising future dosimetry tools for medical applications. The application of polymer dose gels is limited by the sensitivity of dose readout methods and dose gel properties. It is a challenge to find suitable dosimeters for registration of doses delivered to the target by orthovoltage therapy units. The application of metal-particle-enriched polymer composites for dose registration in X-ray therapy might be an elegant solution, especially if recent dose-reading technologies exploring advantages of different physical phenomena are involved. In this work, X-rays from the orthovoltage therapy range were used for the irradiation of experimental samples. In addition, radiation-induced processes of formation of silver nanoparticles in AgNO3–PVA gels and in free standing AgNO3PVA films, also containing some additional solvents, namely glycerol, ethanol, and isopropanol, have been investigated, with the aim to apply the developed composites for medical dosimetry purposes. A simple and environmentally friendly method for the formation of free-standing AgPVA films at room temperature was proposed and realized for preparing AgPVA films for investigation. Radiation-induced synthesis of silver nanoparticles in AgPVA composites was investigated, analyzing LPSR-based UV-VIS spectral changes to the irradiated films with respect to irradiation doses, and dose-related tendencies were also evaluated. It was shown that AgPVA films were more sensitive for detection of doses from the interval 0–1.0 Gy, thus indicating potential application of AgPVA films for dosimetry purposes.
Delamination Behaviour of Embedded Polymeric Sensor and Actuator Carrier Layers in Epoxy Based CFRP Laminates—A Study of Energy Release Rates
Authors: Hornig Andreas , Winkler Anja , Bauerfeind Eric , Gude Maik , Modler Niels
Published: November 2021

Fiber reinforced composites combine low density with high specific mechanical properties and thus became indispensable for today’s lightweight applications. In particular, carbon fibre reinforced plastic (CFRP) is broadly used for aerospace components. However, damage and failure behaviour, especially for complex fibre reinforcement set-ups and under impact loading conditions, are still not fully understood yet. Therefore, relatively large margins of safety are currently used for designing high-performance materials and structures. Technologies to functionalise the materials enabling the monitoring of the structures and thus avoiding critical conditions are considered to be key to overcoming these drawbacks. For this, sensors and actuators are bonded to the surface of the composite structures or are integrated into the composite lay-up. In case of integration, the impact on the mechanical properties of the composite materials needs to be understood in detail. Additional elements may disturb the composite structure, impeding the direct connection of the composite layers and implying the risk of reducing the interlaminar integrity by means of a lower delamination resistance. In the presented study, the possibility of adjusting the interface between the integrated actuator and sensor layers to the composite layers is investigated. Different polymer layer combinations integrated into carbon fibre reinforced composite layups are compared with respect to their interlaminar critical energy release rates GIc and GIIc. A standard aerospace unidirectionally reinforced (UD) CFRP prepreg material was used as reference material configuration. The investigations show that it is possible to enhance the mechanical properties, especially the interlaminar energy release rate by using multilayered sensor–actuator layers with Polyimide (PI) outer layers and layers with low shear stiffness in between.
Effect of Silver Nanopowder on Mechanical, Thermal and Antimicrobial Properties of Kenaf/HDPE Composites
Authors: Sanmuham Vikneswari , Sultan Mohamed Thariq Hameed , Radzi A. M. , Shamsuri Ahmad Adlie , Md Shah Ain Umaira , Safri Syafiqah Nur Azrie , Basri Adi Azriff
Published: November 2021

This study aims to investigate the effect of AgNPs on the mechanical, thermal and antimicrobial activity of kenaf/HDPE composites. AgNP material was prepared at different contents, from 0, 2, 4, 6, 8 to 10 wt%, by an internal mixer and hot compression at a temperature of 150 °C. Mechanical (tensile, modulus and elongation at break), thermal (TGA and DSC) and antimicrobial tests were performed to analyze behavior and inhibitory effects. The obtained results indicate that the effect of AgNP content displays improved tensile and modulus properties, as well as thermal and antimicrobial properties. The highest tensile stress is 5.07 MPa and was obtained at 10wt, TGA showed 10 wt% and had improved thermal stability and DSC showed improved stability with increased AgNP content. The findings of this study show the potential of incorporating AgNP concentrations as a secondary substitute to improve the performance in terms of mechanical, thermal and antimicrobial properties without treatment. The addition of AgNP content in polymer composite can be used as a secondary filler to improve the properties.
Polymer Brush in a Nanopore: Effects of Solvent Strength and Macromolecular Architecture Studied by Self-Consistent Field and Scaling Theory
Authors: Laktionov Mikhail Y. , Zhulina Ekaterina B. , Richter Ralf P. , Borisov Oleg V.
Published: November 2021

To study conformational transition occuring upon inferior solvent strength in a brush formed by linear or dendritically branched macromolecules tethered to the inner surface of cylindrical or planar (slit-like) pore, a self-consistent field analytical approach is employed. Variations in the internal brush structure as a function of variable solvent strength and pore radius, and the onset of formation of a hollow channel in the pore center are analysed. The predictions of analytical theory are supported and complemented by numerical modelling by a self-consistent field Scheutjens–Fleer method. Scaling arguments are used to study microphase segregation under poor solvent conditions leading to formation of a laterally and longitudinally patterned structure in planar and cylindrical pores, respectively, and the effects of confinement on "octopus-like" clusters in the pores of different geometries.
Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation
Authors: Nifant’ev Ilya E. , Tavtorkin Alexander N. , Vinogradov Alexey A. , Korchagina Sofia A. , Chinova Maria S. , Borisov Roman S. , Artem’ev Grigory A. , Ivchenko Pavel V.
Published: November 2021

Ultra-high molecular weight poly-α-olefins are widely used as drag reducing agents (DRAs) for pipeline transportation of oil and refined petroleum products. The synthesis of polyolefin DRAs is based on low-temperature Ziegler–Natta (ZN) polymerization of higher α-olefins. 1-Hexene based DRAs, the most effective at room temperature, typically lose DR activity at low temperatures. The use of 1-hexene copolymers with C8–C12 linear α-olefins appears to offer a solution to the problem of low-temperature drag reducing. The present work aims to develop two-stage synthesis of polyolefin DRAs that is based on selective oligomerization of ethylene in the presence of efficient chromium/aminodiphosphine catalysts (Cr-PNP), followed by polymerization of the olefin mixtures, formed at oligomerization stage, using efficient titanium–magnesium ZN catalyst. We have shown that oligomerization of ethylene in α-olefin reaction media proceeds faster than in saturated hydrocarbons, providing the formation of 1-hexene, 1-octene, and branched C10 and C12 olefins; the composition and the ratio of the reaction products depended on the nature of PNP ligand. Oligomerizates were used in ZN polymerization ‘as is’, without additional treatment. Due to branched character of C10+ hydrocarbons, formed during oligomerization of ethylene, resulting polyolefins demonstrate higher low-temperature DR efficiency at low polymer concentrations (~1 ppm) in comparison with benchmark polymers prepared from the mixtures of linear α-olefins and from pure 1-hexene. We assume that faster solubility and more efficient solvation of the polyolefins, prepared using ‘tandem’ ethylene-based process, represent an advantage of these type polymers over conventional poly(1-hexene) and linear α-olefin-based polymers when used as ‘winter’ DRAs.