Tailoring Homogeneous Hydrogel Nanospheres by Facile Ultra-Sonication Assisted Cross-Linked Copolymerization for Rhodamine B Dye Adsorption.

The present paper describes the design of shape-oriented hydrogel nanospheres using a facile ultrasonication-supported crosslinked copolymerization technique. The effect of variable monomer concentration on the homogeneity of hydrogel nanospheres was investigated. The chitosan-cl-poly(MMA) hydrogel nanospheres were well characterized using various techniques such as FTIR, XRD, TGA, SEM, and TEM. The chitosan-cl-poly(MMA) hydrogel nanospheres were studied for their swelling behavior and could potentially be used as a novel adsorbent for rhodamine B dye remediation from aqueous media. The study found that utilizing chitosan-cl-poly(MMA) nanohydrogel spheres at the optimal pH 5 increased RhB dye adsorption capacity from 7.9 to 17.8 mg/g (pH 2 to 5), followed by a slight reduction. Furthermore, when nanohydrogel concentration increased, adsorption capacity dropped from 18.03 to 2.8 mg/g, but adsorption percentage climbed from 90.2% to 97.8%. At an initial dye concentration of 140 mg/L, rhodamine B adsorption achieved 204.3 mg/g in 60 min. The rhodamine B dye adsorption study includes adsorption kinetics, isotherm, and thermodynamics analyses. The interpretation of the adsorption study revealed that Langmuir isotherms fit best with a qmax value of 276.26 mg/g, which is in close approximation with the experimental value, whereas pseudo-second-order kinetics explains the adsorption process rate. The interaction of RhB dye with chitosan-cl-poly(MMA) hydrogel nanospheres involves multiple forces such as electrostatic interactions, hydrogen bonding, van der Waals forces, etc.

Recent advances in perovskite-based Z-scheme and S-scheme heterojunctions for photocatalytic CO2 reduction.

The dramatic rise in carbon dioxide levels in the atmosphere caused by the continuous use of carbon fuels continues to have a significant impact on environmental degradation and the disappearance of energy reserves. Past few years have seen a significant increase in the interest in photocatalytic carbon dioxide reduction because of its ability to lower CO2 releases from the burning of fossil fuels while also producing fuels and important chemical products. Because of their excellent catalytic efficiency, great uniformity, lengthy charge diffusion layers and texture flexibility that enable accurate band gap and band line optimization, perovskite-based nanomaterials are perhaps the most advantageous among the numerous semiconductors proficient in accelerating CO2 conversion under visible light. Firstly, a brief insight into photocatalytic CO2 conversion mechanism and structural features of perovskites are discussed. Further the classification and selection of perovskites for Z and S-scheme heterojunctions and their role in photocatalytic CO2 reduction analysed. The efficient modification and engineering of heterojunctions via co-catalyst loading, morphology control and vacancy introduction have been comprehensively reviewed. Third, the state-of-the-art achievements of perovskite-based Z-scheme and S-scheme heterojunctions are systematically summarized and discussed. Finally, the challenges, bottlenecks and future perspectives are discussed to provide a pathway for applying perovskite-based heterojunctions for solar-to-chemical energy conversion.

Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior.

In this study, nanocomposites based on polypropylene are synthesized by the in situ polymerization of propene in the presence of mesoporous SBA-15 silica, which acts as a carrier of the catalytic system (zirconocene as catalyst and methylaluminoxane as cocatalyst). The protocol for the immobilization and attainment of hybrid SBA-15 particles involves a pre-stage of contact between the catalyst with cocatalyst before their final functionalization. Two zirconocene catalysts are tested in order to attain materials with different microstructural characteristics, molar masses and regioregularities of chains. Some polypropylene chains are able to be accommodated within the silica mesostructure of these composites. Thus, an endothermic event of small intensity appears during heating calorimetric experiments at approximately 105 °C. The existence of these polypropylene crystals, confined within the nanometric channels of silica, is corroborated by SAXS measurements obtained via the change in the intensity and position of the first-order diffraction of SBA-15. The incorporation of silica also has a very significant effect on the rheological response of the resultant materials, leading to important variations in various magnitudes, such as the shear storage modulus, viscosity and δ angle, when a comparison is established with the corresponding neat iPP matrices. Rheological percolation is reached, thus demonstrating the role of SBA-15 particles as filler, in addition to the supporting role that they exert during the polymerizations.

Study of the synergistic influence of zwitterionic interactions and graphene oxide on water diffusion mechanism and mechanical properties in hybrid hydrogel network.

Hybrid hydrogels based on n-isopropylacrylamide, zwitterionic comonomer, and graphene oxide were synthesized to study their physical and mechanical properties. The compositional variation largely influenced the swelling characteristics of the hybrid hydrogels compared to mechanical properties, i.e., elongation and compression. Additionally, Rheometric swelling measurements on the swollen hydrogels were performed until they reached equilibrium showed a very low phase angle δ indicating strong covalent network, which intrun increases with increasing content of zwitterions and GO. Swelling kinetics were studied and found to follow Fickian dynamics, albeit zwitterion-containing gels showed a peculiar 2-step swelling pattern. Interestingly, differences in the swelling mechanism are also clear for the hydrogels with 2D GO (Graphene oxide) nano-fillers from its 1D nano-filler CNTs (Carbon nanotubes). In elongation, the samples break in a brittle fashion at Hencky strains εmax around 0.4-0.65 with the maximum stress being observed for samples with high Zw-content and 0.2% GO, which can be explained by the stress-rising properties of sharp edges of GO. In contrast, the data in compression profits from higher GO-contents as crack growth is less important in this deformation mode. This work will contribute to future composite gel applications.

Norbornene as Key for a Possible Efficient Chemical Recycling in Structures Based on Ethylene.

Different circular strategies attempt to increase the energy efficiency or reduce the accumulation of plastic in landfills through the development of circular polymers. Chemical recycling is essential to recover the initial monomers from plastic residues for obtaining new goods showing the same properties as those using virgin monomers from the initial feedstocks. This work addresses the preparation of poly(ethylene-co-norbornene) copolymers for a promising generation of materials for energy applications that could be treated by chemical recycling. The thermal and thermo-oxidative stability for these copolymers with norbornene is higher than for the neat PE, while their degradation exhibits an activation energy lower than that observed in PE, pointing out that chemical recycling would require a lower energy consumption.

Correction: Reactions of [60]fullerene with alkynes promoted by OH.

[This corrects the article DOI: 10.1039/D2RA01300B.].

Water-Soluble and -Insoluble Polymers and Biopolymers for Biomedical, Environmental, and Biological Applications.

In this Special Issue, several papers dedicated to biomedical, environmental, and biological applications have been assembled, representing different aspects of the field [...].

Reactions of [60]fullerene with alkynes promoted by OH.

In the current work, the reactions of [60]fullerene with alkynes promoted by OH- (base) are addressed. The treatment of C60 with alkynes in the presence of TBAOH produces alkynylation products (R-C60-H) with high selectivity in o-DCB at 100 °C. Plausible reaction mechanisms were proposed. This work provides a convenient and environmental friendly method for the functionalization of fullerenes.

Gum Acacia-Crosslinked-Poly(Acrylamide) Hydrogel Supported C3N4/BiOI Heterostructure for Remediation of Noxious Crystal Violet Dye.

Herein, we report the designing of a C3N4/BiOI heterostructure that is supported on gum acacia-crosslinked-poly(acrylamide) hydrogel to fabricate a novel nanocomposite hydrogel. The potential application of the obtained nanocomposite hydrogel to remediate crystal violet dye (CVD) in an aqueous solution was explored. The structural and functional analysis of the nanocomposite hydrogel was performed by FTIR (Fourier transform infrared spectroscopy), X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The different reaction parameters, such as CVD concentration, nanocomposite hydrogel dosage, and working pH, were optimized. The C3N4/BiOI heterostructure of the nanocomposite hydrogel depicts Z-scheme as the potential photocatalytic mechanism for the photodegradation of CVD. The degradation of CVD was also specified in terms of COD and HR-MS analysis was carried to demonstrate the major degradation pathways.

Chitosan as a Tool for Sustainable Development: A Mini Review.

New developments require innovative ecofriendly materials defined by their biocompatibility, biodegradability, and versatility. For that reason, the scientific society is focused on biopolymers such as chitosan, which is the second most abundant in the world after cellulose. These new materials should show good properties in terms of sustainability, circularity, and energy consumption during industrial applications. The idea is to replace traditional raw materials with new ecofriendly materials which contribute to keeping a high production rate but also reducing its environmental impact and the costs. The chitosan shows interesting and unique properties, thus it can be used for different purposes which contributes to the design and development of sustainable novel materials. This helps in promoting sustainability through the use of chitosan and diverse materials based on it. For example, it is a good sustainable alternative for food packaging or it can be used for sustainable agriculture. The chitosan can also reduce the pollution of other industrial processes such as paper production. This mini review collects some of the most important advances for the sustainable use of chitosan for promoting circular economy. Hence, the present review focuses on different aspects of chitosan from its synthesis to multiple applications.

Accelerated charge transfer in well-designed S-scheme Fe@TiO2/Boron carbon nitride heterostructures for high performance tetracycline removal and selective photo-reduction of CO2 greenhouse gas into CH4 fuel.

Designing and fabrication of smart hybrid multifunctional materials for energy/fuel production and environmental detoxification is indeed of great significance for sustainable development. Herein, we synthesized a new well-structured S-scheme heterostructure Fe@TiO2/Boron Carbon nitride (FT/BCN) with high performance tetracycline degradation and selective CO2 photo-reduction to CH4. Under visible light irradiation, 96.3% tetracycline was degraded in 60 min using best performing FT30/BCN sample with a high 83.2% total organic carbon removal in 2 h. The tetracycline degradation rate for FT30/BCN composite catalyst was ∼7 times than bare boron carbon nitride (BCN). The impact of reaction parameters as pH, presence of interfering electrolytes, light source and water matrix was also investigated. The FT30/BCN photocatalyst shows dramatic improvement in CO2 photoreduction as exhibited in 24.7 µmol g-1 h-1 CH4 and 2.4 µmol g-1 h-1 CO evolutions with optimal 91.1% CH4 selectivity. Pure BCN shows a poor 39.1% selectivity. Further, effect of alkali activation, CO2/H2O feed ratio, reducing agent and light source onto CH4 production and selectivity was also investigated. The CH4 evolution and selectivity was improved because of enhanced visible light absorption, high adsorption potential, charge carrier separation and high reducing power of photogenerated electrons induced by an effective S-scheme heterojunction between Fe@TiO2 and boron carbon nitride. An S-scheme (step-scheme) charge transfer mechanism is here operative both during tetracycline removal and CO2 reduction. The drug degradation route and photocatalytic mechanism for antibiotic removal and CO2 reduction was also predicted.

MXenes based nano-heterojunctions and composites for advanced photocatalytic environmental detoxification and energy conversion: A review.

Extensive research is being done to develop multifunctional advanced new materials for high performance photocatalytic applications in the field of energy production and environmental detoxification, MXenes have emerged as promising materials for enhancing photocatalytic performance owing to their excellent mechanical properties, appropriate Fermi levels, and adjustability of chemical composition. Numerous experimental and theoretical research works implied that the dimensions of MXenes have a significant impact on their performance. For photocatalysis to thrive in the future, we must understand the current state of the art for MXene in different dimensions. Using MXene co-catalysts in widely used in photocatalytic applications such as CO2 reduction, hydrogen production and organic pollutant oxidation, this study focuses on the most recent developments in MXenes based materials, structural modifications, innovations in reaction and material engineering. It has been reported that using 5 mg of CdS-MoS2-MXene researchers were able to generate as high as 9679 µmol/g/h hydrogen under visible light. The MXenes based heterojunction photocatalyst Co3O4/MXene was utilized to degrade 95% bisphenol A micro-pollutant in just 7 min. Numerous novel materials, their preparations and performances have been discussed. Depending upon the nature of MXene-based materials, the synthesis techniques and photocatalytic mechanism of MXenes as co-catalyst are also summarized. Finally, some final thoughts and prospects for developing highly efficient MXene-based photocatalysts are provided which will indeed motivate researchers to design novel hybrid materials based on MXenes for sustainable solutions to energy and pollution issues.

Concentration Effect over Thermoresponse Derived from Organometallic Compounds of Functionalized Poly(N-isopropylacrylamide-co-dopamine Methacrylamide).

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.

Fabrication and Characterization of Xanthan Gum-cl-poly(acrylamide-co-alginic acid) Hydrogel for Adsorption of Cadmium Ions from Aqueous Medium.

The present research demonstrates the facile fabrication of xanthan gum-cl-poly(acrylamide-co-alginic acid) (XG-cl-poly(AAm-co-AA)) hydrogel by employing microwave-assisted copolymerization. Simultaneous copolymerization of acrylamide (AAm) and alginic acid (AA) onto xanthan gum (XG) was carried out. Different samples were fabricated by changing the concentrations of AAm and AA. A sample with maximum swelling percentage was chosen for adsorption experiments. The structural and functional characteristics of synthesized hydrogel were elucidated using diverse characterization tools. Adsorption performance of XG-cl-poly(AAm-co-AA) hydrogel was investigated for the removal of noxious cadmium (Cd(II)) ions using batch adsorption from the aqueous system, various reaction parameters optimized include pH, contact time, temperature, and concentration of Cd(II) ions and temperature. The maximum adsorption was achieved at optimal pH 7, contact time 180 min, temperature 35 °C and cadmium ion centration of 10 mg·L-1. The XG-cl-poly(AAm-co-AA) hydrogel unveiled a very high adsorption potential, and its adsorption capacities considered based on the Langmuir isotherm for Cd(II) ions was 125 mg·g-1 at 35 °C. The Cd(II) ions adsorption data fitted nicely to the Freundlich isotherm and pseudo-first-order model. The reusability investigation demonstrated that hydrogel retained its adsorption capacity even after several uses without significant loss.

A New Insight into the Comonomer Effect through NMR Analysis in Metallocene Catalysed Propene-co-1-Nonene Copolymers.

The "comonomer effect" is an intriguing kinetic phenomenon in olefin copolymerization that still remains without a detailed explanation. It typically relates to the rate of enhancement undergone in ethylene and propene catalytic polymerization just by adding small fractions of an alpha-olefin. The difficulty lies in the fact that changes caused by the presence of the comonomer in reaction parameters are so conspicuous that it is really difficult to pin down which of them is the primary cause and which ones are side factors with marginal contribution to the phenomenon. Recent investigations point to the modification of the catalyst active sites as the main driving factor. In this work, the comonomer effect in the metallocene copolymerization of propene and 1-nonene is analysed and correlated to the comonomer role in the termination of the chain-growing process. The associated termination mechanisms involved furnish most of chain-free active sites, in which the selective interaction of the comonomer was proposed to trigger the insertion of monomers. A thorough characterisation of chain-end groups by means of the 1H NMR technique allows for detailing of specific transfer processes, ascribed to comonomer insertions, as well as evidencing the influence of the growing chain's microstructure over the different termination processes available.

Effect of Hydrophobic Interactions on Lower Critical Solution Temperature for Poly(N-isopropylacrylamide-co-dopamine Methacrylamide) Copolymers.

For the preparation of thermoresponsive copolymers, for e.g., tissue engineering scaffolds or drug carriers, a precise control of the synthesis parameters to set the lower critical solution temperature (LCST) is required. However, the correlations between molecular parameters and LCST are partially unknown and, furthermore, LCST is defined as an exact temperature, which oversimplifies the real situation. Here, random N-isopropylacrylamide (NIPAM)/dopamine methacrylamide (DMA) copolymers were prepared under a systematical variation of molecular weight and comonomer amount and their LCST in water studied by calorimetry, turbidimetry, and rheology. Structural information was deduced from observed transitions clarifying the contributions of molecular weight, comonomer content, end-group effect or polymerization degree on LCST, which were then statistically modeled. This proved that the LCST can be predicted through molecular structure and conditions of the solutions. While the hydrophobic DMA lowers the LCST especially the onset, polymerization degree has an important but smaller influence over all the whole LCST range.

Fabrication and characterization of Gum arabic-cl-poly(acrylamide) nanohydrogel for effective adsorption of crystal violet dye.

Natural biopolymers are better adsorbents due to better functionality, surface area, bio-compatibility and ease of procurement. The gum arabic in natural biopolymer derived from Acacia Arabic species. In the present work a novel nanohydrogel of gum arabic with acrylamide has been fabricated using microwave synthesis for adsorption of noxious crystal violet dye from aqueous medium. The prepared gum arabic-cl-poly(acrylamide) nanohydrogel (GA-cl-poly(AAm)) NHG was characterized by numerous techniques including SEM, XRD, TEM and FTIR. The GA-cl-poly(AAm) NHG showed promising adsorption ability for crystal violet dye. The effect of various adsorption factors such as concentration of GA-cl-poly(AAm) NHG and crystal violet, pH, temperature and time has been studied and reported. For understanding the adsorption mechanism three models Langmuir, Freundlich and Temkin were applied to adsorption data The kinetics and thermodynamics of adsorption were also investigated The adsorption capacity of crystal violet onto GA-cl-poly(AAm) NHG according to Langmuir model is found to be 90.90 mg/g.

Anticancer Applications of Nanostructured Silica-Based Materials Functionalized with Titanocene Derivatives: Induction of Cell Death Mechanism through TNFR1 Modulation.

A series of cytotoxic titanocene derivatives have been immobilized onto nanostructured silica-based materials using two different synthetic routes, namely, (i) a simple grafting protocol via protonolysis of the Ti-Cl bond; and (ii) a tethering method by elimination of ethanol using triethoxysilyl moieties of thiolato ligands attached to titanium. The resulting nanostructured systems have been characterized by different techniques such as XRD, XRF, DR-UV, BET, SEM, and TEM, observing the incorporation of the titanocene derivatives onto the nanostructured silica and slight changes in the textural features of the materials after functionalization with the metallodrugs. A complete biological study has been carried out using the synthesized materials exhibiting moderate cytotoxicity in vitro against three human hepatic carcinoma (HepG2, SK-Hep-1, Hep3B) and three human colon carcinomas (DLD-1, HT-29, COLO320) and very low cytotoxicity against normal cell lines. In addition, the cells' metabolic activity was modified by a 24-h exposure in a dose-dependent manner. Despite not having a significant effect on TNFα or the proinflammatory interleukin 1α secretion, the materials strongly modulated tumor necrosis factor (TNF) signaling, even at sub-cytotoxic concentrations. This is achieved mainly by upregulation of the TNFR1 receptor production, something which has not previously been observed for these systems.

Mechanical and Transport Properties of Poly(propylene-co-1-heptene) Copolymers and Their Dependence on Monoclinic and/or Mesomorphic Polymorphs.

Poly(propylene-co-1-heptene) copolymers have been evaluated in a wide 1-heptene content range. Two different polymorphs can be observed in this interval under the processing conditions imposed: monoclinic crystallites and mesomorphic entities. The unique presence of one or the other lattice at specific content or the coexistence of both of them at the intermediate composition interval is a key factor affecting some of the exhibited properties. The influence is observed in characteristics mainly dependent on either crystalline structure, like rigidity, or the amorphous regions, as location and intensity of glass transition. To get a deeper understanding, the transition from mesophase to monoclinic crystallites has also been studied by DSC and by WAXS and SAXS experiments using synchrotron radiation. It is observed that this transformation is only partial and just involves one-third of the initial ordered mesomorphic entities. Permeability to different gases is mainly dependent on amorphous content and hindrance that monoclinic or mesomorphic entities impose on those disordered regions.

Study of the cytotoxicity and particle action in human cancer cells of titanocene-functionalized materials with potential application against tumors.

Titanocene dichloride [Ti(η(5)-C(5)H(5))(2)Cl(2)] (1), has been grafted onto dehydrated hydroxyapatite (HAP), Al(2)O(3) and two mesoporous silicas MSU-2 (Michigan State University Silica type 2) and HMS (Hexagonal Mesoporous Silica), to give the novel materials HAP/[Ti(η(5)-C(5)H(5))(2)Cl(2)] (S1) (1.01 wt.% Ti), Al(2)O(3)/[Ti(η(5)-C(5)H(5))(2)Cl(2)] (S2) (2.36 wt.% Ti), HMS/[Ti(η(5)-C(5)H(5))(2)Cl(2)] (S3) (0.75 wt.% Ti) and MSU-2/[Ti(η(5)-C(5)H(5))(2)Cl(2)] (S4) (0.74 wt.% Ti), which have been characterized by powder X-ray diffraction, X-ray fluorescence, nitrogen gas sorption, multinuclear magic angle spinning NMR spectroscopy, IR spectroscopy, thermogravimetry analysis, UV spectroscopy, scanning electronic microscopy and transmission electronic microscopy. The cytotoxicity of the titanocene-functionalized materials toward human cancer cell lines from five different histogenic origins: 8505C (anaplastic thyroid cancer), A253 (head and neck cancer), A549 (lung carcinoma), A2780 (ovarian cancer) and DLD-1 (colon cancer) has been determined. M(50) values (quantity of material needed to inhibit normal cell growth by 50%) and Ti-M(50) values (quantity of anchored titanium needed to inhibit normal cell growth by 50%) indicate that the activity of S1-S4 against studied human cancer cells depended on the surface type as well as on the cell line. In addition, studies on the titanocene release and the interaction of the materials S1-S4 with DNA show that the cytotoxic activity may be due to particle action, because no release of titanium complexes has been observed in physiological conditions, while electrostatic interactions of titanocene-functionalized particles with DNA have been observed.