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Materials Chemistry: Good Beginnings for a Cross-Disciplinary Platform in Molecules

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (30 June 2023) | Viewed by 22153

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Guest Editor
Department of Pharmacy, Health and Nutritional Sciences, University of Calabria, 87036 Rende, Italy
Interests: nanomaterials; biomaterials; carbon nanostructures; composite and hybrid materials; biomedical applications of functional materials; therapeutic devices; surface chemistry
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Guest Editor
Department of Chemistry, Josip Juraj Strossmayer University of Osijek, Cara Hadrijana 8/a, HR-31000 Osijek, Croatia
Interests: solid state chemistry; materials chemistry; condensed matter physics; magnetic properties; structure–property relationship; bandstructure calculation; sol-gel synthesis; crystal structure determination; three-way catalysts; functional materials; nanomaterials; perovskites; multiferroicity; metal–organic frameworks
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Over the last few years, materials chemistry has experienced rapid growth by taking advantage of developments in synthetic and characterization procedures, as well as new technologies available at the micro- and nanoscale. Taking advantage of knowledge in chemistry, biotechnology, chemical engineering, physics, and materials science, materials chemistry can be defined as an interdisciplinary environment where different expertise acts synergistically to focus progress in the field of creating and manipulating new materials. Within this Special Issue, we aim to collect either research or review articles, in order to disseminate theoretical and experimental studies based on the chemical approaches to materials-based problems and provide readers with a vision of their relevance and contribution to the growth of materials science and technology. Covered topics include but are not limited to the synthesis and characterization of organic and inorganic materials, including biomaterials, functional materials, nanomaterials, hybrid materials, core–shell materials, thin films, and self-assembling systems.

Dr. Giuseppe Cirillo
Prof. Dr. Igor Djerdj
Guest Editors

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Keywords

  • organic and inorganic materials
  • biomaterials
  • nanomaterials
  • hybrid materials
  • core–shell materials
  • thin films
  • self-assembling systems

Published Papers (9 papers)

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Research

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12 pages, 3650 KiB  
Article
Synthesis of a New Co Metal–Organic Framework Assembled from 5,10,15,20-Tetrakis((pyridin-4-yl) phenyl)porphyrin “Co-MTPhPyP” and Its Application to the Removal of Heavy Metal Ions
by Henry Arceo-Ruiz, Elba Xochitiotzi-Flores, Héctor García-Ortega, Norberto Farfán, Rosa Santillan, Susana Rincón and Alejandro Zepeda
Molecules 2023, 28(4), 1816; https://doi.org/10.3390/molecules28041816 - 15 Feb 2023
Cited by 2 | Viewed by 1888
Abstract
The synthesis of a Co metal–organic framework assembled from 5,10,15,20-tetrakis((pyridin-4-yl)phenyl)porphyrin; TPhPyP) “Co-MTPhPyP” is reported. The TPhPyP ligand was synthesized via aldehyde condensation in 28% yield and characterized by 1H nuclear magnetic resonance (1H NMR), Fourier-transform infrared (FTIR), high-resolution mass spectrometry [...] Read more.
The synthesis of a Co metal–organic framework assembled from 5,10,15,20-tetrakis((pyridin-4-yl)phenyl)porphyrin; TPhPyP) “Co-MTPhPyP” is reported. The TPhPyP ligand was synthesized via aldehyde condensation in 28% yield and characterized by 1H nuclear magnetic resonance (1H NMR), Fourier-transform infrared (FTIR), high-resolution mass spectrometry (HRMS), and UV-visible spectroscopy (UV-vis). Co-MTPhPyP was prepared by the solvothermal method from TPhPyP and CoCl2·H2O in 55% yield and characterized by X-ray powder diffraction (XRD), FTIR, thermogravimetric analysis (TGA), field-emission scanning electron microscopy with energy-dispersive X-ray (FESEM-EDS), X-ray photoelectron spectroscopy (XPS), and dynamic light scattering (DLS), showing a particle size distribution of 418 ± 58 nm. The sorption properties of the Co-MTPhPyP for the effective removal of Pb(II) and Cu(II) were evaluated in an aqueous medium and Cthe results showed uptake capacities of 383.4 and 168 mg of the metal g−1 after 2 h, respectively. Kinetic studies of Pb(II) adsorption by Co-MTPhPyP were adjusted to the pseudo-second-order model with a maximum adsorption capacity of 458.8 mg g−1 at 30 min of exposition. Full article
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14 pages, 6438 KiB  
Article
Hierarchical Ultrathin Layered GO-ZnO@CeO2 Nanohybrids for Highly Efficient Methylene Blue Dye Degradation
by Marimuthu Karpuraranjith, Yuanfu Chen, Ramadoss Manigandan, Katam Srinivas and Sivamoorthy Rajaboopathi
Molecules 2022, 27(24), 8788; https://doi.org/10.3390/molecules27248788 - 11 Dec 2022
Cited by 2 | Viewed by 1347
Abstract
Highly efficient interfacial contact between components in nanohybrids is a key to achieving great photocatalytic activity in photocatalysts and degradation of organic model pollutants under visible light irradiation. Herein, we report the synthesis of nano-assembly of graphene oxide, zinc oxide and cerium oxide [...] Read more.
Highly efficient interfacial contact between components in nanohybrids is a key to achieving great photocatalytic activity in photocatalysts and degradation of organic model pollutants under visible light irradiation. Herein, we report the synthesis of nano-assembly of graphene oxide, zinc oxide and cerium oxide (GO-ZnO@CeO2) nanohybrids constructed by the hydrothermal method and subsequently annealed at 300 °C for 4 h. The unique graphene oxide sheets, which are anchored with semiconducting materials (ZnO and CeO2 nanoparticles), act with a significant role in realizing sufficient interfacial contact in the new GO-ZnO@CeO2 nanohybrids. Consequently, the nano-assembled structure of GO-ZnO@CeO2 exhibits a greater level (96.66%) of MB dye degradation activity than GO-ZnO nanostructures and CeO2 nanoparticles on their own. This is due to the thin layers of GO-ZnO@CeO2 nanohybrids with interfacial contact, suitable band-gap matching and high surface area, preferred for the improvement of photocatalytic performance. Furthermore, this work offers a facile building and cost-effective construction strategy to synthesize the GO-ZnO@CeO2 nanocatalyst for photocatalytic degradation of organic pollutants with long-term stability and higher efficiency. Full article
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11 pages, 1628 KiB  
Communication
SnSe Nanosheets Mimic Lactate Dehydrogenase to Reverse Tumor Acid Microenvironment Metabolism for Enhancement of Tumor Therapy
by Heng Wang, Beilei Wang, Jie Jiang, Yi Wu, Anning Song, Xiaoyu Wang, Chenlu Yao, Huaxing Dai, Jialu Xu, Yue Zhang, Qingle Ma, Fang Xu, Ruibin Li and Chao Wang
Molecules 2022, 27(23), 8552; https://doi.org/10.3390/molecules27238552 - 05 Dec 2022
Cited by 6 | Viewed by 1953
Abstract
The acidic tumor microenvironment (TME) is unfriendly to the activity and function of immune cells in the TME. Here, we report inorganic nanozymes (i.e., SnSe NSs) that mimic the catalytic activity of lactate dehydrogenase to degrade lactate to pyruvate, contributing to the metabolic [...] Read more.
The acidic tumor microenvironment (TME) is unfriendly to the activity and function of immune cells in the TME. Here, we report inorganic nanozymes (i.e., SnSe NSs) that mimic the catalytic activity of lactate dehydrogenase to degrade lactate to pyruvate, contributing to the metabolic treatment of tumors. As found in this study, SnSe NSs successfully decreased lactate levels in cells and tumors, as well as reduced tumor acidity. This is associated with activation of the immune response of T cells, thus alleviating the immunosuppressive environment of the TME. More importantly, the nanozyme successfully inhibited tumor growth in mutilate mouse tumor models. Thus, SnSe NSs show a promising result in lactate depletion and tumor suppression, which exemplifies its potential strategy in targeting lactate for metabolic therapy. Full article
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15 pages, 3503 KiB  
Article
pH-Responsive Drug Delivery and Imaging Study of Hybrid Mesoporous Silica Nanoparticles
by Zhongtao Li, Jing Guo, Guiqiang Qi, Meng Zhang and Liguo Hao
Molecules 2022, 27(19), 6519; https://doi.org/10.3390/molecules27196519 - 02 Oct 2022
Cited by 9 | Viewed by 1863
Abstract
A system of pH-responsive and imaging nanocarriers was developed using mesoporous silica nanoparticles (MSNs), in which gadolinium (Gd) was doped through in situ doping (Gd2O3@MSN). Sodium alginate (SA) was attached to the surfaces of the amino groups of MSNs [...] Read more.
A system of pH-responsive and imaging nanocarriers was developed using mesoporous silica nanoparticles (MSNs), in which gadolinium (Gd) was doped through in situ doping (Gd2O3@MSN). Sodium alginate (SA) was attached to the surfaces of the amino groups of MSNs (NH2-Gd2O3@MSN) through the electrostatic adsorption between the amino groups and the carboxyl groups with the formation of hybrid SA-Gd2O3@MSN nanoparticles (NPs). The SA-coated NPs were spherical or near-spherical in shape with an average size of nearly 83.2 ± 8.7 nm. The in vitro drug release experiments of a model rhodamine B (RhB) cargo were performed at different pH values. The result confirmed the pH-responsiveness of the nanocarriers. The results of the cytotoxicity studies indicated that the SA-Gd2O3@MSN NPs were not cytotoxic by themselves. The results of the in vivo safety evaluation and the hemolysis assay confirmed that the system is highly biocompatible. It is noteworthy that the T1 contrast of the system was significantly enhanced by the Gd, as indicated by the result of the MR imaging. This study confirms that the synthesized hybrid nanosystem is promising for pH-responsive drug delivery and MR imaging for cancer diagnosis and treatment. Full article
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18 pages, 3314 KiB  
Article
Tropaeolin OO as a Chemical Sensor for a Trace Amount of Pd(II) Ions Determination
by Adrianna Pach, Agnieszka Podborska, Edit Csapo and Magdalena Luty-Błocho
Molecules 2022, 27(14), 4511; https://doi.org/10.3390/molecules27144511 - 14 Jul 2022
Cited by 1 | Viewed by 1827
Abstract
The selective determination of metals in waste solutions is a very important aspect of the industry and environmental protection. Knowledge of the contents and composition of the waste can contribute to design an efficient process separation and recovery of valuable metals. The problematic [...] Read more.
The selective determination of metals in waste solutions is a very important aspect of the industry and environmental protection. Knowledge of the contents and composition of the waste can contribute to design an efficient process separation and recovery of valuable metals. The problematic issue is primarily the correct determination of metals with similar properties such as palladium and platinum. Thus this paper focuses on the development of a selective method that enables Pd(II) determination in the presence of Pt(IV) ions using the azo-dye tropaeolin OO (TR). For this purpose, the process of the metalorganic complex formation and Pd(II) ions determination were studied by using UV–Vis spectrophotometry under different conditions: solvents (water and B-R buffer), pH (2.09–6.09), temperature (20–60 °C), anions and cations concentrations. The formed metalorganic complex between Pd and tropaeolin OO allows for distinguishing Pd(II) ions from both platinum complexes, i.e. Pt(II), Pt(IV). Moreover, the proposed method can be applied to solutions containing both chloride and chlorate ions. The obtained characteristic spectrum with two maxima allows the determination of palladium even in the presence of other cations (Na, K, Mg, Zn, Co, Ni, Al) and changed concentrations of Pt(IV) ions. Furthermore, the developed spectrophotometric method for the Pd(II) ions determination using tropaeolin OO is characterized by high selectivity towards palladium ions. Full article
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17 pages, 8695 KiB  
Article
Chemical Solution Deposition of Barium Titanate Thin Films with Ethylene Glycol as Solvent for Barium Acetate
by Sabi William Konsago, Katarina Žiberna, Brigita Kmet, Andreja Benčan, Hana Uršič and Barbara Malič
Molecules 2022, 27(12), 3753; https://doi.org/10.3390/molecules27123753 - 10 Jun 2022
Cited by 4 | Viewed by 2153
Abstract
Chemical solution deposition (CSD) of BaTiO3 (BT) or BT-based thin films relies on using a carboxylic acid and alcohol as the solvents for alkaline-earth carboxylate and transition-metal alkoxide, respectively; however, the esterification reaction of the solvents may lead to in-situ water formation [...] Read more.
Chemical solution deposition (CSD) of BaTiO3 (BT) or BT-based thin films relies on using a carboxylic acid and alcohol as the solvents for alkaline-earth carboxylate and transition-metal alkoxide, respectively; however, the esterification reaction of the solvents may lead to in-situ water formation and precipitation. To avoid such an uncontrolled reaction, we developed a route in which ethylene glycol (EG) is used as the solvent for Ba-acetate. The EG-based BT coating solutions are stable for at least a few months. The thermal decomposition of the BT xerogel obtained by drying the EG-based solutions depends on the choice of the solvent for the Ti-alkoxide as well: in the case of EG and 2-methoxyethanol solvents carbon residues are removed at only about 1100 °C, while in the case of ethanol it is concluded at about 700 °C. About 100 nm thick BT films derived from the EG-ethanol solution deposited on platinized silicon reveal dense, crack-free columnar microstructure. They exhibit local ferro- and piezoelectric properties. The macroscopic polarization-electric field loops were obtained up to a quite high electric field of about 2.4 MV/cm. The EG-ethanol based CSD route is a viable alternative to the established acetic acid–alcohol route for BT and BT-based films. Full article
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18 pages, 5316 KiB  
Article
Nanostructured, Metal-Free Electrodes for the Oxygen Reduction Reaction Containing Nitrogen-Doped Carbon Quantum Dots and a Hydroxide Ion-Conducting Ionomer
by Ashwini Reddy Nallayagari, Emanuela Sgreccia, Maria Luisa Di Vona, Luca Pasquini, Florence Vacandio and Philippe Knauth
Molecules 2022, 27(6), 1832; https://doi.org/10.3390/molecules27061832 - 11 Mar 2022
Cited by 4 | Viewed by 2404
Abstract
In this work, we studied the combination of nitrogen-doped carbon quantum dots (N-CQD), a hydroxide-ion conducting ionomer based on polysulfone (PSU) and polyaniline (PANI), to explore the complementary properties of these materials in high-performance nanostructured electrodes for the oxygen reduction reaction (ORR) in [...] Read more.
In this work, we studied the combination of nitrogen-doped carbon quantum dots (N-CQD), a hydroxide-ion conducting ionomer based on polysulfone (PSU) and polyaniline (PANI), to explore the complementary properties of these materials in high-performance nanostructured electrodes for the oxygen reduction reaction (ORR) in alkaline solution. N-CQD were made by hydrothermal synthesis from glucosamine hydrochloride (GAH) or glucosamine hydrochloride and N-Octylamine (GAH-Oct), and PSU were quaternized with trimethylamine (PSU-TMA). The nanocomposite electrodes were prepared on carbon paper by drop-casting. Furthermore, we succeeded in preparing PSU-TMA + PANI + GAH-Oct fibers by electrospinning. The capacitance of the electrodes was investigated by cyclic voltammetry and impedance spectroscopy, which gave similar trends. The ORR was investigated by linear sweep voltammetry at rotating disk electrode speeds between 250 and 2000 rpm in an oxygen-saturated 1 M KOH solution. Koutecky–Levich plots showed that four electrons were exchanged for nanocomposite electrodes containing CQD. The highest reduction currents were measured for the electrodes containing GAH-Oct. The Tafel plots gave the lowest slope and the most positive half-wave potential for PSU-TMA + PANI + GAH-Oct fibers. The best electrocatalytic activity of this electrode could be related to the high amount of graphitic nitrogen in GAH-Oct. Long-term cycling tests showed no significant modification of the onset potential, but a change of the current in the mass transport limited region, indicated the evolution of the microstructure of the nanocomposite ORR electrode modifying the mass transport conditions during the first 400 cycles before reaching stationary conditions. FTIR spectra were used to study possible electrode degradation after the ORR in 1 M KOH: the only change was due to the reaction of PANI emeraldine salt to emeraldine base, whereas the other constituents of the multiphase electrode did not show any degradation. Full article
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16 pages, 2175 KiB  
Article
Aliphatic Anion Exchange Ionomers with Long Spacers and No Ether Links by Ziegler–Natta Polymerization: Properties and Alkaline Stability
by Raul Andres Becerra-Arciniegas, Riccardo Narducci, Gianfranco Ercolani, Luca Pasquini, Philippe Knauth and Maria Luisa Di Vona
Molecules 2022, 27(2), 395; https://doi.org/10.3390/molecules27020395 - 08 Jan 2022
Cited by 2 | Viewed by 2565
Abstract
In this work we report the synthesis of poly(vinylbenzylchloride-co-hexene) copolymer grafted with N,N-dimethylhexylammonium groups to study the effect of an aliphatic backbone without ether linkage on the ionomer properties. The copolymerization was achieved by the Ziegler–Natta method, employing the complex ZrCl4 (THF) [...] Read more.
In this work we report the synthesis of poly(vinylbenzylchloride-co-hexene) copolymer grafted with N,N-dimethylhexylammonium groups to study the effect of an aliphatic backbone without ether linkage on the ionomer properties. The copolymerization was achieved by the Ziegler–Natta method, employing the complex ZrCl4 (THF)2 as a catalyst. A certain degree of crosslinking with N,N,N′,N′-tetramethylethylenediamine (TEMED) was introduced with the aim of avoiding excessive swelling in water. The resulting anion exchange polymers were characterized by 1H-NMR, FTIR, TGA, and ion exchange capacity (IEC) measurements. The ionomers showed good alkaline stability; after 72 h of treatment in 2 M KOH at 80 °C the remaining IEC of 76% confirms that ionomers without ether bonds are less sensitive to a SN2 attack and suggests the possibility of their use as a binder in a fuel cell electrode formulation. The ionomers were also blended with polyvinyl alcohol (PVA) and crosslinked with glutaraldehyde. The water uptake of the blend membranes was around 110% at 25 °C. The ionic conductivity at 25 °C in the OH form was 29.5 mS/cm. Full article
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Review

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20 pages, 2214 KiB  
Review
Recent Developments of Liquid Chromatography Stationary Phases for Compound Separation: From Proteins to Small Organic Compounds
by Handajaya Rusli, Rindia M. Putri and Anita Alni
Molecules 2022, 27(3), 907; https://doi.org/10.3390/molecules27030907 - 28 Jan 2022
Cited by 13 | Viewed by 4408
Abstract
Compound separation plays a key role in producing and analyzing chemical compounds. Various methods are offered to obtain high-quality separation results. Liquid chromatography is one of the most common tools used in compound separation across length scales, from larger biomacromolecules to smaller organic [...] Read more.
Compound separation plays a key role in producing and analyzing chemical compounds. Various methods are offered to obtain high-quality separation results. Liquid chromatography is one of the most common tools used in compound separation across length scales, from larger biomacromolecules to smaller organic compounds. Liquid chromatography also allows ease of modification, the ability to combine compatible mobile and stationary phases, the ability to conduct qualitative and quantitative analyses, and the ability to concentrate samples. Notably, the main feature of a liquid chromatography setup is the stationary phase. The stationary phase directly interacts with the samples via various basic mode of interactions based on affinity, size, and electrostatic interactions. Different interactions between compounds and the stationary phase will eventually result in compound separation. Recent years have witnessed the development of stationary phases to increase binding selectivity, tunability, and reusability. To demonstrate the use of liquid chromatography across length scales of target molecules, this review discusses the recent development of stationary phases for separating macromolecule proteins and small organic compounds, such as small chiral molecules and polycyclic aromatic hydrocarbons (PAHs). Full article
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