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Chemistry, Volume 6, Issue 1 (February 2024) – 12 articles

Cover Story (view full-size image): The extensive use of antibiotics by living systems has led to their large accumulation in water streams and the environment. This poses serious risks to human health and environmental well-being. Therefore, it is essential to find a suitable sensing probe for the trace detection of antibiotics in water. We developed a new nanoscale fluorescent Zn(II) coordination polymer, TB-Zn-CP, for differential sensing of various antibiotics in water. TB-Zn-CP exhibited a high binding affinity for chloramphenicol, 1,2-dimethyl-5-nitroimidazole, and sulfamethazine antibiotics with nanomolar levels of sensitivity. The differential sensing responses of TB-Zn-CP for different antibiotics were also reflected by marked visual color changes. This study demonstrates that TB-Zn-CP can be a useful sensor for differential sensing of antibiotics in water. View this paper
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15 pages, 3590 KiB  
Article
Methylene Blue Removal by Copper Oxide Nanoparticles Obtained from Green Synthesis of Melia azedarach: Kinetic and Isotherm Studies
by Wafa K. Essa
Chemistry 2024, 6(1), 249-263; https://doi.org/10.3390/chemistry6010012 - 19 Feb 2024
Viewed by 852
Abstract
In this study, Melia azedarach fruit extract was used as a reducing agent and copper chloride dihydrate (CuCl2·2H2O) was used as a precursor in the synthesis of copper oxide nanoparticles (CuO NPs). The UV–visible spectrum showed a characteristic absorption [...] Read more.
In this study, Melia azedarach fruit extract was used as a reducing agent and copper chloride dihydrate (CuCl2·2H2O) was used as a precursor in the synthesis of copper oxide nanoparticles (CuO NPs). The UV–visible spectrum showed a characteristic absorption peak of CuO NPs at 350 nm. The surface properties of the adsorbent were analyzed through various techniques, indicating the successful formation of CuO NPs. The impacts of several factors, including initial pH (4 to 8), a dose of CuO NPs adsorbent (0.01–0.05 g), dye initial concentration (10–50 mg·L−1), and contact times ranging from 5 to 120 min, were examined in batch adsorption studies. Based on the experimental results, the Langmuir isotherm is well-fitted, indicating MB dye monolayer capping on the CuO NPs surface with 26.738 mg·g−1 as a maximum adsorption capacity Qm value. For the pseudo-second-order kinetic model, the experimental and calculated adsorption capacity values (qe) exhibited good agreement. Full article
(This article belongs to the Special Issue Low-Cost Water Treatment - New Materials and New Approaches)
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12 pages, 5266 KiB  
Article
Differential Fluorescent Chemosensing of Antibiotics Using a Luminescent Zn(II) Coordination Polymer Based on a 4-Amino-1,8-naphthalimide Tröger’s Base Fluorophore
by Purti Patel, Mannanthara Kunhumon Noushija and Sankarasekaran Shanmugaraju
Chemistry 2024, 6(1), 237-248; https://doi.org/10.3390/chemistry6010011 - 07 Feb 2024
Viewed by 745
Abstract
The design and development of useful chemosensors for the ultra-trace detection of environmental pollutants and contaminants is a topical area of research. Herein, we report a new nanoscale emissive Zn(II) coordination polymer (TB-Zn-CP) for differential fluorescence sensing of various antibiotics in [...] Read more.
The design and development of useful chemosensors for the ultra-trace detection of environmental pollutants and contaminants is a topical area of research. Herein, we report a new nanoscale emissive Zn(II) coordination polymer (TB-Zn-CP) for differential fluorescence sensing of various antibiotics in water. TB-Zn-CP was synthesized using a unique V-shaped green emitting 4-amino-1,8-naphthalimide Tröger’s base (TBNap) fluorophore. The structural and morphological features of TB-Zn-CP were characterized by various standard spectroscopic and microscopy techniques. The fluorescence titration studies in water demonstrated a remarkable sensitivity and differential fluorescence sensing properties of TB-Zn-CP for the fast detection of different antibiotics. Among different antibiotics, chloramphenicol (CRP), 1,2-dimethyl-5-nitroimidazole (DMZ), and sulfamethazine (SMZ) displayed the highest fluorescence-quenching efficiency and superior sensitivity in their detection. The differential sensing capability of TB-Zn-CP was also indicated by visualizable color changes. The Stern–Volmer quenching constant KSV was determined to be in the order of 103–104 M−1, and the sensitivity was shown to be at a nanomolar (10−9 M) level. All these results confirm that TB-Zn-CP can be a potential and practically useful polymeric sensor for differential fluorescence and visual detection of different antibiotics in water. Full article
(This article belongs to the Section Supramolecular Chemistry)
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30 pages, 7878 KiB  
Review
Temperature Matters: Enhancing Performance and Stability of Perovskite Solar Cells through Advanced Annealing Methods
by Shengcong Wu, Chi Li, Shui Yang Lien and Peng Gao
Chemistry 2024, 6(1), 207-236; https://doi.org/10.3390/chemistry6010010 - 30 Jan 2024
Viewed by 1200
Abstract
Perovskite solar cells (PSCs) have garnered significant attention in the photovoltaic field owing to their exceptional photoelectric properties, including high light absorption, extensive carrier diffusion distance, and an adjustable band gap. Temperature is a crucial factor influencing both the preparation and performance of [...] Read more.
Perovskite solar cells (PSCs) have garnered significant attention in the photovoltaic field owing to their exceptional photoelectric properties, including high light absorption, extensive carrier diffusion distance, and an adjustable band gap. Temperature is a crucial factor influencing both the preparation and performance of perovskite solar cells. The annealing temperature exerts a pronounced impact on the device structure, while the operational temperature influences carrier transport, perovskite band gap, and interface properties. This paper provides a comprehensive review of the influence of varied annealing temperatures on the hole transport layer, electron transport layer, and perovskite layer. Additionally, we present an overview of innovative annealing methods applied to perovskite materials. The effects of diverse working temperatures on the overall performance of perovskite cells are thoroughly examined and discussed in this review. In the end, different temperature conditions under ISOS testing conditions are summarized. Full article
(This article belongs to the Section Physical Chemistry and Chemical Physics)
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42 pages, 19786 KiB  
Review
Pioneering Synthetic Strategies of 2-Substituted Benzothiazoles Using 2-Aminothiophenol
by Sunita Teli, Ayushi Sethiya and Shikha Agarwal
Chemistry 2024, 6(1), 165-206; https://doi.org/10.3390/chemistry6010009 - 30 Jan 2024
Viewed by 814
Abstract
Heterocycles, compounds featuring heteroatoms like nitrogen, sulfur, and oxygen, are integral in fields such as synthesis, pharmacology, and medicine. Among these, benzothiazoles, formed by fusing thiazole with benzene, hold significant prominence. Their unique reactivity, especially at the carbon position between nitrogen and sulfur, [...] Read more.
Heterocycles, compounds featuring heteroatoms like nitrogen, sulfur, and oxygen, are integral in fields such as synthesis, pharmacology, and medicine. Among these, benzothiazoles, formed by fusing thiazole with benzene, hold significant prominence. Their unique reactivity, especially at the carbon position between nitrogen and sulfur, has sparked wide interest. Notably, 2-substituted benzothiazoles exhibit diverse biological activities, including anticonvulsant, antimicrobial, and antioxidant properties, making them valuable in drug discovery. This review unveils an array of mesmerizing methods employed by chemists to prepare these compounds using 2-aminothiophenol as one of the precursors with other varied reactants. From novel strategies to sophisticated methodologies, each section of this review provides a glimpse into the fascinating world of synthetic chemistry of 2-substituted benzothiazoles. Delving into the diverse synthetic applications of 2-substituted benzothiazoles, this paper not only enriches our understanding of their synthesis but also sparks the imagination with the possibilities for future advancements. Full article
(This article belongs to the Section Medicinal Chemistry)
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12 pages, 1453 KiB  
Article
Unveiling the Molecular Signature of High-Temperature Cooking: Gas Chromatography-Mass Spectrometry Profiling of Sucrose and Histidine Reactions and Its Derivatives Induce Necrotic Death on THP1 Immune Cells
by Vaiyapuri Subbarayan Periasamy, Jegan Athinarayanan and Ali A. Alshatwi
Chemistry 2024, 6(1), 153-164; https://doi.org/10.3390/chemistry6010008 - 15 Jan 2024
Viewed by 919
Abstract
High-temperature cooking processes like frying, baking, smoking, or drying can induce chemical transformations in conventional food ingredients, causing deteriorative modifications. These reactions, including hydrolytic, oxidative, and thermal changes, are common and can alter the food’s chemical composition. This study transformed a combination of [...] Read more.
High-temperature cooking processes like frying, baking, smoking, or drying can induce chemical transformations in conventional food ingredients, causing deteriorative modifications. These reactions, including hydrolytic, oxidative, and thermal changes, are common and can alter the food’s chemical composition. This study transformed a combination of sucrose and histidine (Su-Hi) through charring or pyrolysis. The GC-MS profiling study showed that when sucrose and histidine (Su-Hi) were exposed to high temperatures (≈240 °C), they produced carbonyl and aromatic compounds including beta-D-Glucopyranose, 1,6-anhydro (10.11%), 2-Butanone, 4,4-dimethoxy- (12.89%), 2(1H)-Quinolinone-hydrazine (5.73%), Benzenamine (6.35%), 2,5-Pyrrolidinedione, 1-[(3,4-dimethylbenzoyl)oxy]- (5.82%), Benzene-(1-ethyl-1-propenyl) (5.62%), and 4-Pyridinamine-2,6-dimethyl (5.52%). The compounds mentioned can permeate the cell membrane and contribute to the development of cell death by necrosis in human immune cells. The evidence suggests that a specific set of pyrolytic compounds may pose a risk to immune cells. This investigation reveals the complex relationship between high-temperature cooking-induced transformations, compound permeation inside the cells, and downstream cellular responses, emphasizing the significance of considering the broader health implications of food chemical contaminants. Full article
(This article belongs to the Section Food Science)
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55 pages, 11356 KiB  
Review
Recent Developments in Enantioselective Scandium-Catalyzed Transformations
by Hélène Pellissier
Chemistry 2024, 6(1), 98-152; https://doi.org/10.3390/chemistry6010007 - 11 Jan 2024
Viewed by 785
Abstract
This review collects the recent developments in the field of enantioselective scandium-catalyzed transformations published since the beginning of 2016, illustrating the power of chiral scandium catalysts to promote all types of reactions. Full article
(This article belongs to the Section Catalysis)
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3 pages, 154 KiB  
Editorial
Special Issue “Functional Biomolecule-Based Composites and Nanostructures: Current Developments and Applications—A Themed Issue in Honor of Prof. Dr. Itamar Willner”
by Di Li
Chemistry 2024, 6(1), 95-97; https://doi.org/10.3390/chemistry6010006 - 11 Jan 2024
Viewed by 542
Abstract
This Special Issue of Chemistry is a themed issue of “Functional Biomolecule-Based Composites and Nanostructures: Current Developments and Applications” in honor of Itamar Willner to celebrate his innovative research career [...] Full article
14 pages, 1686 KiB  
Article
A Sensor (Optode) Based on Cellulose Triacetate Membrane for Fe(III) Detection in Water Samples
by Zulhan Arif, Sri Sugiarti, Eti Rohaeti and Irmanida Batubara
Chemistry 2024, 6(1), 81-94; https://doi.org/10.3390/chemistry6010005 - 27 Dec 2023
Viewed by 776
Abstract
Iron is a heavy metal that often contaminates water. High iron concentrations are toxic to human health, so monitoring its presence in water is necessary. Iron in water can be detected using an optical sensor (optode). This research aims to fabricate an optode [...] Read more.
Iron is a heavy metal that often contaminates water. High iron concentrations are toxic to human health, so monitoring its presence in water is necessary. Iron in water can be detected using an optical sensor (optode). This research aims to fabricate an optode based on a cellulose triacetate membrane with a selective reagent against Fe(III). The optode was fabricated by mixing cellulose triacetate polymer, a plasticiser (a mixture of oleic acid and acetophenone), aliquot-336, and thiocyanate as a selective reagent. Membrane performance was tested based on working range, linearity, limit of detection and quantitation, precision, and accuracy. The performance of the membrane showed a linear response in the concentration range of 0.1–4 mg/L with a coefficient of determination (R2) of 0.9937, limit of detection of 0.0250 mg/L, limit of quantitation of 0.0757 mg/L, repeatability precision with a relative standard deviation of 3.31%, and an accuracy of 100.49%. Optode selectivity was good for interfering ions Cr(VI) and Pb(II). The colour complex of the optode was stable until the 10th day. The application of iron detection in water samples shows an average concentration of 0.2541 mg/L with good precision and accuracy. Full article
(This article belongs to the Section Green and Environmental Chemistry)
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19 pages, 6385 KiB  
Article
4,4-Bis(isopropylthio)-1,1-diphenyl-2-azabuta-1,3-diene Adducts with Cadmium(II), Mercury(II) and Copper(I) Iodides: Crystal, Molecular and Electronic Structures of d10 Transition Metal Chelate Complexes
by Rodolphe Kinghat, Abderrahim Khatyr, Michael Knorr, Carsten Strohmann and Marek M. Kubicki
Chemistry 2024, 6(1), 62-80; https://doi.org/10.3390/chemistry6010004 - 25 Dec 2023
Viewed by 742
Abstract
The thioether-functionalized 2-azabutadiene (iPrS)2C=C(H)-N=CPh2 L ligates to CdI2 and HgI2 to form the chelate compounds [CdI2{(iPrS)2C=C(H)-N=CPh2] (1) and [HgI2(iPrS)2C=C(H)-N=CPh [...] Read more.
The thioether-functionalized 2-azabutadiene (iPrS)2C=C(H)-N=CPh2 L ligates to CdI2 and HgI2 to form the chelate compounds [CdI2{(iPrS)2C=C(H)-N=CPh2] (1) and [HgI2(iPrS)2C=C(H)-N=CPh2] (2). Their crystal structures were solved via X-ray diffraction. Both crystallize in the non-centrosymmetric space groups: monoclinic P21 (1) and orthorhombic P212121 (2), respectively. The closed-shell d10 metal centers are four-coordinated (two iodides and S and N coordinating atoms from the ligand L) in both complexes. The geometrical indexes τ indicate that a highly distorted trigonal pyramidal is adopted for 1 and a seesaw geometry for 2. The comparative nature of metal–ligand bonds is discussed on the basis of metric parameters and of QT-AIM (quantum theory of atoms in molecules) calculations. L was also treated with CuI to obtain the dinuclear species [LCu(μ2-I2)CuL] (3), in which the two Cu(I) centers are linked by a short metal–metal bond. The geometric and electronic properties of 3 are compared with those of 1 and 2. Full article
(This article belongs to the Section Crystallography)
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11 pages, 2061 KiB  
Article
New Polymorph of β-Cyclodextrin with a Higher Bioavailability
by Askar K. Gatiatulin, Ilya S. Balakhontsev, Sofia M. Talashmanova, Marat A. Ziganshin and Valery V. Gorbatchuk
Chemistry 2024, 6(1), 51-61; https://doi.org/10.3390/chemistry6010003 - 23 Dec 2023
Viewed by 745
Abstract
A new polymorph of anhydrous β-cyclodextrin (polymorph III) was obtained and characterized for the first time using powder X-ray diffraction, infrared spectroscopy, and thermal analysis. The solution enthalpy and time of dissolution in water were determined using solution calorimetry for this polymorph and [...] Read more.
A new polymorph of anhydrous β-cyclodextrin (polymorph III) was obtained and characterized for the first time using powder X-ray diffraction, infrared spectroscopy, and thermal analysis. The solution enthalpy and time of dissolution in water were determined using solution calorimetry for this polymorph and compared with those of the dried commercial form of β-cyclodextrin (polymorph I), its amorphous form, and 2-hydroxypropyl-β-cyclodextrin. The specific heat capacities of polymorphs I and III were determined using differential scanning calorimetry across a wide range of temperatures, providing enthalpy and Gibbs energy values for the polymorphic transition at 298 K. The affinities of polymorph III and 2-hydroxypropyl-β-cyclodextrin for water were characterized by determining their hydration isotherms, which provided values of hydration Gibbs energy. Being energy-rich, the new-found polymorph of β-cyclodextrin has a significantly higher dissolution rate and an increased affinity for water compared with the dried commercial form of β-cyclodextrin. These properties render the new polymorph promising in industrial applications for guest inclusion in aqueous solutions and pastes, and may be a desirable alternative for water-soluble β-cyclodextrin derivatives. Full article
(This article belongs to the Section Supramolecular Chemistry)
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38 pages, 6005 KiB  
Review
Pure Hydrolysis of Polyamides: A Comparative Study
by Mathis Mortensen Brette, Allan Hjarbæk Holm, Aleksey D. Drozdov and Jesper de Claville Christiansen
Chemistry 2024, 6(1), 13-50; https://doi.org/10.3390/chemistry6010002 - 20 Dec 2023
Cited by 1 | Viewed by 1925
Abstract
Polyamides (PAs) undergo local environmental degradation, leading to a decline in their mechanical properties over time. PAs can experience various forms of degradation, such as thermal degradation, oxidation, hydrothermal oxidation, UV oxidation, and hydrolysis. In order to better comprehend the degradation process of [...] Read more.
Polyamides (PAs) undergo local environmental degradation, leading to a decline in their mechanical properties over time. PAs can experience various forms of degradation, such as thermal degradation, oxidation, hydrothermal oxidation, UV oxidation, and hydrolysis. In order to better comprehend the degradation process of PAs, it is crucial to understand each of these degradation mechanisms individually. While this review focuses on hydrolysis, the data from degrading similar PAs under pure thermal oxidation and/or hydrothermal oxidation are also collected to grasp more perspective. This review analyzes the available characterization data and evaluates the changes in molecular weight, crystallinity, chemical structure, and mechanical properties of PAs that have aged in oxygen-free water at high temperatures. The molecular weight and mechanical strength decrease as the crystallinity ratio rises over aging time. This development is occurring at a slower rate than degradation in pure thermal oxidation. By combining the data for the changes in mechanical properties with the ones for molecular weight and crystallinity, the point of embrittlement can be not only predicted, but also modeled. This prediction is also shown to be dependent on the fibers, additives, types of PA, pH, and more. Full article
(This article belongs to the Topic Molecular Topology and Computation)
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12 pages, 1072 KiB  
Article
Synthesis, Antibacterial Activity, and Cytotoxicity of Azido-Propargyloxy 1,3,5-Triazine Derivatives and Hyperbranched Polymers
by Anna V. Tsyganova, Artem O. Petrov, Alexey V. Shastin, Natalia V. Filatova, Victoria A. Mumyatova, Alexander E. Tarasov, Alina V. Lolaeva and Georgiy V. Malkov
Chemistry 2024, 6(1), 1-12; https://doi.org/10.3390/chemistry6010001 - 19 Dec 2023
Viewed by 769
Abstract
A new method for the synthesis of azido-propargyloxy derivatives of 1,3,5-triazine has been developed utilizing the nitrosation of hydrazyno-1,3,5-triazines. New hydrazines (2-hydrazino-4,6-bis(propargyloxy)-1,3,5-triazine and 2,4-dihydrazino-6-propargyloxy-1,3,5-triazine) were synthesized and characterized via FTIR, NMR spectroscopy and elemental analysis. The hyperbranched polymers with azide (diazide monomer) and [...] Read more.
A new method for the synthesis of azido-propargyloxy derivatives of 1,3,5-triazine has been developed utilizing the nitrosation of hydrazyno-1,3,5-triazines. New hydrazines (2-hydrazino-4,6-bis(propargyloxy)-1,3,5-triazine and 2,4-dihydrazino-6-propargyloxy-1,3,5-triazine) were synthesized and characterized via FTIR, NMR spectroscopy and elemental analysis. The hyperbranched polymers with azide (diazide monomer) and propargyloxy terminal groups were obtained via the azide-alkyne polycycloaddition reaction of diazide and monoazide AB2-type monomers. The antibacterial activity against Escherichia coli bacteria of 2,4,6-trispropargyloxy-1,3,5-triazine, 2-azido-4,6-bispropargyloxy-1,3,5-triazine, and 2,4-diazido-6-propargyloxy-1,3,5-triazine and their hyperbranched polymers was studied. Only 2,4-diazido-6-propargyloxy-1,3,5-triazine has weak antibacterial activity in comparison with ampicillin. The cytotoxicity of these compounds against M-HeLa, FetMSC, and Vero cell lines was also studied. 2,4,6-trispropargyloxy-1,3,5-triazine does not show any cytotoxic effect (IC50 ≥ 280 µM). It was shown that the presence of an azide group in the compound directly affects the cytotoxic effect. Hyperbranched polymers have a less cytotoxic effect against M-HeLa (IC50 > 100) in comparison with monomers (IC50 = 90–99 µM). This makes it possible to use these polymers as the basis for biocompatible materials in biomedical applications. Full article
(This article belongs to the Section Medicinal Chemistry)
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