Search Results (28)

Background: Nedaplatin is a platinum-based anticancer drug that combines the benefits of Cisplatin and Carboplatin, retaining Cisplatin’s anticancer activity while reducing toxicity similar to Carboplatin. After hydrolysis, Nedaplatin targets purines in DNA and forms cross-links that induce cell death via apoptosis. However, it is important to consider how the presence of other chemical compounds with structural similarities to Adenine or Guanine, such as aromatic, purine, or pyrimidine compounds containing a nitrogen atom with a free electron pair, might influence its activity at the cellular level. Alkaloids with structures similar to DNA nucleobases are common, and their influence on Nedaplatin’s activity requires investigation. Methods: In this study, the interactions between Nedaplatin (including its hydrolyzed forms, such as [Pt(NH₃)₂(H₂O)₂]²⁺ and [Pt(NH₃)₂(H₂O)(OH)]⁺) and nucleobases (Adenine and Guanine) and purine alkaloids (Caffeine, Theobromine and Theophylline) were thoroughly investigated using theoretical (density functional theory, DFT) and experimental (UV-Vis spectroscopy) methods. DFT calculations were performed at the B3LYP/6-31G(d,p)/LANL2DZ and MN15/def2-TZVP levels, with structure optimization and harmonic analysis in the gas phase and aqueous solution (modeled using IEF-PCM). UV-Vis spectroscopy was used to verify theoretical findings by examining changes in absorption spectra. Results: Both theoretical and experimental studies confirmed that Nedaplatin forms complexes with both nucleobases and purine alkaloids. Nedaplatin was found to exhibit a higher affinity for nucleobases than for purine alkaloids. Furthermore, this affinity was dependent on the computational method used and on the hydrolyzed form of Nedaplatin. Theoretical calculations showed the formation of stable complexes through bonding with nitrogen atoms in the ligand molecules, which was confirmed by changes in UV-Vis spectra, indicating adduct formation. Conclusions: The results indicate that Nedaplatin readily forms complexes with both nucleobases and purine alkaloids, showing a stronger affinity for nucleobases. This finding highlights the potential importance of Nedaplatin’s interactions with other compounds present in the body, which may influence its effectiveness and mechanism of action in cancer therapy. These studies provide new insights into the molecular mechanisms of Nedaplatin’s action and may contribute to a better understanding of its pharmacological interactions. However, research requires confirmation not only in in vivo studies but also in clinical trials. Full article

Broad lateral size and thickness distributions impede the application of hexagonal boron nitride nanosheets (BNNSs) as friction modifiers in base oil, although they possess remarkable potential for lubrication performance promotion. In this work, a cascade centrifugation-assisted liquid-phase exfoliation approach was presented to prepare BNNSs from hexagonal boron nitride (h-BN) efficiently and scalably. Subsequently, they were ultrasonically dispersed into gas-to-liquid (GTL) base oil, and their lubrication performance promotion was evaluated by a four-ball tribotester. Tribological tests demonstrated that BNNS possesses excellent friction-reducing and anti-wear properties in GTL. Furthermore, the findings indicate that at a BNNS content of 0.8 wt.%, the system displayed the lowest COF and WSD. Particularly, with an addition of 0.8 wt.% BNNS into GTL, the AFC and WSD are reduced significantly by 40.1% and 35.4% compared to pure base oil, respectively, and the surface roughness, wear depth, and wear volume were effectively reduced by 91.0%, 68.5%, and 76.8% compared to GTL base oil, respectively. Raman, SEM-EDS, and XPS results proved that the outstanding friction-reducing and anti-wear properties of BNNS can mainly be ascribed to the presence of physical adsorption film and tribo-chemical film, which were composed of FeOOH, FeO, Fe₃O₄, and B₂O₃. Full article

Prototropic conversion (prototropy) for heterocyclic nucleobases was already signaled by Watson and Crick about seventy years ago as one of the reasons for nucleic acids mutations. This isomeric phenomenon has been investigated for neutral derivatives by means of both experimental and theoretical procedures, and their favored tautomers discussed in numerous articles published in the last fifty years. Protonation/deprotonation reactions in the gas phase have also been studied using both quantum-chemical calculations and experimental techniques. Some thermochemical parameters of these processes have been documented. However, prototropy has not always been taken into account in protonation/deprotonation reactions. Most frequently, tautomeric heterocycles have been treated as simple polyfunctional compounds without possible intramolecular protontransfers. Taking into account the lack of data for the complete tautomeric mixtures, quantum-chemical investigations have been undertaken by us about twenty-five years ago for prototropic heterosystems. In this work, the pyrimidine base uracil (U) was chosen. It possesses two identical exo groups (=O/OH) at the 2- and 4-positions, two labile (tautomeric) protons, and five conjugated sites (N1, N3, C5, O7, and O8). Different types of isomerism, prototropy and OH-rotation, were considered for the neutral, protonated, and deprotonated forms. Using quantum-chemical methods, thermochemical stabilities of all possible tautomers-rotamers were examined in vacuo and the potential isomers selected. The selected isomeric mixtures for the neutral and ionic forms were applied for the determination of the thermochemical parameters in the four-step acid/base equilibria: B²⁻ BH⁻ BH₂ BH₃⁺ BH₄²⁺, where BH₂ indicates U. For each step, the microscopic (kinetic) and macroscopic (thermodynamic) acid/base parameters were estimated, and sites of the proton gain and proton loss examined. The similarities and differences between the acid/base equilibria for uracil and other pyrimidine nucleobases were discussed. Full article

Currently, NiFe-LDH exhibits an excellent oxygen evolution reaction (OER) due to the interaction of the two metal elements on the layered double hydroxide (LDH) platform. However, such interaction is still insufficient to compensate for its poor electrical conductivity, limited number of active sites and sluggish dynamics. Herein, a feasible two-step hydrothermal strategy that involves coupling low-conductivity NiFe-LDH with 3D porous graphene aerogel (GA) is proposed. The optimized NiFe-LDH/GA (1:1) produced possesses a 257 mV (10 mA cm⁻²) overpotential and could operate stably for 56 h in an OER. Our investigation demonstrates that the NiFe-LDH/GA has a three-dimensional mesoporous structure, and that there is synergistic interaction between LDH and GA and interfacial reconstruction of NiOOH. Such an interface synergistic coupling effect promotes fast mass transfer and facilitates OER kinetics, and this work offers new insights into designing efficient and stable GA-based electrocatalysts. Full article

Hydrogen peroxide (H₂O₂) is an important chemical with a diverse range of industrial applications in chemical synthesis and medical disinfection. The traditional anthraquinone oxidation process, with high energy consumption and complexity, is being replaced by cost-effective and environmentally friendly alternatives. In order to explore suitable catalysts for the electrocatalytic synthesis of H₂O₂, the stability of B,N-doped graphene loaded with various p-block metal (PM) single atoms (i.e., PM-N_xB_y: x and y represent the number of atoms of N and B, respectively) and the effects of different numbers and positions of B dopants in the second coordination shell on the catalytic performance were studied by density functional theory (DFT) calculations. The results show that Ga-N₄B₆ and Sb-N₄B₆ exhibit enhanced stability and 2e⁻ oxygen reduction reaction (ORR) activity and selectivity. Their thermodynamic overpotential η values are 0.01 V, 0.03 V for Ga-N₄B₆’s two configurations and 0.02 V, 0 V for Sb-N₄B₆’s two configurations. Electronic structure calculations indicate that the PM single atom adsorbs OOH* intermediates and transfers electrons into them, resulting in the activation of the O-O bond, which facilitates the subsequent hydrogenation reaction. In summary, Sb-N₄B₆ and Ga-N₄B₆ exhibit extraordinary 2e⁻ ORR performance, and their predicted activities are comparable to those of known outstanding catalysts (such as PtHg₄ alloy). We propose effective strategies on how to enhance the 2e⁻ ORR activities of carbon materials, elucidate the origin of the activity of potential catalysts, and provide insights for the design and development of electrocatalysts that can be used for H₂O₂ production. Full article

Thermal transport is of grave importance in many high-value applications. Heat dissipation can be improved by utilizing liquid metals as thermal interface materials. Yet, liquid metals exhibit corrosivity towards many metals used for heat sinks, such as aluminum, and other electrical devices (i.e., copper). The compatibility of the liquid metal with the heat sink or device material as well as its long-term stability are important performance variables for thermal management systems. Herein, the compatibility of the liquid metal Galinstan, a eutectic alloy of gallium, indium, and tin, with diamond coatings and the stability of the liquid metal in this environment are scrutinized. The liquid metal did not penetrate the diamond coating nor corrode it. However, the liquid metal solidified with the progression of time, starting from the second year. After 4 years of aging, the liquid metal on all samples solidified, which cannot be explained by the dissolution of aluminum from the titanium alloy. In contrast, the solidification arose from oxidation by oxygen, followed by hydrolysis to GaOOH due to the humidity in the air. The hydrolysis led to dealloying, where In and Sn remained an alloy while Ga separated as GaOOH. This hydrolysis has implications for many devices based on gallium alloys and should be considered during the design phase of liquid metal-enabled products. Full article

Ferromanganese (Fe-Mn) polymetallic nodules are significant marine mineral resources containing various metal elements of substantial economic and scientific research value. Previous studies have primarily focused on the mineralogy and geochemistry of the nodules, while research on their nano-mineralogy is still lacking. In this study, we conducted scanning electron microscopy (SEM), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR), Brunauer–Emmett–Teller (BET) porous structure gas adsorption/desorption, and specific surface area analysis to examine the nano-mineralogy and mineralization of the polymetallic nodules from the interbasin of seamounts in the western Pacific Ocean (IBSWP). The results indicate that the growth profiles of the IBSWP polymetallic nodules exhibit microstructural features such as laminated, stromatolithic, columnar, and mottled structures. The mineral compositions are primarily composed of Fe-Mn minerals and detritus, including quartz; minerals from the feldspar group; and minerals from the clay group. The Fe-Mn phase minerals are relatively poorly crystallized. The Mn-phase minerals contain vernadite and small amounts of todorokite, buserite, and birnessite, while the Fe-phase minerals are mainly comprised of amorphous FeOOH. The main ore-forming minerals consist of nano-minerals, and the nanostructures of the polymetallic nodules endow them with unusually large specific surface areas and pore volumes, resulting in strong adsorption properties. The unique nano-properties and surface/interface adsorption effects of Fe-Mn minerals play a crucial role in controlling the enrichment of ore-forming elements. Full article

GaOOH, having a bandgap of 4.7–4.9 eV, can be regarded as one of several ultrawide-bandgap (UWBG) semiconductors, although it has so far mainly been used as a precursor material of Ga₂O₃. To examine the possibility of valence control and application in electronics, impurity levels in GaOOH are investigated using the first-principles density-functional theory calculation. The density values of the states of a supercell including an impurity atom are calculated. According to the results, among the group 14 elements, Si is expected to introduce a shallow donor level, i.e., a free electron is introduced. On the other hand, Ge and Sn introduce a localized state about 0.7 eV below the conduction band edge, and thus cannot act as an effective donor. While Mg and Ca can introduce a free hole and act as a shallow acceptor, Zn and Cd introduce acceptor levels away from the valence band. The transition metal elements (Fe, Co, Ni, Cu) are also considered, but none of them are expected to act as a shallow dopant. Thus, the results suggest that the carrier concentration can be controlled if Si is used for n-type doping, and Mg and Ca for p-type doping. Since GaOOH can be easily deposited using various chemical techniques at low temperatures, GaOOH will potentially be useful for transparent electronic devices. Full article

An effective strategy for achieving cost-effective and environmentally friendly desulfurization wastewater in coal-fired power plants involves the incorporation of desulfurization wastewater into the slag water system. The objective of this study was to analyze the corrosion behavior of Q235-A slag-picker shell material upon the introduction of FGD wastewater into the slag water system. The dynamic weight loss method, electrochemical testing method and microscopic phase characterization were employed to investigate the impact of varying chloride ion concentrations (ranging from 1000 mg/L to 30,000 mg/L) of flue gas desulfurization wastewater (FGD wastewater) on the corrosion of Q235-A slag-picker shell material. The test results indicate that as the concentration of chloride ions increases, the corrosion rate increases from 1.1487 mm/a to 1.5590 mm/a when the concentration is less than 10,000 mg/L. However, when the concentration exceeds 10,000 mg/L, the corrosion rate decreases from 1.559 mm/a to 1.0393 mm/a. The corrosion rate is above 1 mm/a at all concentrations. As the Cl⁻ concentration, the quality of the corrosion product film initially increases and then decreases. The primary components of the corrosion product are α- FeOOH, γ-FeOOH, β-FeOOH, Fe₃O₄ and γ-Fe₂O₃. Full article

The quantitative structure–electrochemistry relationship (QSER) method was applied to a series of transition-metal-coordinated porphyrins to relate their structural properties to their electrochemical CO₂ reduction activity. Since the reactions mainly occur within the core of the metalloporphyrin catalysts, the cluster model was used to calculate their structural and electronic properties using density functional theory with the M06L exchange–correlation functional. Three dependent variables were employed in this work: the Gibbs free energies of H*, C*OOH, and O*CHO. QSER, with the genetic algorithm combined with multiple linear regression (GA–MLR), was used to manipulate the mathematical models of all three Gibbs free energies. The obtained statistical values resulted in a good predictive ability (R² value) greater than 0.945. Based on our QSER models, both the electronic properties (charges of the metal and porphyrin) and the structural properties (bond lengths between the metal center and the nitrogen atoms of the porphyrin) play a significant role in the three Gibbs free energies. This finding was further applied to estimate the CO₂ reduction activities of the metal–monoamino–porphyrins, which will prove beneficial in further experimental developments. Full article

In this work, Ga₂O₃ nanorods were converted from GaOOH nanorods grown using the hydrothermal synthesis method as the sensing membranes of NO₂ gas sensors. Since a sensing membrane with a high surface-to-volume ratio is a very important issue for gas sensors, the thickness of the seed layer and the concentrations of the hydrothermal precursor gallium nitrate nonahydrate (Ga(NO₃)₃·9H₂O) and hexamethylenetetramine (HMT) were optimized to achieve a high surface-to-volume ratio in the GaOOH nanorods. The results showed that the largest surface-to-volume ratio of the GaOOH nanorods could be obtained using the 50-nm-thick SnO₂ seed layer and the Ga(NO₃)₃·9H₂O/HMT concentration of 12 mM/10 mM. In addition, the GaOOH nanorods were converted to Ga₂O₃ nanorods by thermal annealing in a pure N₂ ambient atmosphere for 2 h at various temperatures of 300 °C, 400 °C, and 500 °C, respectively. Compared with the Ga₂O₃ nanorod sensing membranes annealed at 300 °C and 500 °C, the NO₂ gas sensors using the 400 °C-annealed Ga₂O₃ nanorod sensing membrane exhibited optimal responsivity of 1184.6%, a response time of 63.6 s, and a recovery time of 135.7 s at a NO₂ concentration of 10 ppm. The low NO₂ concentration of 100 ppb could be detected by the Ga₂O₃ nanorod-structured NO₂ gas sensors and the achieved responsivity was 34.2%. Full article

Inter- and intra-molecular proton-transfers between functional groups in nucleobases play a principal role in their interactions (pairing) in nucleic acids. Although prototropic rearrangements (intramolecular proton-transfers) for neutral pyrimidine bases are well documented, they have not always been considered for their protonated and deprotonated forms. The complete isomeric mixtures in acid-base equilibria and in acidity–basicity parameters have not yet been examined. Taking into account the lack of literature and data, research into the question of prototropy for the ionic (protonated and deprotonated) forms has been undertaken in this work. For the purposes of this investigation, two isomeric pyrimidine bases (C—cytosine and iC—isocytosine) were chosen. They exhibit analogous (symmetrical) general acid-base equilibria (intermolecular proton-transfers). Being similar polyfunctional tautomeric systems, C and iC possess two labile protons and five conjugated tautomeric sites. However, positions of exo groups are different. Consequently, structural conversions such as prototropy, rotational, and geometrical isomerism of exo groups (=O/−OH and =NH/−NH₂) and their intramolecular interactions with endo groups (=N−/>NH) possible in neutral C and iC and in their ionic forms lead to some differences in compositions of isomeric mixtures. By application of quantum–chemical methods to the isolated (in vacuo) species, stability of all possible neutral and ionic isomers has been examined and the candidate isomers selected. The complete isomeric mixtures have been considered for the first time for di-deprotonated, mono-deprotonated, mono-protonated, and di-protonated forms. Protonation–deprotonation reactions have been analyzed in the gas phase that models non-polar environment. The gas-phase microscopic (kinetic) and macroscopic (thermodynamic) acidity–basicity parameters have been estimated for each step of acid-base equilibria. When proceeding from di-anion to di-cation in four steps of protonation–deprotonation reaction, the macroscopic proton affinities for C and iC differ by less than 10 kcal mol⁻¹. Their DFT-calculated values are as follows: 451 and 457, 340 and 339, 228 and 224, and 100 and 104 kcal mol⁻¹, respectively. Differences between the microscopic proton affinities for analogous isomers of C and iC seem to be larger for the exo than endo groups. Owing to variations of relative stabilities for neutral and ionic isomers, in some cases they are even larger than 10 kcal mol⁻¹. Full article

The initial corrosion behavior of 20# steel under the condition of gas–liquid (CO₂/aqueous solution) two-phase bubble flow was studied through weight loss, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results showed that the corrosion rate decreased rapidly when the corrosion time was less than 3 h, increased rapidly, even to 19.4% of the initial corrosion rate, when the corrosion time was from 3 h to 5 h, and then decreased slowly to about 63% of the initial corrosion rate after the corrosion time exceeded 5 h under different CO₂ pressure conditions. The corrosion happened first at the defects area with a high activity such as the cross points of scratches, gradually formed corrosion pits, and then extended around until the corrosion products covered the whole pipe wall surface. At the beginning stage of the corrosion process, the corrosion products were composed of acicular corrosion products and a small number of flocculent corrosion products and formed the corrosion product layer with micro-cracks. With the extension of the corrosion time, the spherical corrosion particles started to form on the initial corrosion product layer’s surface and gradually covered the initial corrosion product layer completely. The whole corrosion product layer with dual-structure characteristics formed. The inner corrosion product sub-layer was composed of initial corrosion products with columnar characteristics from the cross-section perspective, and the outer corrosion product sub-layer was composed of spherical corrosion products that were relatively dense. There was no obvious interface between the inner columnar sub-layer and the dense outer sub-layer. As time went on, the corrosion product particles with a broccoli shape characteristic formed on the dual-structure corrosion product layer’s surface and finally formed the outermost layer of the whole corrosion product layer. In the end, the whole corrosion product layer with three sub-layers formed, namely, the columnar bottom sub-layer, the relatively dense middle sub-layer, and the surface dense sub-layer composed of particles with a broccoli shape. The main components of the corrosion products were Fe, C, and O, and the main phases of the corrosion products were Fe₃C, FeCO₃, Fe₃O₄, Fe₂O₃, and FeOOH. Full article

The fabrication of earth-abundant electrocatalysts by green-chemistry approaches for electrochemical water splitting could diminish or alleviate the use or generation of hazardous substances, which could be highly desirable to achieve efficient, green alkaline water electrolysis for clean energy production (H₂). This review started by introducing the importance of the green-chemistry approaches. Later, this paper reviewed the fabrication of high-performance earth-abundant electrocatalysts using green-chemistry approaches for electrochemical water splitting (HER and OER). Moreover, this review discussed the green-chemistry approaches for the fabrication of earth-abundant electrocatalysts including phosphide/pyrophosphate-, carbon-, oxide-, OH/OOH/LDH-, alloy/B/nitride-, and sulfide/selenide (chalcogenide)-based earth-abundant electrocatalysts. Moreover, this review discussed various green-chemistry approaches, including those used to alleviate toxic PH₃ gas emission during the fabrication of transition-metal phosphide-based electrocatalysts, to design energy-efficient synthesis routes (especially room-temperature synthesis), to utilize cheap or biodegradable substrates, and to utilize biomass waste or biomass or biodegradable materials as carbon sources for the fabrication of earth-abundant electrocatalysts. Thus, the construction of earth-abundant electrocatalysts by green-chemistry approaches for electrochemical water splitting could pave an efficient, green way for H₂ production. Full article

Rational design and constructing earth-abundant electrocatalysts for efficient electrocatalytic water splitting is a crucial challenge. Herein, we report a simple and efficient one-step electrochemical synthetic route of the NiFe₂O₄@FeOOH composite electrocatalyst for the oxygen evolution reaction. The unique morphology of the NiFe₂O₄ nanoflowers loaded on FeOOH nanosheets allows more active sites to be exposed and promote charge transfer as well as gas release, and the resulting electrode enables a current density of 10 mA cm⁻² at a low overpotential of 255 mV with outstanding stability at a current density of 100 mA cm⁻² for 300 h. Full article