Reaction Of Precursor Research Articles

Study of the Properties of YBCO Superconductor Compound in Various Preparation Methods: A Short Review

Superconductors have entered into many applications and advanced technological fields, due to their excellent properties identified by zero resistance and expelling the magnetic field applied to them. Superconductivity is a viable technology to prevent energy losses contributed by electrical resistivity. Also, the magnetic flux is repelled entirely out of the body of superconducting material which makes the Meissner Effect. High-Temperature Superconductors (HTS) have become the focus of researchers and scientists. This is because it uses liquid nitrogen "LN" in cooling, which gives it significant critical temperatures compared to traditional materials based on liquid helium "LHe" in cooling. From this point of view, began to employ these materials in most disciplines and modern technologies. In this article, the phenomenon of Superconductivity will define with explain its most prominent characteristics and focus on the preparation of the HTS (Yttrium-Barium-Copper-Oxide) compound (Abbreviated as YBCO) in different methods "The Sol-Gel and Citrate Pyrolysis Methods", to creating ultrafine superconducting (Y-123) powders. Generally known that by adopting any preparation technique, the superconducting transition temperature (Tc) value of ≈ 92 K could be achieved in the bulk samples. The Citrate Pyrolysis method is a unique route to prepare reactive precursor mixtures through an ignition process of a concentrated aqueous solution including metallic ions of stoichiometric composition. This procedure enables to synthesize of highly homogeneous and fine powders for functional materials, in comparison to the Sol-gel technique.

Morphological effect of one-dimensional ZnO nanostructures on the photocatalytic activity

The chemical and physical properties, including photocatalytic activity, can be tuned by altering the morphology of the ZnO nanostructures. Herein, the correlation between the physical properties (optical and shape) of various one-dimensional (1-D) ZnO and their photocatalytic performance was evaluated. The 1-D ZnO nanostructure (nanorods (NRs), nanowires (NWs), and nanotubes (NTs)) on a glass substrate were successfully synthesized using a hydrothermal method with varying precursor concentrations and reaction temperatures. By reducing the seeding precursor concentration, the morphology of ZnO changed from NRs to NWs, whereas the NRs were transformed into NTs when the incubation time was prolonged. XRD and SEM analysis confirmed the formation of hexagonal wurtzite ZnO NRs, NWs, and NTs with trunk diameters of 151 nm, 60 nm, and 157 nm, respectively. Furthermore, the UV-light photocatalytic efficiency test using methylene blue exhibited that the one with the highest degradation efficiency was ZnO NTs (67.43%), followed by ZnO NWs (53.76%) and ZnO NRs (46.10%). The morphology and physicochemical properties study revealed that the large polar face owned by ZnO NT, which is augmented by the high UV absorption and large photocurrent density, enhanced their photocatalytic efficiency.

Interpretable Machine Learning Enabled Inorganic Reaction Classification and Synthesis Condition Prediction

Data-driven synthesis planning with machine learning is a key step in the design and discovery of novel inorganic compounds with desirable properties. Inorganic materials synthesis is often guided by heuristics and chemists’ prior knowledge and experience, built upon experimental trial-and-error that can be both time and resource consuming. Recent developments in natural language processing have enabled large-scale text mining of scientific literature, providing open-source databases of synthesis information on realized compounds, material precursors, and reaction conditions (temperatures, times). We employ supervised classification machine learning (ML) models to distinguish between solid-state, sol–gel, and solution (hydrothermal, precipitation) synthesis routes based on specified reaction target material and/or precursor materials. We demonstrate regression ML models that are able to predict suitable temperatures and times for the crucial inorganic synthesis steps of calcination and sintering given the reaction target and precursor materials. We contrast this regression-based condition modeling with a conditional variational autoencoder neural network that can generate appropriate distributions for the synthesis conditions of interest. We evaluate model interpretability using the Shapley additive explanations approach to gain insight into factors influencing suitability of synthesis route and reaction conditions. We find that the aforementioned models are capable of learning subtle differences in target material composition, precursor compound identities, and choice of synthesis route that are present in the inorganic synthesis space. Moreover, they generalize well to unseen chemical entities, outperform common heuristics in the field, and show promise for predicting appropriate reaction routes and conditions for previously unsynthesized compounds of interest.

On-Surface Synthesis of Self-Assembled Covalently Linked Wavy Chains with Site-Selective Conformational Switching.

Conformational arrangements in polymers on surfaces determine the overall shape as well as the potential properties. It is generally believed that conformational diversity leads to uncontrollable or disordered structures in on-surface synthesis. However, in this study, we obtain two well-ordered self-assembled covalently linked wavy chains with site-selective conformational switching via the Ullmann reaction of 1,2-bis(3-bromophenyl)ethane with multiple conformations on Ag(111). Two kinds of wavy chains exhibit distinct conformational arrangements, where chain I contains one repeating unit conformation of -cis-trans1-cis-trans1-cis-cis-trans1-, while the adjacent parallel parts in wavy chain II have two different conformational arrangements of -cis-cis-trans1- and -cis-cis-trans2-. Wavy chains coassemble with dissociated bromine atoms, suggesting that the Br···H-C interactions between Br atoms and molecular chains are crucial for the construction of ordered wavy chains. High-resolution scanning tunneling microscopy is employed to reveal the surface reaction process at the molecular scale. In depth growth mechanism analysis combined with density functional theory calculations unveils that the substrate also plays an important role in the fabrication of well-ordered wavy chains. The present work extends the surface reaction of conformational flexible precursors.

Priming Effects of Maillard Reaction Precursors on Rice Straw Decomposition at Different Incubation Temperatures

To verify the priming effects of Maillard reaction precursors on the microbial decomposition of rice straw at different incubation temperatures, the method of indoor incubation at a constant temperature was adopted. In the process, the addition of glucose, catechol or glycine solution alone or in mixed solution was conducted at incubation temperatures of 10 °C, 15 °C and 28 °C, respectively. The C content of humic-extracted acid (CHLE), humification index (the ratio of C content of humic-like acid to fulvic-like acid, CHLA/CFLA), ∆logK value of humic-like acid (HLA), and C content of humin-like acid (CHLu) were dynamically analyzed at 0, 30, 60, and 90 d, respectively. At the same time, the differences in the atomic ratio and FTIR spectra before and after incubation were systematically analyzed. The results showed that (1) the additions of glucose alone and mixed precursors were both beneficial to increasing the CHLE content at three tested temperatures, especially at two low temperatures (10 °C and 15 °C), and glucose alone manifested the most significant improvement in CHLE. In contrast, following the addition of glycine alone, the CHLE content decreased by 2.4% at 15 °C and 4.6% at 28 °C after incubation. (2) Glucose as the sole precursor was more beneficial to improving the quality of the humic substance (HS) at 28 °C, but only enhanced the condensation degree of HLA molecules at 15 °C. Compared with the results at 15 °C and 28 °C, the HLA molecules had the lowest condensation degree at 10 °C, regardless of whether a single precursor or mixed Maillard precursors were used. (3) After incubation, the amounts of N compounds in the HLA molecules decreased to varying degrees, especially at 28 °C. The O-containing functional groups, such as carboxyl groups, from HLA molecules decreased following the addition of a single precursor, while the mixed precursors resulted in an increase in O-containing functional groups. Increasing the catechol content directly enriched the unsaturated bonds of HLA. With the decomposition of rice straw, regardless of how the precursors were added, the polysaccharide content decreased to different degrees. The decomposition of polysaccharides in HLA was more temperature-sensitive, and an increase in temperature might encourage more polysaccharide consumption. Under each temperature, the molecular structure of HLA was simplified initially and then gradually became complex. Finally, the addition of glucose alone at 15 °C was more favorable for the complexity of HLA molecules, while at 28 °C, it could only alleviate the degree of simplification of the HLA molecular structure to a certain extent. (4) At the three tested temperatures, compared with the CK control, either one precursor or a mixture of three precursors could more effectively promote the decomposition of CHLu. Under the conditions of 10 °C and 15 °C, the addition of mixed precursors was more beneficial to the decomposition of CHLu, causing the CHLu content to decrease by 37.9% and 44.7%, respectively, followed by the addition of glucose alone.

Hydrolysis of Poly(fluoroacrylate) Thin Films Synthesized from the Vapor Phase.

The post-synthesis surface reaction of vapor-deposited polymer thin films is a promising technique in engineering heterogeneous surface chemistry. Because the existing research has neglected marginally reactive precursor films in preference of their highly reactive counterparts, our knowledge of kinetics and loss of film integrity during the reaction are limited. To address these limitations, we characterize hydrolysis of two fluoroacrylates, poly(1H,1H,2H,2H-perfluorooctyl acrylate) (pPFOA) and poly(2,2,3,4,4,4-hexafluorobutyl acrylate) (pHFBA), with sodium hydroxide using X-ray photoelectron spectroscopy. Without crosslinking with di(ethylene glycol)divinyl ether (DEGDVE) and grafting with trichlorovinyl silane, the films degrade rapidly during hydrolysis. An SN2 mechanism describes hydrolysis well, with rate constants of 0.0029 ± 0.0004 and 0.011 ± 0.001 L mol-1s-1 at 30 °C for p(PFOA-co-DEGDVE) and p(HFBA-co-DEGDVE), respectively. Our detailed study of hydrolysis kinetics of marginally reactive fluoroacrylates demonstrates the full capability and limitations of the post-synthesis reaction. Importantly, copolymers are characterized using a density correction new to polymer chemical vapor deposition.

Protection against Chemical Warfare Agents and Biological Threats Using Metal–Organic Frameworks as Active Layers

The SARS-CoV-2 pandemic outbreak and the unfortunate misuse of toxic chemical warfare agents (CWAs) highlight the importance of developing functional materials to protect against these chemical and pathogen threats. Metal–organic frameworks (MOFs), which comprise a tunable class of crystalline porous materials built from inorganic nodes and organic linkers, have emerged as a class of heterogeneous catalysts capable of rapid detoxification of multiple classes of these harmful chemical or biological hazards. In particular, zirconium-based MOFs (Zr-MOFs) feature Lewis acidic nodes that serve as active sites for a wide range of catalytic reactions, including the hydrolysis of organophosphorus nerve agents within seconds in basic aqueous solutions. In addition, postsynthetic modification of Zr-MOFs enables the release of active species capable of reacting with and deactivating harmful pathogens. Despite this impressive performance, utilizing Zr-MOFs in powder form is not practical for application in masks or protective uniforms.To address this challenge, our team sought to develop MOF/fiber composite systems that could be adapted for use under realistic operating conditions to protect civilians, military personnel, and first responders from harmful pathogens and chemical warfare agents. Over the last several years, our group has designed and fabricated reactive and biocidal MOF/fiber composites that effectively capture and deactivate these toxic species. In this Account, we describe the evolution of these porous and reactive MOF/fiber composites and focus on key design challenges and considerations.First, we devised a scalable method for the integration of Zr-MOFs onto textile substrates using aqueous precursor solutions and without using pretreated textiles, highlighting the potential scalability of this method. Moving beyond standard textiles, we also developed a microbial synthesis strategy to prepare hierarchically porous MOF/bacterial cellulose nanofiber composite sponges that can both capture and detoxify nerve agents when exposed to contaminated gas flows. The mass loading of the MOF in the nanofibrous composite sponge is up to 90%, affording higher work capacities compared to those of textile-fiber-based composites with relatively lower MOF loadings. Next, we demonstrated that heterogeneous polymeric bases are suitable replacements for volatile liquid bases typically used in solution-phase reactions, and we showed that these composite systems are capable of effectively hydrolyzing nerve agents in the solid state by using only water that is present as humidity. Moreover, incorporating a reactive dye precursor into the composite affords a dual function sensing and detoxifying material that changes color from white to orange upon reaction with the byproduct following nerve agent hydrolysis, demonstrating the versatility of this platform for use in decontamination applications. We then created chlorine-loaded MOF/fiber composites that act as biocidal and reactive textiles that are capable of not only detoxifying sulfur-mustard-based chemical warfare agents and simulants but also deactivating both bacteria and the SARS-CoV-2 virus within minutes of exposure. Finally, we synthesized a mixed-metal Ti/Zr-MOF coating on cotton fibers to afford a photoactive biocidal cloth that shows fast and broad-spectrum biocidal performance against viruses and Gram-positive and Gram-negative bacteria under visible light irradiation.Given the tunable, multifunctional nature of these MOF/fiber composites, we believe that this Account will offer new insights for the rational design and preparation of functional MOF/fiber composites and pave the way toward the development of next-generation reactive and protective textiles.

On the Sustainable Utilization of Geopolymers for Safe Management of Radioactive Waste: A Review

The application of geopolymers for the safe management of radioactive waste has not been implemented on a large scale, where they are tirelessly examined with the purpose of facilitating the practicality and feasibility of the actual application towards the sustainable performance of these materials. This review therefore compiles the findings of the utilization of geopolymers as sorbents for removal of radio-contaminants from aqueous waste streams and as immobilization matrices for the containment of different radioactive wastes. The investigated geopolymer base materials encompass a wide range of reactive aluminosilicate precursor sources that include natural materials, industrial wastes, and chemicals. This work introduces to the reader the scientific interest in the field of geopolymer studies, their sustainability analysis, and their application in the nuclear industry, in particular in radioactive waste treatment and immobilization. The geopolymer classification, radiation stability, and structural characterizations were summarized with special reference to the characterization of the structure alteration due to the inclusion of functional materials or radioactive wastes. The effect of the application of metakaolin-based materials, fly ash-based materials and other base materials, and their blend on radio-contaminant removal from aqueous solutions and the immobilization of different problematic radioactive waste streams were reviewed and analyzed to identify the gaps in the sustainable performance of these materials. Finally, perspectives on geopolymer sustainability are presented, and the identified gaps in sustainable application included the need to investigate new areas of application, e.g., in pretreatment and membrane separation. The reusability and the regeneration of the geopolymer sorbents/exchangers need to be addressed to reduce the material footprints of this application. Moreover, there is a need to develop durability tests and standards based on the record of the application of the geopolymers.

Continuous Flow Synthesis of N-Sulfonyl-1,2,3-triazoles for Tandem Relay Cu/Rh Dual Catalysis.

The continuous flow synthesis of N-sulfonyl-1,2,3-triazoles, which are convenient reactive azavinyl carbene precursors, for tandem relay Cu/Rh dual catalysis has been developed. Most reactions readily proceeded at 75 °C in a short residence time of 13.09 min in the presence of 2.5 mol % of CuTC. The scope of the reactions was explored by synthesizing diversely functionalized N-sulfonyl and sulfamoyl triazoles in yields ranging from 92 to 98%. To demonstrate the scalability of the process, the reaction was conducted on a 5.4 mmol scale with residence and collection times of 13.09 and 60 min, respectively. Furthermore, a series of controlled experiments were performed to investigate the compatibility of Cu and Rh in a batch or a continuous flow system. Finally, the first integrated flow system using the azavinyl carbene intermediate under the tandem relay Cu/Rh dual catalysis was developed for the synthesis of various cis-diamino enones from alkynes and sulfonyl azides.

Theoretical understanding of stability of mechanically interlocked carbon nanotubes and their precursors.

Dispersion-corrected DFT calculations were performed on (a,a) nanotubes (a = 5-10) attached by a U-shaped functional group consisting of p-xylene-linked double 9,10-di(1,3-dithiol-2-ylidene)-9,10-dihydro anthracene terminated by CnH2n chains (n = 6, 8, and 9), and their ring-closing macrocycles containing tubes. The reactant precursors and macrocycles are denoted by UP-n-(a,a) and (a,a)@Cycle-n, respectively. We found that UP-n-(a,a) are energetically preferable relative to the dissociation limit toward a U-shaped functional group (UP-n) and a tube (initial state) due to the attractive CH-π and π-π interactions. The attractive interactions are enhanced by increasing the tube diameters and CnH2n chain lengths because UP-n structures can be easily adjusted to interact with the tubes. The stability of (a,a)@Cycle-n and related (a,b)@Cycle-n is sensitive to tube diameters due to the restriction of ring structures. When diameter differences between a Cycle-n and a tube (D-d) are larger than 5 Å, (a,a)@Cycle-n plus C2H4 are energetically preferable relative to the initial state. However, the (a,a)@Cycle-n plus C2H4 byproduct is always energetically unstable relative to UP-n-(a,a). The DFT calculations found that the energy differences were low at D-d values ranging from 7 to 8 Å, explaining the tube-diameter-selective formation of the mechanically-interlocked tubes, observed experimentally.

The protometabolic nature of prebiotic chemistry.

The field of prebiotic chemistry has been dedicated over decades to finding abiotic routes towards the molecular components of life. There is nowadays a handful of prebiotically plausible scenarios that enable the laboratory synthesis of most amino acids, fatty acids, simple sugars, nucleotides and core metabolites of extant living organisms. The major bottleneck then seems to be the self-organization of those building blocks into systems that can self-sustain. The purpose of this tutorial review is having a close look, guided by experimental research, into the main synthetic pathways of prebiotic chemistry, suggesting how they could be wired through common intermediates and catalytic cycles, as well as how recursively changing conditions could help them engage in self-organized and dissipative networks/assemblies (i.e., systems that consume chemical or physical energy from their environment to maintain their internal organization in a dynamic steady state out of equilibrium). In the article we also pay attention to the implications of this view for the emergence of homochirality. The revealed connectivity between those prebiotic routes should constitute the basis for a robust research program towards the bottom-up implementation of protometabolic systems, taken as a central part of the origins-of-life problem. In addition, this approach should foster further exploration of control mechanisms to tame the combinatorial explosion that typically occurs in mixtures of various reactive precursors, thus regulating the functional integration of their respective chemistries into self-sustaining protocellular assemblies.

The one/two atom size-reduction of [Au23SCy16]- induced by the [Au6(dppp)4]2+ cluster.

The recent progress in atomically precise metal (Au, Ag etc.) nanoclusters has greatly enriched the molecular-level mechanistic understanding of metal nanomaterials. Herein, using two meta-stable (easy formation, easy transformation) clusters, i.e. [Au23SCy16]- and [Au6(dppp)4]2+ (HSCy and dppp denote cyclohexanethiol and 1,3-bis(diphenylphosphino)propane), as the reaction precursors, the etching of Au23 occurs smoothly, giving the one/two-atom size-reduced [Au21SCy12(dppp)2]+ and [Au22SCy14(dppp)]2+ as the major products. Structural analysis and DFT calculations indicate that the active reaction site of Au23 lies in the core-shell interference of the bi-capped icosahedral Au15 core and the AuS2 motifs. The fluorescence, band gap, and thermostability of the Au21 cluster products are improved compared to that of the Au23 precursors.

Synthesis and structural properties of high-entropy nanoalloys made by physical and chemical routes.

The development of synthesis methods with enhanced control over the composition, size and atomic structure of High Entropy Nano-Alloys (HENA) could give rise to a new repertoire of nanomaterials with unprecedented functionalities, notably for mechanical, catalytic or hydrogen storage applications. Here, we have developed two original synthesis methods, one by a chemical route and the other by a physical one, to fabricate HENA with a size between 3 and 10 nm and a face centered cubic structure containing three (CoNiPt), four (CoNiPtCu and CoNiPtAu) or five (CoNiPtAuCu) metals close to the equiatomic composition. The key point in the proposed chemical synthesis method is to compensate the difference in reactivity of the different metal precursors by increasing the synthesis temperature using high boiling solvents. Physical syntheses were performed by pulsed laser ablation using a precise alternating deposition of the individual metals on a heated amorphous carbon substrate. Finally, we have exploited aberration-corrected transmission electron microscopy to explore the nanophase diagram of these nanostructures and reveal intrinsic thermodynamic properties of those complex nanosystems. In particular, we have shown (i) that the complete mixing of all elements can only occur close to the equiatomic composition and (ii) how the Ostwald ripening during HENA synthesis can induce size-dependent deviations from the equiatomic composition leading to the formation of large core-shell nanoparticles.

Engineering polymorphs in colloidal metal dichalcogenides: precursor-mediated phase control, molecular insights into crystallisation kinetics and promising electrochemical activity

We present a solution-based crystal phase engineering approach for layered transition metal disulphide nanosheets by modulating the reactivity of the molecular precursors.

Aerobic epoxidation of β-ionone in water under mild conditions using aldehydes as catalyst precursors

Aldehydes were employed as catalyst precursors for the epoxidation reaction of β-ionone to produce 5,6-epoxy-β-ionone in as high as 83% yield. Notably, the reaction occurred in water and O2 was employed as the mild, cheap and safe oxidant.

Substitution pattern in ruthenium octa-n-butoxyphthalocyanine complexes influence their reactivity in N-H carbene insertions.

Ruthenium phthalocyanine complexes bearing n-OBu substituents in the peripheral or non-peripheral positions are efficient catalysts for the selective double or single carbene insertion to the amine N-H bonds. This complementary reactivity of two Ru complexes can be used for the synthesis of asymmetric tertiary amines and diamines bearing different substituents and has been demonstrated by two examples of readily available primary amines using different carbene precursors in successive reactions.

Unravelling the synthetic and therapeutic aspects of five, six and fused heterocycles using Vilsmeier-Haack reagent.

The aim of this review is to encapsulate the synthetic protocols and medicinal aspects of a wide range of heterocyclic compounds using the Vilsmeier-Haack (V. H.) reagent. These derivatives act as excellent precursors having different aryl ring functionalities and could be used for the synthesis of a variety of heterocyclic scaffolds. The V. H. reagent, a versatile reagent in organic chemistry, is used to formylate various heterocyclic compounds of medicinal interest. Due to the different chemical interactions, efficacy, and potency of V. H. reagents, plenty of heterocyclic compounds can be synthesized which serve as a constituent in various novel medications and acts as a bridge between biology and chemistry. These carboxylate moieties can effectively cooperate as precursors for several multi-component reactions (MCR) including Strecker synthesis, Bucherer-Berg reaction and post-MCR cyclization, modified variants with various pharmaceutical applications such as anti-tumor, anti-convulsant, anti-chitosomal and so on.

Heterometallic Ru–Ir carbonyl clusters as catalyst precursors for hydrogenation and hydrogen transfer reactions

Heterometallic Ru–Ir hydride carbonyl clusters were synthesized and tested as catalyst precursors for hydrogenation of 4-fluoroacetophenone and trans-cinnamaldehyde.

An overlooked oxidation mechanism of toluene: computational predictions and experimental validations.

Secondary organic aerosols (SOAs) influence the Earth's climate and threaten human health. Aromatic hydrocarbons (AHs) are major precursors for SOA formation in the urban atmosphere. However, the revealed oxidation mechanism dramatically underestimates the contribution of AHs to SOA formation, strongly suggesting the importance of seeking additional oxidation pathways for SOA formation. Using toluene, the most abundant AHs, as a model system and the combination of quantum chemical method and field observations based on advanced mass spectrometry, we herein demonstrate that the second-generation oxidation of AHs can form novel epoxides (TEPOX) with high yield. Such TEPOX can further react with H2SO4 or HNO3 in the aerosol phase to form less-volatile compounds including novel non-aromatic and ring-retaining organosulfates or organonitrates through reactive uptakes, providing new candidates of AH-derived organosulfates or organonitrates for future ambient observation. With the newly revealed mechanism, the chemistry-aerosol box modeling revealed that the SOA yield of toluene oxidation can reach up to 0.35, much higher than 0.088 based on the original mechanism under the conditions of pH = 2 and 0.1 ppbv NO. This study opens a route for the formation of reactive uptake SOA precursors from AHs and significantly fills the current knowledge gap for SOA formation in the urban atmosphere.

Evaluation of the biological responses of silver nanoparticles synthesized using Pelargonium x hortorum extract.

Silver nanoparticles (AgNPs) are one of the widely studied nanomaterials for diverse biomedical applications, in particular, as antimicrobial agents to kill bacteria, fungi, and viruses. In this report, AgNPs were synthesized using a geranium (Pelargonium x hortorum) leaves extract and tested for their antimicrobial and cytotoxic activity and reactive oxygen species (ROS) production. Using green biosynthesis, the leaves extract was employed as a reducing and stabilizing agent. Synthesis parameters like reaction time and precursor (silver nitrate AgNO3) volume final were modified, and the products were tested against Streptococcus mutans. For the first time, the metabolomic analysis of extract, we have identified more than 50 metabolites. The UV-Vis analysis showed a peak ranging from 410-430 nm, and TEM confirmed their nearly spherical morphology for all NPs. The antimicrobial activity of the NPs revealed a minimum inhibitory concentration (MIC) of 10 μg mL-1. Concerning cytotoxicity, a dose-time-dependent effect was observed with a 50% cellular cytotoxicity concentration (CC50) of 4.51 μg mL-1 at 24 h. Interestingly, the cell nuclei were visualized using fluorescence microscopy, and no significant changes were observed. These results suggest that synthesized spherical AgNPs are promising potential candidates for medical applications.