Synthetic Reagents Research Articles

Processing of low-grade Indian coking coal using air fluidized dense medium bed separator and flotation technique

ABSTRACT A dry coal beneficiation process was developed on a batch scale using a gas-solid fluidized bed separator to upgrade the low-grade coking coal from the Jharia Coalfield. Coal collected from Ena open cast mines of Kusunda area, Dhanbad was crushed to 50 mm and 25 mm sizes for dry processing using the dense medium fluidized bed separator followed by froth flotation for particles below 500 microns. Coal with a + 6 mm size fraction was processed via the dry route, while coal with a −6 mm size fraction and pre-concentrate from the dry route was further crushed to 0.5 mm for the froth flotation process using various reagents. The effect of various process parameters of the dry separator such as bed height, dense medium size, air flow rate were studied using CFD software in a simple 2D plane. The study revealed that the dry process for the −50 + 6 mm fraction achieves higher organic efficiency (90%) compared to −25 + 6 mm (81%) due to better washing characteristics. Dry deshaling of high-ash coking coal (−50 + 6 mm) can reduce the ash content from 35.3% to 29.6% with a yield of 75.4%. The flotation process using NALCO synthetic reagents is highly effective, reducing the feed ash content from 27.3% to 17.5% with a notable yield of 85.0%.

Synthesis, characterization and photo catalytic activity of silver nano particle derived from Arachis hypogaea L. seed peel extracts

Abstract The study focuses on the green synthesis of silver nanoparticles (AgNPs) using Arachis hypogaea L. seed peel extract (AHSPE) and evaluates their photocatalytic activity against Rhodamine B and Congo Red dyes. The synthesis involved reducing aqueous silver metal ions with AHSPE, characterized by various techniques including UV–visible spectroscopy, X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), and FT-Raman spectroscopy. UV–visible spectroscopy indicated characteristic absorption peaks at 428 and 439 nm, confirming the formation of AgNPs. XRD analysis revealed an average particle size of 4.77–5.6 nm. FT-IR spectra identified biomolecules such as amines, peptides, amides, lactones, and polyphenols in the extract, acting as reducing and capping agents, thereby stabilizing the AgNPs. SEM analysis showed pristine silver nanoparticles with diameters ranging from 1 to 10 µm. The biosynthesized AgNPs demonstrated strong photocatalytic activity in degrading Rhodamine B and Congo Red dyes. This method did not use any synthetic reagents, making it an environmentally safe and cost-effective alternative for synthesizing silver nanoparticles. The process aligns with green chemistry principles, offering potential applications in photocatalysis and environmental cleanup. The study underscores the importance of biosynthesized nanoparticles due to their unique biological properties and the role of plant secondary metabolites in facilitating green synthesis.

Characterization of Biocompatible Gellan Gum Fractions for Prolonged Retention in Ocular Drug Delivery Systems

ABSTRACTGellan gum (GG) emerges as a promising candidate for developing polymeric carriers with extended retention on the ocular surface, aiming to enhance the efficacy of topical ocular drug delivery systems. This study undertakes the purification of commercial GG through fractional dissolution and ultrasonic treatment, producing fractions characterized by 1H, 13C NMR, FTIR spectroscopy and thermogravimetric analysis. The intrinsic viscosity of GG samples was measured in a 0.025 M tetramethylammonium chloride solution and their molecular weights were calculated via the Mark‐Kuhn‐Houwink equation. Methodological choices regarding synthetic procedures, solvents and reagents were guided by considerations of biocompatibility, aligning with the end goal of drug delivery applications. The study further explores the mucoadhesive potential of GG fractions with varying molecular weights for ocular drug delivery, utilizing an in vitro flow‐through technique with fluorescent detection on freshly excised bovine corneal mucosa surfaces. The findings under‐score the viability of GG formulations in enhancing ocular drug retention and pave the way for future applications in topical ocular therapeutics.

Advances and Prospects on Flotation Enhancement of Difficult-to-Float Coal by Emulsion: A Review

Coal is expected to continue dominating the global energy landscape for a considerable period in the future. However, the depletion of high-quality coal resources and the increasing proportion of difficult-to-float coals are exacerbating environmental issues and leading to significant waste of carbon resources, making the clean and efficient utilization of such coals imperative. Enhancing the quality of coal through flotation is a prerequisite for the resource utilization of coal. Difficult-to-float coal, characterized by high hydrophilicity, complex pore structures, and fine particle size, poses challenges for efficient flotation using conventional collectors. Emulsions, owing to their exceptional surface and interfacial regulation capabilities and environmental adaptability, have been employed as flotation collectors for various minerals and have garnered significant attention in recent years for their application in the flotation of difficult-to-float coals. In the pursuit of green and cost-effective flotation technologies for such coals, this paper systematically reviews the causes of poor floatability in difficult-to-float coals and their latest research progress by emulsion flotation. It summarizes the impact of emulsion types and preparation methods on their properties and application areas, with a particular focus on the key mechanisms by which emulsion collectors enhance the flotation of difficult-to-float coals, including surface charge regulation, surface hydrophobicity modification, and interfacial tension control. Finally, this paper outlines future research directions on emulsion flotation, which will likely focus on the precise control of emulsion structure and size, the targeted separation of organic components by emulsion collectors under complex conditions, the development of low-cost and highly biocompatible synthetic reagents, and the development of efficient emulsion storage and transportation equipment.

Reactivities of N-Nitrosamines against Common Reagents and Reaction Conditions.

The knowledge of the reactivity of N-nitrosamines (NSAs) with common organic reagents in synthesis is essential in determining their presence in pharmaceutical products, if formed and retained during synthesis. In this study, we carried out a comprehensive survey of the Reaxys database for all reactions in which the NSA functional group is consumed. Very different reactivities for different classes of NSAs, e.g., N,N-dialkylnitrosamines and N,N-diphenylnitrosamine, were identified, suggesting substrates which should be included in any future reactivity screening. A classification of NSAs based on their reactivities, and corresponding reagents and transformations, was drawn up based on the data. Furthermore, the survey identified missing areas in the reported reactivities of NSAs with different reagents. This led to an experimental reactivity screening of 8 commercial NSAs with common synthetic reagents in the Mirabilis tool for purge assessment. The results showed Na2S2O4 in 1 M aqueous NaOH at 50 °C to be highly effective at destroying NSAs without damaging other organic compounds.

N-Heteroocyclic Carbenes and N-Heterocycles as Synthetic Reagents and Building Blocks.

N-Heterocyclic carbenes (NHCs) have become important tools in modern synthetic chemistry due to their versatility as organocatalysts and ligands in organometallic complexes. Since their first isolation and characterization, NHCs have demonstrated significant utility in various catalytic processes, offering advantages such as strong σ-electron donation and the ability to stabilize reactive intermediates. However, beyond their well-documented roles in catalysis, the potential of NHCs as stoichiometric reagents and synthetic building blocks remains an underexplored yet promising area. This Mini-review aims to shed light on these lesser-known applications of NHCs and their N-heterocyclic precursors or derivatives in organic synthesis. Furthermore, we discuss how the unique electronic and steric properties of NHCs can be harnessed to develop new synthetic methodologies or construct interesting organic frameworks. By highlighting these emerging uses, we hope to encourage further research into the non-catalytic applications of NHCs, broadening their scope and impact in synthetic chemistry.

Efficacy of radical reactions of isocyanides with heteroatom radicals in organic synthesis.

Isocyanide is a promising synthetic reagent not only as a one-carbon homologation reagent but also as a nitrogen source for nitrogen-containing molecules. Because of their isoelectronic structure with carbon monoxide, isocyanides also react with nucleophiles, electrophiles, carbon radicals, and transition metal reagents, and are widely used in organic synthesis. On the other hand, the use of isocyanides in reactions with heteroatom radicals is limited. However, the reaction of isocyanides with heteroatom radicals is a promising synthetic tool for the construction of nitrogen-containing organic molecules modified with a variety of heteroatoms. In this Perspective, we review the addition and cyclization reactions of heteroatom radicals with isocyanides and discuss the synthetic prospects of the reaction of isocyanides with heteroatom radicals.

Design of Cr-Based Molecular Electrocatalyst Systems for the CO2 Reduction Reaction.

ConspectusHuman influence on the climate system was recently summarized by the sixth Intergovernmental Panel on Climate Change (IPCC) Assessment Report, which noted that global surface temperatures have increased more rapidly in the last 50 years than in any other 50-year period in the last 2000 years. Elevated global surface temperatures have had detrimental impacts, including more frequent and intense extreme weather patterns like flooding, wildfires, and droughts. In order to limit greenhouse gas emissions, various climate change policies, like emissions trading schemes and carbon taxes, have been implemented in many countries. The most prevalent anthropogenic greenhouse gas emitted is carbon dioxide (CO2), which accounted for 80% of all U.S. greenhouse gas emissions in 2022. The reduction of CO2 through the use of homogeneous electrocatalysts generally follows a two-electron/two-proton pathway to produce either carbon monoxide (CO) with water (H2O) as a coproduct or formic acid (HCOOH). These reduced carbon species are relevant to industrial applications: the Fischer-Tropsch process uses CO and H2 to produce fuels and commodity chemicals, while HCOOH is an energy dense carrier for fuel cells and useful synthetic reagent. Electrochemically reducing CO2 to value-added products is a potential way to address its steadily increasing atmospheric concentrations while supplanting the use of nonrenewable petrochemical reserves through the generation of new carbon-based resources. The selective electrochemical reduction of CO2 (CO2RR) by homogeneous catalyst systems was initially achieved with late (and sometimes costly) transition metal active sites, leading the field to conclude that transition metal complexes based on metals earlier in the periodic table, like chromium (Cr), were nonprivileged for the CO2RR. However, metals early in the table have sufficient reducing power to mediate the CO2RR and therefore could be selective in the correct coordination environment. This Account describes our efforts to develop and optimize novel Cr-based CO2RR catalyst systems through redox-active ligand modification strategies and the use of redox mediators (RMs). RMs are redox-active molecules which can participate cocatalytically during an electrochemical reaction, transferring electrons─often accompanied by protons─to a catalytic active site. Through mechanistic and computational work, we have found that ligand-based redox activity is key to controlling the intrinsic selectivity of these Cr compounds for CO2 activation. Ligand-based redox activity is also essential for developing cocatalytic systems, since it enables through-space interactions with reduced RMs containing redox-active planar aromatic groups, allowing charge transfer to occur within the catalyst assembly. Following a summary of our work, we offer a perspective on the possibilities for future development of catalytic and cocatalytic systems with early transition metals for small molecule activation.

Hypervalent Iodine (III)-Based Complexation for Chiroptical Supramolecular Glass, Deep Eutectic Solvent and Luminescent Switch.

Hypervalent iodine(III) have widely been utilized for organic synthetic reagents. They are also recognized as positive charge-assisted, exceptionally robust biaxial halogen bond donors, while their potential in supramolecular materials is barely explored. This work reports a cyclic diaryliodonium ion as biaxial halogen bonding donor that displays remarkable binding affinity toward phenanthroline or acridine acceptors with chiral pendants. Biaxial halogen bonding enables chiroptical evolution in solution, allowing for rational control over supramolecular chirality. Leveraging their strong binding affinity, the halogen bonding complexes manifested amorphous properties and deep eutectic behavior in the solid state. Capitalizing on these attributes, this work achieves the successful preparation of supramolecular glasses and deep eutectic solvents. Additionally, halogen bonding appended light irradiation-triggered luminescence through a hydrogen atom transfer process, showing applications in anti-counterfeit and display.

TNA-Mediated Antisense Strategy to Knockdown Akt Genes for Triple-Negative Breast Cancer Therapy.

Triple-negative breast cancer (TNBC) remains a significant challenge in terms of treatment, with limited efficacy of chemotherapy due to side effects and acquired drug resistance. In this study, a threose nucleic acid (TNA)-mediated antisense approach is employed to target therapeutic Akt genes for TNBC therapy. Specifically, two new TNA strands (anti-Akt2 and anti-Akt3) are designed and synthesized that specifically target Akt2 and Akt3 mRNAs. These TNAs exhibit exceptional enzymatic resistance, high specificity, enhance binding affinity with their target RNA molecules, and improve cellular uptake efficiency compared to natural nucleic acids. In both 2D and 3D TNBC cell models, the TNAs effectively inhibit the expression of their target mRNA and protein, surpassing the effects of scrambled TNAs. Moreover, when administered to TNBC-bearing animals in combination with lipid nanoparticles, the targeted anti-Akt TNAs lead to reduced tumor sizes and decreased target protein expression compared to control groups. Silencing the corresponding Akt genes also promotes apoptotic responses in TNBC and suppresses tumor cell proliferation in vivo. This study introduces a novel approach to TNBC therapy utilizing TNA polymers as antisense materials. Compared to conventional miRNA- and siRNA-based treatments, the TNA system holds promise as a cost-effective and scalable platform for TNBC treatment, owing to its remarkable enzymatic resistance, inexpensive synthetic reagents, and simple production procedures. It is anticipated that this TNA-based polymeric system, which targets anti-apoptotic proteins involved in breast tumor development and progression, can represent a significant advancement in the clinical development of effective antisense materials for TNBC, a cancer type that lacks effective targeted therapy.

Environmental Dyeing and Functionalization of Silk Fabrics with Natural Dye Extracted from Lac.

Most traditional synthetic dyes and functional reagents used in silk fabrics are not biodegradable and lack green environmental protection. Natural dyes have attracted more and more attention because of their coloring, functionalization effects, and environmental benefits. In this study, natural dyes were extracted from lac and used for coloring and functionalization in silk fabrics without any other harmful dyes. The extraction conditions were studied and analyzed by the univariate method. The optimal extraction process was that the volume ratio of ethanol to water was 60:40 with a solid-liquid ratio of 1:10, and reacting under the neutrality condition for 1 h at 70 °C. Silk fabric can be dyed dark owing to the certain lifting property of lac. After being dyed by Al3+ post-medium, the levels of the washing fastness, light fastness, and friction fastness of silk fabric are all above four with excellent fastness. The results show that the dyed silk fabrics have good UV protection, antioxidation, and antibacterial properties. The UV protection coefficient UPF is 42.68, the antioxidant property is 98.57%, and the antibacterial property can reach more than 80%. Therefore, the dyeing and functionalization of silk fabrics by utilizing naturally lac dyes show broad prospects in terms of the application of green sustainable dyeing and functionalization.

Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements.

The impact of organometallic chemistry on the terpene field only really blossomed in the 1960s and 1970s with the realisation that carbon-carbon bond formation under mild conditions could be achieved by using nickel or iron carbonyls as synthetic reagents. Concomitantly, the development of palladium derivatives capable of the controlled coupling of isoprene units attracted the attention of numerous highly talented researchers, including future Nobel laureates. We discuss briefly how early work on the syntheses of simple monoterpenes soon progressed to sesquiterpenes and diterpenes of increasing complexity, such as humulene, flexibilene, vitamin A, or pheromones of commercial value, in particular those used in perfumery (muscone, lavandulol), or grandisol and red scale pheromone as replacements for harmful pesticides. As the field progressed, there has been more emphasis on developing organometallic routes to enantiopure rather than racemic products, as well as gaining precise mechanistic data on the transformations, notably the course of metal-promoted molecular rearrangements that have long been a feature of terpene chemistry. We note the impact of the enormously enhanced analytical techniques, high-field NMR spectroscopy and X-ray crystallography, and their use to re-examine the originally proposed structures of terpenes and their organometallic derivatives. Finally, we highlight the very recent ground-breaking use of the crystalline sponge method to acquire structural data on low-melting or volatile terpenes. The literature cited herein covers the period 1959 to 2023.

Bespoke Metal Nanoparticle Synthesis at Room Temperature and Discovery of Chemical Knowledge on Nanoparticle Growth via Autonomous Experimentations

AbstractThe optimization of nanomaterial synthesis using numerous synthetic variables is considered to be an extremely laborious task because conventional combinatorial explorations are prohibitively expensive. In this work, an autonomous experimentation platform developed for the bespoke design of metal nanoparticles (NPs) with targeted optical properties is reported. This platform operates in a closed‐loop manner between the batch synthesis module of metal NPs and the UV–vis spectroscopy module, based on the feedback of the AI optimization modeling. With silver (Ag) NPs as a representative example, it is demonstrated that the Bayesian optimizer implemented with the early stopping criterion can efficiently produce Ag NPs at room temperature precisely possessing the desired absorption spectra within only 200 iterations (when optimizing among five aqueous synthetic reagents). In addition to the outstanding material developmental efficiency, the analysis of synthetic variables further reveals a novel chemistry involving the quantitative effects of citrate in Ag NP synthesis. The amount of citrate is key to controlling the competition between spherical and plate‐shaped NPs and, as a result, affects the shapes of the absorption spectra as well. This study highlights both capabilities of the platform to enhance search efficiencies and to provide novel chemical knowledge by analyzing datasets accumulated from autonomous experimentations.

Unification of requirements for the use of reagents for the treatment of sewage sludge from urban sewage treatment plants

This paper describes the experience of unification of requirements for the use of natural and synthetic reagents at all stages of wastewater sludge treatment. The practical necessity of this study is due to the tightening of environmental requirements around the world and the increasingly active introduction of closed-loop technologies of the economy. To date, products from sewage sludge are unclaimed not only by construction and road enterprises, but also by municipalities, which could more actively use the soil for landscaping urban areas. The most promising in terms of results and costs is the use of reagents at all stages of wastewater sludge treatment. Their use makes it possible to significantly reduce the costs of such technological processes as dehydration and stabilization. Reagents are an indispensable component in modern approaches to composting and disinfection.

Cu-Pd bimetal-decorated siloxene nanosheets for semi-hydrogenation of acetylene.

Metallic Pd has been proved highly promising when paired with Cu for industrially important acetylene semi-hydrogenation. Herein, we demonstrate that high-surface-area siloxene can feasibly enable alloying between Pd and Cu via room-temperature reduction with Si-H bonds. Unprecedentedly small Cu nanoparticles with isolated Pd were in situ loaded on siloxene, addressing the core problem of low selectivity of Pd and low activity of Cu. This devised structure outclassed the traditional impregnated SiO2 in every aspect of the catalytic performance for the semi-hydrogenation of acetylene under industry conditions, with a 91% acetylene conversion and an impressive 93% selectivity to ethylene at 200 °C, and showed long-term stability with negligible activity decay at this harsh temperature. This work provides new insights for the design of economic bimetallic loaded catalysts for balancing the activity-selectivity dilemma, demonstrating the viability of siloxene as both a synthetic reagent and a carrier material for efficient catalysis.

Harnessing the Power of Saussurea obvallata Zinc Oxide Nanoparticles for Accelerated Wound Healing and Antimicrobial Action.

Zinc oxide nanoparticles (ZnONPs) have been the subject of substantial research by virtue of their utility across extensive downstream applications. Moreover, the ZnONPs are inexpensive, reliable, and easy to produce. Green synthesis employing biological systems, particularly plant extracts, has arisen as a subject of study in nanotechnology and is gaining importance due to its multiple applications in biology, chemistry, physics, and medicine. Aqueous extract of S. obvallata was prepared and ZnONPs were synthesised using zinc acetate as a substrate. UV-Vis spectrophotometric measurement confirmed the production of ZnONPs. The ZnONPs were characterized by employing SEM, EDS, XRD, and FTIR. The ZnONPs were screened for its antimicrobial and wound healing potential. The peak of absorbance for UV-Vis was observed at 370 nm. The average dimension of the particles was found to be 22.58 nm. The antibacterial activity of ZnONPs was efficient in countering a broad spectrum of bacteria and the fungi C. albicans. The results of in vitro and in vivo wound healing assays indicate that the ZnONPs possess potent wound healing potential. In the cell migration assay, the percentage of wound closure was observed to be 84.70% (p < 0.001) for ZnONPs compared to the untreated group (8.12%). In the excision wound healing rat model, the animals treated with ZnONPs and Povidone-Iodine showed a significant (p < 0.01) wound contraction in comparison to the untreated animals. The ZnONPs promoted wound healing processes and showed promise as a therapeutic agent. However, further research is needed to understand the mechanisms of action and evaluate the long-term safety and effectiveness of ZnONPs in wound healing applications. By using renewable biological materials, the green synthesis of ZnONPs minimizes the need for synthetic reagents and lowers the total carbon footprint related to the production of nanoparticles.

Synthesis of Axially Chiral Boron Compounds

Boron-doped organic compounds display unique properties as a result of the presence of an empty p orbital on boron and the ability to switch between a trigonal planar and a tetrahedral geometry. In recent years, they have found several applications not only as synthetic reagents, e.g., in the Suzuki–Miyaura reaction, but also as pharmaceuticals and as specialized materials due to their optical and electronic properties. Some boron compounds may exist as atropisomers, and these rotamers may have different properties according to their sense of rotation. Synthetic strategies to separate them and, more recently, to obtain them in an asymmetric manner are becoming popular. In this review, we survey the literature on this emerging field of research.

CuNPs@Al2O3-cellulose composite for the ligand-free Suzuki cross-coupling reactions in batch and continuous flow process

In the present work, we synthesized recyclable CuNPs@Al2O3-CELL composite from an inexpensive and commercially available synthetic reagent by a simple method. The catalyst was characterized by various techniques such as TGA (Thermogravimetric analysis), SEM (Scanning electron microscope), TEM (Transmission electron microscopy), XPS (X-ray photoelectron spectroscopy), EDS (Energy dispersive spectroscopy), and AAS (Atomic Absorption Spectroscopy). The composite was applied for the Suzuki coupling reactions in the batch and flow process. The aryl halides were easily coupled with arylboronic acids in 95 % ethanol at 78 °C. We systematically investigated the role of reaction temperature, solvent, and catalyst loading, on the transient and steady-state behavior of the flow reactor through an automated flow chemistry platform. The CuNPs@Al2O3-CELL catalytic particles demonstrate minimal deactivation and leaching over a continuous Suzuki coupling reaction at a 20 min nominal residence time at 100 °C. Moreover, the catalyst can be recovered by simple filtration and reused at least five times with a moderate decrease in product yield. The excellent activity and stability of the catalyst have been attributed to the strong chelation of the Cu species with hydroxyl functional groups of the Al2O3-CELL composite. The catalytic system was highly efficient in Suzuki coupling of various aryl bromides with different aryl boronic acids, yielding good to excellent product yields (80–96 %) with a TON of 15.914–19.066 and TOF of 2.649–9.533 h−1.

Reagent Engineering for Group Transfer Biocatalysis.

Biocatalysis has become a major driver in the innovation of preparative chemistry. Enzyme discovery, engineering and computational design have matured to reliable strategies in the development of biocatalytic processes. By comparison, substrate engineering has received much less attention. In this Minireview, we highlight the idea that the design of synthetic reagents may be an equally fruitful and complementary approach to develop novel enzyme-catalysed group transfer chemistry. This Minireview discusses key examples from the literature that illustrate how synthetic substrates can be devised to improve the efficiency, scalability and sustainability, as well as the scope of such reactions. We also provide an opinion as to how this concept might be further developed in the future, aspiring to replicate the evolutionary success story of natural group transfer reagents, such as adenosine triphosphate (ATP) and S-adenosyl methionine (SAM).

An N terminomics toolbox combining 2-pyridinecarboxaldehyde probes and click chemistry for profiling protease specificity

Proteomic profiling of protease-generated N termini provides key insights into protease function and specificity. However, current technologies have sequence limitations or require specialized synthetic reagents for N-terminal peptide isolation. Here, we introduce an N terminomics toolbox that combines selective N-terminal biotinylation using 2-pyridinecarboxaldehyde (2PCA) reagents with chemically cleavable linkers to enable efficient enrichment of protein N termini. By incorporating a commercially available alkyne-modified 2PCA in combination with Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC), our strategy eliminates the need for chemical synthesis of N-terminal probes. Using these reagents, we developed PICS2 (Proteomic Identification of Cleavage Sites with 2PCA) to profile the specificity of subtilisin/kexin-type proprotein convertases (PCSKs). We also implemented CHOPPER (chemical enrichment of protease substrates with purchasable, elutable reagents) for global sequencing of apoptotic proteolytic cleavage sites. Based on their broad applicability and ease of implementation, PICS2 and CHOPPER are useful tools that will advance our understanding of protease biology.