Chemical Route Research Articles

Z-Selective hydrosulfoxidation of alkynes with thiols and hydrogen peroxide Enabled by a Multifunctional octamolybdate

Although sulfoxide is an important structural motif found in biological molecules and prevalent feedstocks in synthetic chemistry, a general and sustainable access route to (Z)-α,β-unsaturated sulfoxides remains highlychallenging due to the thermodynamic instability of Z-type geometric and the notorious sulfur nucleophiles poisoning of metal catalyst. Here we report a new protocol based on homogeneous octamolybdate-catalyzed anti-hydrothiolation and after Z-retentive sulfoxidation methodology, allowing access to (Z)-α,β-unsaturated sulfoxides from commercially available alkynes, thiols and H2O2. Control experiment investigations indicate that the molecular molybdenum is a thiyl radical initiator, Z-type geometric mediator and sulfoxidation catalyst. Notably, this one-pot reaction features broad substrate scopes with high stereoselectivity (Z/E up to > 99:1) and mild reaction conditions, thus providing a promising approach for the preparation of Z-vinyl sulfoxide compounds.

Magnetic Nanoparticles: Advances in Synthesis, Sensing, and Theragnostic Applications

The synthesis of magnetic nanoparticles (MNPs) via the chemical, biological, and physical routes has been reported on along with advantages and attendant limitations. This study focuses on the sensing and emerging theragnostic applications of this category of nanoparticles (NPs) in clinical sciences by unveiling the unique performance of these NPs in the biological sensing of bacteria and nucleotide sequencing. Also, in terms of medicine and clinical science, this review analyzes the emerging theragnostic applications of NPs in drug delivery, bone tissue engineering, deep brain stimulation, therapeutic hyperthermia, tumor detection, magnetic imaging and cell tracking, lymph node visualization, blood purification, and COVID-19 detection. This review presents succinct surface functionalization and unique surface coating techniques to confer less toxicity and biocompatibility during synthesis, which are often identified as limitations in medical applications. This study also indicates that these surface improvement techniques are useful for refining the selective activity of MNPs during their use as sensors and biomarkers. In addition, this study unveils attendant limitations, especially toxicological impacts on biomolecules, and suggests that future research should pay attention to the mitigation of the biotoxicity of MNPs. Thus, this study presents a proficient approach for the synthesis of high-performance MNPs fit for proficient medicine in the detection of microorganisms, better diagnosis, and treatment in medicine.

3D nanocomposites of β-TCP-H3BO3-Cu with improved mechanical and biological performances for bone regeneration applications

Recently, 3-D porous architecture of the composites play a key role in cell proliferation, bone regeneration, and anticancer activities. The osteoinductive and osteoconductive properties of β-TCP allow for the complete repair of numerous bone defects. Herein, β-TCP was synthesized by wet chemical precipitation route, and their 3-D porous composites with H3BO3 and Cu nanoparticles were prepared by the solid-state reaction method with improved mechanical and biological performances. Several characterization techniques have been used to investigate the various characteristics of fabricated porous composites. SEM and TEM studies revealed the porous morphology and hexagonal sheets of the β-TCP for the composite THC8 (82TCP-10H3BO3-8Cu). Moreover, the mechanical study showed excellent compressive strength (188 MPa), a high Young’s modulus (2.84 GPa), and elevated fracture toughness (9.11 MPa.m1/2). An in vitro study by MTT assay on osteoblast (MG-63) cells demonstrated no or minimal cytotoxicity at the higher concentration, 100 µg/ml after 24 h and it was found a more pronounced result at 20 µg/ml on increasing the concentration of Cu nanoparticles after incubating 72 h. The THC12 composite showed the highest antibacterial potency exclusively against B. subtilis. S. pyogene, S. typhi and E. coli. at 10 mg/ml, indicating its potential effectiveness in inhibiting all of these pathogens. Genotoxicity and cytotoxicity tests were also performed on rearing Drosophila melanogaster, and these findings did not detect any trypan blue-positive staining, which further recommended that the existence of composites did not harm the larval gut. Therefore, the fabricated porous composites THC8 and THC12 are suitable for bone regrowth without harming the surrounding cells and protect against bacterial infections.

Wet Chemical Co-precipitation Route of CuS Nanoparticles: Synthesis and Characteristics Studies Towards Photo-Degradation of 2-Chlorophenol

Wet Chemical Co-precipitation Route of CuS Nanoparticles: Synthesis and Characteristics Studies Towards Photo-Degradation of 2-Chlorophenol

Integration of p-Type PdPc and n-Type SnZnO into Hybrid Nanofibers Using Simple Chemical Route for Enhancement of Schottky Diode Efficiency

Palladium phthalocyanine (PdPc) and palladium phthalocyanine integrated with tin–zinc oxide (PdPc:SnZnO) were prepared using a simple chemical approach, and their structural and morphological properties were identified using X-ray diffraction, energy dispersive X-ray analysis, scanning electron microscopy, and transmission electron microscopy techniques. The PdPc:SnZnO nanohybrid revealed a polycrystalline structure combining n-type metal oxide SnZnO nanoparticles with p-type organic PdPc molecules. The surface morphology exhibited wrinkled nanofibers decorated with tiny spheres and had a large aspect ratio. The thin film revealed significant optical absorption within the ultraviolet and visible spectra, with narrow band gaps measured at 1.52 eV and 2.60 eV. The electronic characteristics of Al/n-Si/PdPc/Ag and Al/n-Si/PdPc:SnZnO/Ag Schottky diodes were investigated using the current–voltage dependence in both the dark conditions and under illumination. The photodiodes displayed non-ideal behavior with an ideality factor greater than unity. The hybrid diode showed considerably high rectification ratio of 899, quite a low potential barrier, substantial specific photodetectivity, and high enough quantum efficiency, found to be influenced by dopant atoms and the unique topological architecture of the nanohybrid. The capacitance/conductance–voltage dependence measurements revealed the influence of alternative current signals on trapped centers at the interface state, leading to an increase in charge carrier density.

Cerium oxide nanoparticles decorated on graphene oxide nanosheets as battery-type cathode material for supercapacitors.

Designing advanced materials that effectively mitigate the poor cycle life of battery-type electrodes with high specific capacities is crucial for next-generation energy storage systems. Herein, graphene oxide-ceria (GO-CeO2) nanocomposite synthesized via a facile wet chemical route is explored as cathode for high-performance supercapacitors. The morphological analysis suggests fine ceria (CeO2) nanoparticles dispersed over ultrathin graphene oxide (GO) sheets while structural studies reveal face-centered cubic phase of CeO2 in the nanocomposite. In-depth electrochemical performance investigation of the nanocomposite in 6M KOH aqueous electrolyte demonstrated its excellent battery-type behavior with least ion diffusion resistance and a superior cycle life resulting from the synergistic effect of redox-active CeO2 and 2D GO with abundant oxygen functionalities. Specifically, GO-CeO2 composite electrode delivered a maximum specific capacitance of 625.9F/g (52.2mAh/g) at 3 A/g current density, which is substantially higher than the capacitance values obtained for GO and CeO2 electrodes, and demonstrated an excellent cycling stability with∼100% capacitance retention after 10,000 CV cycles. Furthermore, a novel aqueous asymmetric supercapacitor (ASC) is explored with GO-CeO2 as positive and iron(III) oxyhydroxide (FeOOH) as negative electrode material in 6M KOH electrolyte which has also displayed good energy-power density combination along with excellent cycle stability. The study thus endorses rational design of nanocomposite materials with suitable functionalities as an excellent strategy in augmenting the performance of futuristic energy storage devices.

Chemical and Enzymatic Mechanosynthesis of Organocatalytic Peptide Materials Based on Proline and Phenylalanine.

In recent years, mechanosynthesis of peptides through either chemical or enzymatic routes has been accomplished. In part, this advancement has been driven due to the organocatalytic properties of peptide-based biomaterials. In this work, we report the merging of chemical and enzymatic protocols under mechanochemical conditions to synthesize peptide materials based on L-proline and L-phenylalanine. Compared to traditional step-by-step peptide synthesis in solution, our mechanochemical approach combining peptide coupling reagents with the proteolytic enzyme papain offers a more sustainable route by reducing the number of synthetic steps, shortening reaction times, increasing chemical yields, and minimizing waste production. Notably, the mechanosynthesized peptides exhibited organocatalytic activity in the asymmetric aldol reaction between cyclohexanone and 4-nitrobenzaldehyde.

Structural, magnetic, dielectric properties of double perovskite- La2NiFeO6 synthesized by wet chemical route

Structural, magnetic, dielectric properties of double perovskite- La2NiFeO6 synthesized by wet chemical route

Efficient Synthesis of cis,cis-Muconic Acid by Catechol Oxidation of Ozone in the Presence of a Base.

Muconic acid, a crucial precursor in synthesizing materials like PET bottles and nylon, is pivotal for the anticipated growth in the textiles and plastics industries. This study presents a novel chemical synthesis route for cis,cis-muconic acid (ccMA) using catechol. Biochemical methods face scale-up challenges due to microorganism sensitivity and complex extraction processes, while chemical methods involve environmentally harmful substances and have low yields. Our research introduces a method that enhances ccMA yield to 56% by employing ozonation in the presence of an alkali, significantly simplifying the synthesis process. This one-step synthesis reduces reagent use and labor, aligns with green chemistry principles, and avoids using toxic chemicals. The methodology, involving the low-temperature ozonation of catechol with base addition, reduces ccMA degradation and improves yield, as confirmed by an HPLC analysis and replicated experiments. This promising approach could lead to sustainable industrial synthesis of muconic acid derivatives. Further investigations will focus on refining this method for larger-scale applications and testing its economic viability, aiming to optimize conditions for maximum efficiency and yield.

Room-temperature synthesis of triple-cation green perovskite quantum dots for optoelectronic applications.

The development of multi-cation perovskite quantum dots (PQDs) is limited by the low availability of fitting A-site cations due to the unsuitable radii of a large gamut of amine cations. The impact of oversized or undersized cations on the perovskite structure is detrimental to the structural stabilization and electroluminescence efficiency of the PQDs. Researchers are actively seeking suitable-sized cations to mitigate perovskite defect formation and optimize charge carrier confinement within the PQDs. In contrast to cesium (Cs) or formamidine (FA), which are exposed to degradation pathways, guanidinium (GA)-doping has been to provide a suitable radius and the lack a dipole moment. The triple nitrogen functionality of GA enables it to passivate both the PbBr6 octahedra and surface defects through vacant A-sites and entropically stabilize the perovskite. Furthermore, the insertion of GA into the PQD lattice is enthalpically facilitated by the presence and arrangement of smaller Cs and Br atoms. Herein, we have synthesized a Cs-FA PQD reference into which GA is doped via two chemical routes. Our triple-cation system exhibits substantially improved optical properties and was applied for the fabrication of a PeLED device. The optimized triple-cation PQDs-based PeLED device exhibited an external quantum efficiency of 5.87% and a luminescence of 13726 cd m-2.

Comparative Assessment of the Antibacterial Property of Cotton Fabric Coated with the Zinc Oxide Nanoparticles Synthesized Using Chemical and Green Approach

AbstractWorldwide, increasing pollution and bacterial infections are posing a serious risk to human well‐being and society. Clothing and textiles are the major pathways for the transmission and aggravation of infectious diseases. Thus, imparting antibacterial properties to the textiles is perceived with great interest. With this motivation, this study aims to fabricate durable antibacterial cotton fabrics to protect the wearer from pathogenic microorganisms. Herein, the synthesis of zinc oxide nanoparticles (ZnO NPs) via chemical (ZOCM) and green (ZOGM) routes, which were eventually applied onto the cotton fabric using the padding‐drying‐curing technique. The synthesized ZnO NPs and ZnO‐deposited cotton fabrics were analyzed by various characterization techniques. Including UV–vis, FTIR, BET, XRD, SEM‐EDAX, and TGA analysis. Additionally, the antibacterial effectiveness, washing durability, and mechanical properties of finished cotton (ZOCMC, ZOGMC) and uncoated fabric were investigated. The results indicate that ZOGM and ZOGMC show higher antibacterial efficiency than ZOCM and ZOCMC. Moreover, TGA analysis reveals the amount of ZnO loading before and its retention after multiple washing cycles. ZOGMC exhibits good adherence of NPs and better washing durability than ZOCMC. This study underscores the significance of environmentally friendly green synthesis methods for producing ZnO NPs, showcasing the potential for advancement in healthcare textiles.

Nanospheres of TiO2/MoS2 composites synthesized via two-step chemical route for high-performance supercapacitor electrodes

Nanospheres of TiO2/MoS2 composites synthesized via two-step chemical route for high-performance supercapacitor electrodes

Metastable layered lithium-rich niobium and tantalum oxides via nearly instantaneous cation exchange.

Lithium-rich early transition metal oxides are the source of excess removeable lithium that affords high energy density to lithium-rich battery cathodes. They are also candidates for solid electrolytes in all-solid-state batteries. These highly ionic compounds are sparse on phase diagrams of thermodynamically stable oxides, but soft chemical routes offer an alternative to explore new alkali-rich crystal chemistries. In this work, a new layered polymorph of Li3NbO4 with coplanar [Nb4O16]12- clusters is discovered through ion exchange chemistry. A more detailed study of the ion exchange reaction reveals that it takes place almost instantaneously, changing the crystal volume by more than 22% within seconds. The transformation of coplanar [Nb4O16]12- in L-Li3NbO4 into the supertetrahedral [Nb4O16]12- clusters found in the stable cubic c-Li3NbO4 is also explored. Furthermore, this synthetic pathway is extended to access a new layered polymorph of Li3TaO4. NMR crystallography with 6,7Li, 23Na, and 93Nb NMR, X-ray diffraction, neutron diffraction, and first-principles calculations is applied to A3MO4 (A = Li, Na; M = Nb, Ta) to identify local and long-range atomic structure, to monitor the unusually rapid reaction progression, and to track the phase transitions from the metastable layered phases to the known compounds found using high-temperature synthesis. A mechanism is proposed whereby some sodium is retained at short reaction times, which then undergoes proton exchange during water washing, forming a phase with hydrogen bonds bridging the coplanar [Nb4O16]12- clusters. This study has implications for lithium-rich transition metal oxides and associated battery materials and for ion exchange chemistry in non-framework structures. The role of techniques that can detect light elements, local structure, and subtle structural changes in soft-chemical synthesis is emphasized.

Gas-phase Formation of Large, Astronomically Relevant Polycyclic Aromatic Hydrocarbon Clusters

As one class of important carbon reservoirs in interstellar clouds, large polycyclic aromatic hydrocarbons (PAHs) and their derivative species play an important role in the formation and evolution of interstellar carbonaceous compounds. To understand these chemical routes, the gas-phase ion–molecular collision reaction between large, astronomically relevant PAH (dicoronylene, DC, C48H20) cations and smaller neutral superhydrogenated PAHs (2, 3–benzofluorene, C17H12) are investigated. Series of large DC/2, 3–benzofluorene cluster cations (e.g., [(C17H12)6C48H14]+, 236 atoms, and [(C17H12)5C48]+, 193 atoms) are efficiently formed by gas-phase condensation under laser irradiation conditions. With theoretical calculations, the structure of newly formed DC/2, 3-benzofluorene cluster cations and the bonding energy for these formation reactions are obtained. Moreover, the IR spectra of DC/2, 3-benzofluorene cluster cations are also calculated. The gas-phase reactions between large PAH species occur relatively easily, resulting in a very large number of reactions and very complex molecular clusters. The adduct processes and the formed molecular structure relatively depend on the carbon reaction sites. The carbon edge sites have different chemical reactivity, which may affect the abundance of these relevant interstellar substances. Furthermore, intermolecular hydrogen transfer plays an important role in cluster formation processes, which can lead the newly formed clusters to become more stable. We infer that small superhydrogenated PAH molecules (e.g., 2, 3-benzofluorene) can effectively aggregate on the large PAH molecules (e.g., dehydrogenated DC cations or carbon clusters) in the gas phase, which provides proposed chemical-evolution routes (ion–molecular reaction pathways) for the formation of the nanometer-sized dust grains in a bottom-up process (in building block pathways) in the interstellar medium.

Contactless manufacturing of TERS-active AFM tips by bipolar electrodeposition.

Tip-enhanced Raman spectroscopy (TERS) is a powerful technique for nanoscale chemical imaging. However, its worldwide expansion is still limited by the challenging fabrication of cheap, robust and efficient TERS tips as optical nanosources to amplify the Raman signal. An original method based on bipolar electrodeposition is described here to prepare gold-coated AFM cantilevers used as TERS tips. This wireless method is simple to implement, cost-effective, and allows for the parallel fabrication of several TERS tips with good reproducibility of the metal thickness and a relatively long lifetime. The TERS activity was confirmed by imaging graphene oxide flakes with high spatial resolution (below 10 nm). A promising yield of 64% was achieved for the fabrication of active TERS tips. Therefore, this method could pave the way for the development of new chemical routes for the preparation of TERS tips and other plasmonic nanostructures.

Scalable electrocatalyzed formation of C–O bonds using flow reactor technology

A scalable C–O bond formation via continuous-flow Ni-electrocatalysis was developed, enabling the gram-scale preparation of a key delamanid intermediate, a pharmaceutical used to treat multidrug-resistant tuberculosis.

Sn-doped ZnO nanostructure deposited with free-catalyst chemical vapor deposition route: optical, electrical and photocatalytic properties

Sn-doped ZnO nanostructure deposited with free-catalyst chemical vapor deposition route: optical, electrical and photocatalytic properties

Air‐Mediated Biomimetic Synthesis of Polyhydroxyalkanoate with C4 Diol

AbstractPoly(4‐hydroxybutyrate) (P4HB) is a high‐performance, well‐recyclable, and biodegradable polyhydroxyalkanoate (PHA). However, conventional bioproduction of homopolymeric P4HB involves complex and costly processes with C4 feedstocks, particularly 1,4‐butanediol (BDO), and enzyme‐coenzyme systems in genetically engineered bacteria. An alternative extracellular chemical route utilizing aerial oxidation of BDO offers cost and energy benefits but struggle with conversion efficiency. Inspired by efficient intracellular oxidation of primary alcohols, we propose a ruthenium‐phosphine synergistic catalytic system that mimics enzyme‐coenzyme functionality. This system effectively catalyzed the air‐mediated, solvent‐free oxidation of BDO to produce γ‐butyrolactone (γ‐BL) and oligomeric P4HB, with a space‐time yield (10.37 g [γ‐BL unit] g−1 catalyst h−1) surpassing the values (<5.5) of previous approaches. The oligomer‐containing products were reversibly converted to γ‐BL and then to P4HB (28.9 kDa) via ring‐opening polymerization, exceeding reported values (<16 kDa). This study provides the potential for large‐scale synthesis of high‐value PHAs from diverse non‐grain‐based diols, offering economic and environmental advantages.

Uncovering Hericenones from the Fruiting Bodies of Hericium erinaceus through Interdisciplinary Collaboration.

Hericium erinaceus is an edible and medicinal mushroom. Previously, we found hericenones C-H from the fruiting bodies and erinacines A-I from the mycelia of the fungus. These compounds stimulated nerve growth factor (NGF) synthesis both in vitro and in vivo; some have been suggested to be effective in the prevention and treatment of dementia. Recently, the total synthesis of hericenones C-H and their derivatives (1-4) was reported by one of the authors. We considered that the chemical synthetic route would also be reasonable as a biosynthetic pathway of the compounds. Based on the hypothesis, we investigated the endogenous existence of synthetic intermediates and products of the chemical synthesis in the fruiting bodies. The n-hexane-soluble part of the fruiting bodies of H. erinaceus was fractionated, and all the fractions were subjected to a product ion scan and multiple reaction monitoring (MRM) analysis by LC-MS/MS and compared to the authentic synthesized compounds. The analysis indicated the endogenous existence of 1-4 and the dehydrated form of 2 or 3. The dehydrated form was elucidated to be (Z)-5 by chemical synthesis, and a plausible biosynthetic pathway was proposed.

Engineering of Cd x Zn1-x S Nanomaterials for Fabrication of Hybrid Cd x Zn1-x S/Si Heterojunction Broadband Photo Detectors.

Effective engineering of nanostructured materials provides a scope to explore the underlying photoelectric phenomenon completely. A simple cost-effective chemical reduction route is taken to grow nanoparticles of Cd x Zn1-x S with varying x = 1, 0.7, 0.5, 0.3, and 0. X-ray diffraction confirms the formation of different phases of targeted Cd x Zn1-x S, while field emission scanning electron microscopy shows change of nanostructures. Energy-dispersive X-ray spectroscopy determines the composition of the grown nanostructures as CdS, Cd0.7Zn0.3S, Cd0.5Zn0.5S, Cd0.3Zn0.7S, and ZnS. The optical absorption study determines the band gap shift with change of composition as well as with quantum confinement. The fluorescence lifetime for each nanomaterial is determined by time-correlated single photon counting, and Raman analysis revealed that ZnS exhibits the highest blue shift. Thus, there is a possibility to apply such grown nanomaterials for fabrication of heterojunction-based photodetectors (PDs) in a broad wavelength region. Cd x Zn1-x S nanostructures on n-type bulk silicon (Si) were successfully fabricated by a simple cost-effective spin coating method and present hybrid heterojunction PDs. The fabricated p-n heterojunction exhibits good rectifying behavior at room temperature under a reverse bias condition. Also, it was observed that the heterojunction is extremely sensitive to the irradiation of visible light because of the significant optoelectric effect with a good I light/I dark ratio (here, I light is the current in the presence of light and I dark is the dark current), quick response time (40 to 1005 ms), and good reproducibility (three cycles of I light/I dark for each sample are observed). It was observed that the responsivity value gradually decreases for x = 1 to x = 0 in the Cd x Zn1-x S/n-Si heterojunction, i.e., it is maximum for CdS NRs (6.74 × 10-3 mA/W), intermediate for Cd0.5Zn0.5S NPs (4.49 × 10-3 mA/W), and minimum for ZnS NPs (2.72161 × 10-4 mA/W). A similar nature has been observed in the case of detectivity, and hence it is a maximum (1.45 × 106 Jones) for CdS NRs. The photocurrent generation at the heterojunction showed excellent "on" and "off" switching behavior in the presence and absence of light illumination. Response time and gain change significantly with change of composition. The responsivity and detectivity with good photoresponse originated from the realization of special microstructures, enhancing the photoelectric behavior of Cd x Zn1-x S materials for applications in low-dimensional PDs covering a large wavelength region.