Why Single-Chain Nanoparticles from Weak Polyelectrolytes Can Be Synthesized at Large Scale in Concentrated Solution?

Here, the unresolved question of why single-chain nanoparticles (SCNPs) prepared from a weak polyelectrolyte (PE) precursor can be synthesized on a large is addresses, unlike SCNPs obtained from an equivalent neutral (nonamphiphilic) polymer precursor. The combination of the standard elastic single-chain nanoparticles (ESN) model -developed for neutral chains- with the classical scaling theory of PE solutions provides the key. Essentially, the long-range repulsion between electrostatic blobs in a weak PE precursor restricts the cross-linking process during SCNPs formation to the interior of each blob. Consequently, the maximum concentration at which PE-SCNPs can be prepared without interchain cross-linking is not determined by the full size of the PE precursor but, instead, by the smaller size of its electrostatic blobs. Therefore, PE-SCNPs can be synthesized up to a critical concentration where electrostatic blobs from different chains touch each other. This concentration can be 30 times higher than that for non-PE polymer precursors. Upon progressive dilution, the size of PE-SCNPs synthesized in concentrated solution increases until it reaches the bigger size of PE-SCNPs prepared under highly diluted conditions. PE-SCNPs do not adopt a globular conformation either in concentrated or in diluted solution. It shows that the main model predictions agree with experimental results.

Large Scale Synthesis of a Stable Prefunctionalized Silver Nanocluster.

Due to the stability issue, It is difficult to prepare a silver nanocluster bearing functional sites, especially at a large scale. We report the synthesis and structure of a stable silver nanocluster bearing multiple surface aldehyde groups [Ag21(Ph2PO2)10(p-CHOPhC≡C)6]SbF6, which allows for postsynthesis modification such as surface functionalization through aldimine condensation to give homochiral clusters. Remarkably, the preparation of this cluster can be done in ~90% high yield at gram scale, which facilitates further studies and potential applications. Through DFT calculations and geometric structure analysis, the high stability of this cluster is attributed to the geometric closure and electronic structure. This is the first time that an effective one-pot method has been developed to synthesize functional silver nanoclusters in high yield. The title cluster will be useful in the development of a variety of cluster-based materials.

Upscaling and Risk Evaluation of the Synthesis of the 3,5-Diamino-1H-Pyrazole, Disperazol.

This paper presents the work performed to transition a lab-scale synthesis (1 g) to a large-scale (400 g) synthesis of the 3-5-diamino-1H-Pyrazole Disperazol, a new pharmaceutical for treatment of antibiotic-resistant Pseudomonas aeruginosa biofilm infections. The potentially hazardous diazotisation step in the lab-scale synthesis was transformed to a safe and easy-to-handle flow chemistry step. Additionally, the paper presents an OSHA-recommended safety assessment of active compound E, as performed by Fauske and Associates, LLC, Burr Ridge, IL, USA.

Large-Scale Synthesis of High-Purity Isoguanosine and Resolution of its Crystal Structure by Microcrystal Electron Diffraction.

Isoguanosine (isoG) is a natural structural isomer of guanosine (G) with significant potential for applications in ionophores, genetics, gel formation, and cancer therapy. However, the cost of commercially available isoG on a gram scale is relatively high. To date, a detailed method for the large-scale preparation of high-purity isoG has not been reported. This study presented a simple and convenient approach for the large-scale synthesis of isoG through the diazotization of 2,6-diaminopurine riboside with sodium nitrite and acetic acid at room temperature. Further, this method could synthesize isoG derivatives (2'-fluoro-isoguanosine (1) and 2'-deoxy-isoguanosine (2)) from 2,6-diaminopurine nucleoside derivatives using diazotization. The structural information of natural and modified nucleosides is crucial for the modification and substitution of DNA/RNA. This study obtained the single-crystal structure of isoG for the first time and analyzed it in detail using microcrystal electron diffraction. The three-dimensional supramolecular structure of isoG adopted similarly base-pair motifs from π-π stacking interaction of diverse layers, intramolecular hydrogen bonding, and distinct hydrogen bonding interactions from sugar residues. This study has contributed to further isoG modification and its applications in medicinal chemistry and materials.

Photostimulated Pyrothermoelectric Coupling in Two-Dimensional Tin Monoselenide Enabling Zero-Biased Multimodal Transducers.

Despite the advancement of the Internet of Things (IoT) and portable devices, the development of zero-biased sensing systems for the dual detection of light and gases remains a challenge. As an emerging technology, direct energy conversion driven by intriguing physical properties of two-dimensional (2D) materials can be realized in nanodevices or a zero-biased integrated system. In this study, we unprecedentedly attempted to exploit the photostimulated pyrothermoelectric coupling of two-dimensional SnSe for use in zero-biased multimodal transducers for the dual detection of light and gases. We synthesized homogeneous, large-area 6 in SnSe multilayers via a rational synthetic route based on the thermal decomposition of a solution-processed single-source precursor. Zero-biased SnSe transducers for the dual monitoring of light and gases were realized by exploiting the synergistic coupling of the photostimulated pyroelectric and thermoelectric effects of SnSe. The extracted photoresponsivity at 532 nm and NO2 gas responsivity of the SnSe-based transducers corresponded to 1.07 × 10-6 A/W and 13263.6% at 0 V, respectively. To bring universal applicability of the zero-biased SnSe transducers, the wide operation bandwidth photoelectrical properties (visible to NIR) and dynamic current responses toward two NO2/NH3 gases were systematically evaluated.

Hydroxide-Derived Nanostructures: Scalable Synthesis, Characterization, Properties, and Potential Applications.

Metal oxide nanostructures have received an increasing attention owing to their unique chemical and physical properties along with their widespread applications in various fields. This article provides an overview of the recent discovery - christened Hydroxides-Derived Nanostructures, or HDNs - in which hydroxide aqueous solutions (mostly tetramethylammonium hydroxide, TMAH) are reacted at temperatures < 100 °C and under atmospheric pressure with various metal-containing precursors to scalably prepare novel metal oxide nanostructures. In one case, a dozen commercial and earth abundant Ti-containing powders such as binary carbides, nitrides, borides, among others, are converted into new, 1D TiO2-based lepidocrocite (1DL) nanofilaments (NFs). Application-wise, the 1DLs show outstanding performance in a number of energy, environmental, and biomedical fields such as photo- and electrocatalysis, water splitting, lithium-sulfur and lithium-ion batteries, water purification, dye degradation, cancer therapy, and polymer composites. In addition to 1DL, the HDNs family encompasses other metal oxides nanostructures including magnetic Fe3O4 nanoparticles and MnO2 birnessite-based crystalline 2D flakes. The latter showed promise in electrochemical energy conversion and storage applications. The developed recipe provides a new vista in the molecular self-assembly synthesis of nanomaterials that can advance the field with a library of novel nanostructures with substantial implications in a multitude of fields.

Solvent-Induced Structural Rearrangement in Ultrasound-Assisted Synthesis of Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are crystalline extended structures featuring permanent porosity, assembled from metal ions and organic ligands, often synthesized by the solvothermal method (50-260 °C, 12-72 h). Here, an alternative synthetic approach-solvent-induced structural rearrangement in ultrasound-assisted synthesis is presented. Six representative Zn-based MOFs, each composed of distinct secondary building units, are synthesized within 2-180 min consuming less solvent (>0.03 m) at room temperature. It is observed that ultrasonication induces the construction of a coordination network, and subsequent solvent exchange triggers structural rearrangement to yield MOFs of high crystallinity and porosity. Furthermore, the scalability of this method is demonstrated through the bulk synthesis of MOF-5, MOF-74, ZIF-8, and MFU-4l within 90 min. The initiation of nucleation through ultrasound and the subsequent transformation induced by solvent exchange offer an alternative method for efficiently synthesizing MOFs in bulk, potentially broadening their range of applications.

Large-Scale Green Synthesis of Magnesium Whitlockite from Environmentally Benign Precursor.

Magnesium whitlockite (Mg-WH) powders were synthesized with remarkable efficiency via the dissolution-precipitation method by employing an environmentally benign precursor, gypsum. Under optimized conditions, each 5.00 g of initial gypsum yielded an impressive amount of 3.00 g (89% yield) of Mg-WH in a single batch. Remarkably, no XRD peaks attributable to impurity phases were observed, indicating the single-phase nature of the sample. FT-IR analysis confirmed the presence of the PO43- and HPO42- groups in the obtained Mg-WH phase. The SEM-EDX results confirmed that Mg-WH crystals with homogeneous Ca, Mg, P, and O distributions were obtained. In previously published research papers, the synthesis of Mg-WH has been consistently described as a highly intricate process due to material formation within a narrow pH and temperature range. Our proposed synthesis method is particularly compelling as it eliminates the need for meticulous monitoring, presenting a notable improvement in the quest for a more convenient and efficient Mg-WH synthesis. The proposed procedure not only emphasizes the effectiveness of the process, but also highlights its potential to meet significant demands, providing a reliable solution for large-scale production needs in various promising applications.

Short-Wave Infrared Detection and Imaging Employing Size-Customized HgTe Nanocrystals.

HgTe nanocrystals (NCs) possess advantages including tunable infrared absorption spectra, solution processability, and low fabrication costs, offering new avenues for the advancement of next-generation infrared detectors. In spite of great synthetic advances, it remains essential to achieve customized synthesis of HgTe NCs in terms of industrial applications. Herein, by taking advantage of a high critical nucleation concentration of HgTe NCs, a continuous-dropwise (CD) synthetic approach that features the addition of the anion precursors in a feasible drop-by-drop fashion is demonstrated. The slow reaction dynamics enable size-customized synthesis of HgTe NCs with sharp band tails and wide absorption range fully covering the short- and mid-infrared regions. More importantly, the intrinsic advantages of CD process ensure high-uniformity and scale-up synthesis from batch to batch without compromising the excitonic features. The resultant HgTe nanocrystal photodetectors show a high room-temperature detectivity of 8.1 × 1011 Jones at 1.7 µm cutoff absorption edge. This CD approach verifies a robust method for controlled synthesis of HgTe NCs and might have important implications for scale-up synthesis of other nanocrystal materials.

Solid-Liquid Interfacial Engineered Large-Area Two-Dimensional Covalent Organic Framework Films.

Constructing uniform covalent organic framework (COF) film on substrates for electronic devices is highly desirable. Here, a simple and mild strategy is developed to prepare them by polymerization on a solid-liquid interface. The universality of the method is confirmed by the successful preparation of five COF films with different microstructures. These films have large lateral size, controllable thickness, and high crystalline quality. And COF patterns can also be directly achieved on substrates via hydrophilic and hydrophobic interface engineering, which is in favor of preparing device array. For application studies, the PyTTA-TPA (PyTTA: 4,4',4'',4'''-(1,3,6,8-Tetrakis(4-aminophenyl)pyrene and TPA: terephthalaldehyde) COF film has a high photoresponsivity of 59.79 µA W-1 at 420 nm for photoelectrochemical (PEC) detection. When employed as an active material for optoelectronic synaptic devices for the first attempt, it shows excellent light-stimulated synaptic plasticity properties such as short-term plasticity (STP), long-term plasticity (LTP), and the conversion of STP to LTP, which can be used to simulate biological synaptic functions.

Pro-aromatic Dihydroquinazolinones - From Multigram Synthesis to Reagents for Gram-scale Metallaphotoredox Reactions.

Dihydroquinazolinone (DHQZ) has recently been harnessed as a ketone-derived pro-aromatic reagent extensively employed in (metalla)photoredox reactions as versatile group transfer agents. In this work, we outline a column chromatography-free protocol for the multigram-scale synthesis of pro-aromatic DHQZs as well as its use in a gram-scale nickel/photoredox dual-catalyzed cross-coupling in single-batch, photoflow, and simultaneous multiple smaller batches. While the single-batch approach leveraged moderate yields, a simple plug-flow photoreactor also exhibited amenable productivity (up to 45 % yield) despite the use of a heterogeneous base. Meanwhile, performing the metallaphotoredox-catalyzed reaction in multiple smaller batches in an improvised photoreactor facilitated high yields of up to 59 % and good reproducibility, implying a convenient alternative in the absence of photoflow setups.

Mass production of morin-stabilized silver nanoparticles: Characterization, antioxidant, and antimicrobial activities.

Phytochemical-conjugated silver nanoparticles (AgNPs) are believed to act as a bridge between nanotechnology and therapy. There is a significant need for green and mass production of such materials due to their extensive applications, especially in the biomedical sector. In this study, morin-stabilized silver nanoparticles (morin/AgNPs) were synthesized on a massive scale using a one-pot solid-state technique. The reaction is achieved by ball milling of morin and silver nitrate powders at ambient temperature without any solvent or toxic reagent. The prepared morin/AgNPs exhibited a semi-hexagonal shape and ranged in size from 21 to 43 nm. The x-ray diffraction results elucidated the formation of highly crystalline AgNPs. Fourier transform infrared and x-ray photoelectron spectroscopic analyses prove that the hydroxyl, carbonyl, and aromatic functionalities in morin are playing major roles in the reduction and stabilization of AgNPs. The antioxidant potential of morin/AgNPs was evaluated utilizing 2,2-Diphenyl-1-picryl-hydrazyl (DPPH) assay. Morin/AgNPs exhibited better free radical scavenging activity (IC50 = 11.7 µg/mL) than morin (IC50 = 14.8 µg/mL). Furthermore, the synthesized AgNPs showed promising antimicrobial activity against Escherichia coli, Klebsiella pneumonia, Staphylococcus aureus, Streptococcus mutans, and Candida albicans. The largest inhibition zones were observed against S. aureus (21.2 ± 0.6 mm) and K. pneumonia (20.3 ± 0.5 mm) bacteria. The foregoing results highlighted the prospective application of morin/AgNPs as a promising antioxidant and antimicrobial material for safe medical applications. RESEARCH HIGHLIGHTS: A simple green route for the large-scale production of AgNPs was developed. Morin acts as reducing/stabilizing agent in solid-state synthesis of AgNPs. Morin/AgNPs exhibited promising antimicrobial and antioxidant activity.

Recent Advances on Pulsed Laser Deposition of Large-Scale Thin Films.

2D thin films, possessing atomically thin thickness, are emerging as promising candidates for next-generation electronic devices, due to their novel properties and high performance. In the early years, a wide variety of 2D materials are prepared using several methods (mechanical/liquid exfoliation, chemical vapor deposition, etc.). However, the limited size of 2D flakes hinders their fundamental research and device applications, and hence the effective large-scale preparation of 2D films is still challenging. Recently, pulsed laser deposition (PLD) has appeared to be an impactful method for wafer-scale growth of 2D films, owing to target-maintained stoichiometry, high growth rate, and efficiency. In this review, the recent advances on the PLD preparation of 2D films are summarized, including the growth mechanisms, strategies, and materials classification. First, efficacious strategies of PLD growth are highlighted. Then, the growth, characterization, and device applications of various 2D films are presented, such as graphene, h-BN, MoS2 , BP, oxide, perovskite, semi-metal, etc. Finally, the potential challenges and further research directions of PLD technique is envisioned.

From CPG to hybrid support: Review on the approaches in nucleic acids synthesis in various media.

Solid-phase synthesis is, to date, the preferred method for the manufacture of oligonucleotides, in quantities ranging from a few micrograms for research purposes to several kilograms for therapeutic or commercial use. But for large-scale oligonucleotide manufacture, scaling up and hazardous waste production pose challenges that necessitate the investigation of alternate synthetic techniques. Despite the disadvantages of glass supports, using soluble supports as a substitute presents difficulties because of their high overall yield and complex purification steps. To address these challenges, various independent approaches have been developed; however, other problems such as insufficient cycle efficiency and synthesis of oligonucleotide chains of desired length continue to exist. In this study, we present a review of the current developments, advantages, and difficulties of recently reported alternatives to supports based on controlled pore glass, and discuss the importance of a support choice to resolve issues arising during oligonucleotide synthesis.

Large-Scale Synthesis of Tunable Fluorescent Carbon Dots Powder for Light-Emitting Diodes and Fingerprint Identification.

The emergence and fast development of carbon dots (CDs) provide an unprecedented opportunity for applications in the field of photoelectricity, but their practicability still suffers from complicated synthesis procedures and the substrate dependence of solid-state fluorescence. In this study, we design a unique microwave-assisted solid-phase synthesis route for preparing tunable fluorescent CD powders with yellow, orange, and red fluorescence (Y-CDs, O-CDs, R-CDs) by simply adjusting the mass ratio of reactants, a method which is suitable for the large-scale synthesis of CDs. The Y-/O-/R-CDs were systematically characterized using physics and spectroscopy techniques. Based on the perfect solid-state fluorescence performance of the proposed fluorescent CD powders, the Y-/O-/R-CDs were successfully applied for the construction of multi-color and white light-emitting diode devices at low cost. Furthermore, the Y-CDs displayed much higher yield and luminous efficiency than the O-CDs and R-CDs and were further used for fingerprint identification on the surfaces of glass sheets and tinfoil. In addition, the R-CD aqueous solution fluorescence is sensitive to pH, suggesting its use as a pH indicator for monitoring intracellular pH fluctuations. The proposed series of fluorescent powders composed of CDs may herald a new era in the application of optical components and criminal investigation fields.

Room-Temperature, Homogeneous, Single-Step, and Large-Scale Synthesis of Perovskite Nanoplatelets for Blue Light-Emitting Diodes.

Inorganic perovskite nanocrystals (IPNCs) have attracted considerable attention due to their excellent optoelectronic properties. However, problems arise from anion migration during the preparation of a blue light-emitting diode (LED), and only small-scale syntheses have been conducted on a laboratory scale. By using only Br as the anion here, CsPbBr3 was synthesized in the form of nanoplatelets to eliminate the effects of anion migration and to prepare an inorganic perovskite nanoplatelet (IPNPL) emitting blue light. In addition, the synthesis was performed under ambient conditions at room temperature, and the synthetic process was shortened to enable large-scale synthesis. We used a 1 L bottle for large-scale synthesis, and a photoluminescence quantum yield (PLQY) of 78% was observed at 460 nm. We fabricated LEDs by using IPNPLs, and we observed an electroluminescence peak at 461 nm. The developed synthetic method is expected to pave the way for commercialization of IPNCs and the next-generation display market.

Large-scale in situ self-assembly and doping engineering of zinc ferrite nanoclusters for high performance bioimaging.

Iron oxide nanomaterials has good biocompatibility and safety, and has been used as contrast agents for magnetic resonance imaging (MRI). However, its clinical usefulness is hampered by its difficult preparation on large scale, its rapid clearance in vivo and low target tissue enrichment efficiency. Here, we report the synthesis of water-soluble, biocompatible, superparamagnetic non-stoichiometric zinc ferrite nanoclusters (nZFNCs) of approximately 50 g in a single batch using a one-pot synthesis technique. nZFNCs is a secondary cluster structure with a size of about 40 nm composed of zinc-doped iron oxide nanoparticles with a size of about 6 nm. The surface of nZFNCS is endowed with a large number of carboxyl groups as active sites. By simply controlling the synthesis process and adjusting the proportion of metal precursors, the amount of zinc doping can be controlled, while maintaining the same size to ensure similar pharmacokinetics. Compared with undoped, the magnetic responsiveness and relaxation efficiency of nZFNCs are significantly improved, and the transverse relaxation efficiency (r2) can reach 425.5 mM-1 s-1 (doping amount x = 0.25), which is 7 times higher than that of commercial Resovist and 10 times higher than that of Feridex. In vivo imaging results also further confirmed the excellent contrast enhancement performance of the nanoclusters, which can achieve high contrast for more than 2 h in the liver. The advantage of this platform over comparable systems is that the contrast enhancement features are derived from simple techniques that do not require complex physical and chemical methods.

Preparative Scale Applications of C-H Activation in Medicinal Chemistry.

C-H activation is an attractive methodology to increase molecular complexity without requiring substrate prefunctionalization. In contrast to well-established cross-coupling methods, C-H activation is less explored on large scales and its use in the production of pharmaceuticals faces substantial hurdles. However, the inherent advantages, such as shorter synthetic routes and simpler starting materials, motivate medicinal chemists and process chemists to overcome these challenges, and exploit C-H activation steps for the synthesis of pharmaceutically relevant compounds. In this review, we will cover examples of drugs/drug candidates where C-H activation has been implemented on a preparative synthetic scale (range between 355 mg and 130 kg). The optimization processes will be described, and each example will be examined in terms of its advantages and disadvantages, providing the reader with an in-depth understanding of the challenges and potential of C-H activation methodologies in the production of pharmaceuticals.

Spectro-Microscopic Perceptions into Oxidation Behavior of Large-Scale Molybdenum Disulfide and its Photoelectrical Correlation.

Despite the encouraging properties and research of 2D MoS2 , an ongoing issue associated with the oxidative instability remains elusive for practical optoelectronic applications. Thus, in-depth understanding of the oxidation behavior of large-scale and homogeneous 2D MoS2 is imperative. Here the structural and chemical transformations of large-area MoS2 multilayers by air-annealing with altered temperature and time via combinatorial spectro-microscopic analyses (Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy) are surveyed. The results gave indications pertaining to temperature- and time-dependent oxidation effects: i) heat-driven elimination of redundant residues, ii) internal strain stimulated by the formation of MoO bonds, iii) deterioration of the MoS2 crystallinity, iv) layer thinning, and v) morphological transformation from 2D MoS2 layers to particles. Photoelectrical characterization of the air-annealed MoS2 is implemented to capture the link between the oxidation behavior of MoS2 multilayers and their photoelectrical properties. The photocurrent based on MoS2 air-annealed at 200 °C is assessed to be 4.92 µA, which is 1.73 times higher than that of pristine MoS2 (2.84 µA). The diminution in the photocurrent of the photodetector based on MoS2 air-annealed above 300 °C in terms of the structural, chemical, and electrical conversions induced by the oxidation process is further discussed.

Large-Scale Synthesis of Multifunctional Single-Phase Co2 C Nanomaterials.

Achieving scalable synthesis of nanoscale transition-metal carbides (TMCs), regarded as substitutes for platinum-group noble metals, remains an ongoing challenge. Herein, a 100-g scale synthesis of single-phased cobalt carbide (Co2 C) through carburization of Co-based Prussian Blue Analog (Co-PBA) is reported in CO2 /H2 atmosphere under mild conditions (230 °C, ambient pressure). Textural property investigations indicate a successful preparation of orthorhombic-phased Co2 C nanomaterials with Pt-group-like electronic properties. As a demonstration, Co2 C achieves landmark photo-assisted thermal catalytic CO2 conversion rates with photo-switched product selectivity, which far exceeds the representative Pt-group-metal-based catalysts. This impressive result is attributed to the excellent activation of reactants, colorific light absorption, and photo-to-thermal conversion capacities. In addition to CO2 hydrogenation, the versatile Co2 C materials show huge prospects in antibacterial therapy, interfacial water evaporation, electrochemical hydrogen evolution reaction, and battery technologies. This study paves the way toward unlocking the potential of multi-functional Co2 C nanomaterials.