Current Synthesis Methods Research Articles

Towards the clinical translation of a silver sulfide nanoparticle contrast agent: large scale production with a highly parallelized microfluidic chip.

Ultrasmall silver sulfide nanoparticles (Ag2S-NP) have been identified as promising contrast agents for a number of modalities and in particular for dual-energy mammography. These Ag2S-NP have demonstrated marked advantages over clinically available agents with the ability to generate higher contrast with high biocompatibility. However, current synthesis methods for inorganic nanoparticles are low-throughput and highly time-intensive, limiting the possibility of large animal studies or eventual clinical use of this potential imaging agent. We herein report the use of a scalable silicon microfluidic system (SSMS) for the large-scale synthesis of Ag2S-NP. Ag2S-NP produced using this system were compared to bulk synthesis and a commercially available microfluidic device through characterization, contrast generation, in vivo imaging, and clearance profiles. Using SSMS chips with 1 channel, 10 parallelized channels, and 256 parallelized channels, we determined that the Ag2S-NP produced were of similar quality as measured by core size, concentration, UV-visible spectrometry, and in vitro contrast generation. Moreover, by combining parallelized chips with increasing reagent concentration, we were able to increase output by an overall factor of 5,100. We also found that in vivo imaging contrast generation was consistent across synthesis methods and confirmed renal clearance of the ultrasmall nanoparticles. Finally, we found best-in-class clearance of the Ag2S-NP occurred within 24h. These studies have identified a promising method for the large-scale production of Ag2S-NP, paving the way for eventual clinical translation.

Visible‐Light‐Induced Stereoselective C(sp3)−C(sp3)−H Glycosylation for the Synthesis of C‐Glycoamino Acid Derivatives

AbstractChiral C‐Glycosyl amino acids are prevalent structural motifs found in pharmaceuticals and natural products, making them a significant dimension for exploration in modern pharmaceutical and medicinal chemistry. However, the current synthesis methods for these compounds face numerous environmental and practical challenges, highlighting the critical need to establish more sustainable approaches. Herein, we report a simple and powerful strategy for the stereoselective synthesis of C‐glycoamino acids derivatives. This method features the design and use of (−)/(+)‐camphorsultam as an ideal chiral auxiliary, shielding one prochiral face of the glycine α‐carbon efficiently and imposing a high kinetic barrier for the epimerization of thus‐generated chiral α‐carbon that two configuration products of R and S could be achieved independently. It proceeds under mild conditions, shows broad scope, and allows for the direct stereoselective glycosylation without metal and chiral ligand.

Microenvironment regulation to synthesize sub-3 nm Pt-based high-entropy alloy nanoparticles enabling compressed lattice to boost electrocatalysis

Platinum (Pt) is inevitably employed to facilitate various electrocatalysis including hydrogen oxidation/evolution and oxygen reduction reactions (HOR/HER/ORR), the foundation for renewable energy conversion and storage. Pt-based high-entropy-alloy (HEA) catalysts have been recently presenting promises to improve intrinsic activity of unit mass Pt. However, their current synthesis methods always produce large particles—some can control small size but have to use complicated recipe and/or highly toxic and expensive chemicals. Alternatively, a facile microenvironment regulation strategy is herein proposed to tune solvent polarity and nanoparticle-support interactions within the precursors for carbon-thermal shock pyrolysis. We found that the decreased solvent polarity and enhanced particle-support affinity can jointly control the nanoparticle size ultimately to ~2.68nm with ~10wt % Pt loading. The compressed lattice fringe in such HEA particles leads to electron accumulation at Pt atoms and build a moderate charge density rearrangement, showing superior multifunctional HER/HOR/ORR activity to Pt/C in acidic media.

Sustainable synthesis of pyrochlore gadolinium zirconate through the molten salt method: A green approach

Gadolinium zirconate (GZO) with pyrochlore phase exhibits exceptional promise for thermal barrier coatings due to its notable low thermal conductivity. Current synthesis methods for GZO, however, are frequently complex, energy-intensive, and environmentally hazardous. A more sustainable and eco-friendly synthesis route for GZO is thus imperative. This research introduces a green synthesis process for pyrochlore GZO utilizing the molten salt method.Experimental synthesis at varying temperatures revealed changes in the phase composition of GZO via the molten salt method. Fluorite GZO formed at 1200 °C, while pyrochlore GZO appeared at 1400 °C. XRD refinement, TEM, and Raman spectroscopy confirmed these results. Density Functional Theory (DFT) calculations established the minimum theoretical synthesis temperature for pyrochlore GZO at 1370 °C. Limiting factors for reactions at different temperatures during the molten salt synthesis process were identified. DFT calculations and experiments verified that the fluorite structure GZO transitions to pyrochlore GZO at temperatures exceeding 1370 °C. Property tests on pyrochlore GZO samples synthesized through two pathways showed minimal differences. This study thus lays a theoretical foundation for the eco-friendly synthesis of pyrochlore GZO material using the molten salt method and offers insights for future process development.

Equilibrium densities of intrinsic defects in transition metal diselenides of molybdenum and tungsten.

Point defects are thermodynamically stabilized in all crystalline materials, with increased densities negatively impacting the properties and performance of transition metal dichalcogenides (TMDs). While recent point defect reduction methods have led to considerable improvements in the optoelectronic properties of TMDs, there is a clear need for theoretical work to establish the lower limit of defect densities, as represented by thermal equilibrium. To that end, an abinitio and thermodynamic analysis of the equilibrium densities of intrinsic point defects in MoSe2 and WSe2 is presented. The intrinsic defect formation energies at the limits of the selenium and metal-rich regimes are determined by density functional theory (DFT) and then augmented with elemental chemical potential functions to determine temperature- and pressure-dependent formation energies. Equilibrium defect densities are determined for MSe, SeM, vM, and vSe, where M and v, respectively, represent the metal and the vacancy, as a function of synthesis temperature and pressure. The effects of vibrational free energy contributions and treatment of the DFT exchange-correlation potential are found to be non-negligible. Calculated equilibrium densities are several orders of magnitude below reported defect densities in TMDs made by chemical vapor deposition, chemical vapor transport, and flux methods, thereby establishing that current synthesis methods are either kinetically limited or impurity dominated.

Microwave-Assisted Hydrothermal Synthesis of Photocatalytic Truncated-Bipyramidal TiO2/Ti3CN Heterostructures Derived from Ti3CN MXene.

TiO2/MXene heterostructure has garnered significant interest as a photocatalyst due to its large surface area and efficient charge carrier separation at the interface. However, current synthesis methods produce TiO2 without clear crystal faceting and often require complicated postprocessing step, limiting its practical applications. We demonstrate a facile and controlled microwave-assisted hydrothermal synthesis for transforming multilayered Ti3CN MXene to a truncated-bipyramidal TiO2/Ti3CN heterostructure. The resulting TiO2 nanocrystals at the Ti3CN surface exhibited crystalline anatase truncated bipyramids, exposing {001} and {101} facets. We further tailored an indirect optical band gap of the TiO2/Ti3CN heterostructure in the range of 3.17-3.23 eV by varying the hydrothermal synthesis time from 15 min to 5 h at a fixed temperature of 160 °C. Efficient charge separation allowed us to decompose 97% of methylene blue (MB) within 30 min of ultraviolet (UV) light irradiation, ∼3.9-fold faster than the benchmark P25, higher than any other TiO2/MXene heterostructures. With simulated white light, we achieved over 60% efficiency of the dye decomposition within 2 h of irradiation, which resulted in 1.5-fold faster kinetics than P25. We also observed a similar excellent performance of Ti3CN-derived TiO2 in decomposing various persistent synthetic dyes, including commercial textile dye, methyl orange, and rhodamine B. In conclusion, our study provides a strategy for utilizing MXene chemical reactivity to produce highly crystalline optically active TiO2/Ti3CN heterostructure. The developed heterostructure can serve as an efficient photocatalyst for the degradation of organic pollutants.

Synthesis of pyrazolopyrano pyrimidines via one-pot solvent free greener approach utilizing lanthanum trifluoroacetate and trichloroacetate Lewis acids supported on mesoporous silica: An experimental and DFT studies

Herein, an economic, environment-benign and sustainable greener protocol was developed for the production of pyrazolopyrano pyrimidines utilizing water competent Lanthanum trifluoroacetate and trichloroacetate Lewis acids based over silica via one-pot reaction involving aromatic aldehydes, ethyl acetoacetate, hydrazine hydrate and barbituric acid. The capability to incorporate a broad spectrum of functional groups, fast reaction times, best product yield, gentle reaction medium, solvent-free synthesis and the easy recoverability and multiple-time reusability of catalysts are notable advantages of the present synthetic approach. Furthermore, DFT studies was employed to study the pyrazolopyrano pyrimidines (5a-l), highlighting role of computational methods in predicting and understanding reactivity. Consequently, the integration of DFT studies with synthesis has proven to be a potent strategy for creating the current synthesis method.

Synthesis of submillimeter-size two-dimensional metal iodides single crystal via undercooling control strategy

Two-dimensional (2D) metal iodides have attracted significant attention in recent years due to their superior optoelectronic properties. However, the current synthesis methods for 2D metal iodides are either time-consuming or not able to synthesize large size crystal. Here we develop an undercooling control strategy based on hot plate assisted vertical vapor deposition for the synthesis of submillimeter-size 2D bismuth iodide (BiI3) single crystal. The whole synthesis process is efficient and only takes one minute in atmosphere. The problem of high nucleation density can be addressed by undercooling control, avoiding the collide of crystals before they grow into large size. This general approach is versatility and can be expanding to synthesize other 2D metal iodides. In addition, nonlinear optical property investigation of BiI3 crystal reveals a thickness-dependent and power-dependent second harmonic response. Our strategy presents a new solution for facile preparation of large-size 2D metal iodides, facilitating their fundamental physics studies and next-generation optoelectronics development.

Advances in Engineering Circular RNA Vaccines.

Engineered circular RNAs (circRNAs) are a class of single-stranded RNAs with head-to-tail covalently linked structures that integrate open reading frames (ORFs) and internal ribosome entry sites (IRESs) with the function of coding and expressing proteins. Compared to mRNA vaccines, circRNA vaccines offer a more improved method that is safe, stable, and simple to manufacture. With the rapid revelation of the biological functions of circRNA and the success of Severe Acute Respiratory Coronavirus Type II (SARS-CoV-2) mRNA vaccines, biopharmaceutical companies and researchers around the globe are attempting to develop more stable circRNA vaccines for illness prevention and treatment. Nevertheless, research on circRNA vaccines is still in its infancy, and more work and assessment are needed for their synthesis, delivery, and use. In this review, based on the current understanding of the molecular biological properties and immunotherapeutic mechanisms of circRNA, we summarize the current preparation methods of circRNA vaccines, including design, synthesis, purification, and identification. We discuss their delivery strategies and summarize the challenges facing the clinical application of circRNAs to provide references for circRNA vaccine-related research.

In Situ Formation of Iodide Precursor for Perovskite Quantum Dots with Application in Efficient Solar Cells.

Perovskite quantum dots (PQDs) become a kind of competitive material for fabricating high-performance solar cells due to their solution processability and outstanding optoelectronic properties. However, the current synthesis method of PQDs is mostly based on the binary-precursor method, which results in a large deviation of the I/Pb input ratio in the reaction system from the stoichiometric ratio of PQDs. Herein, a ternary-precursor method with an iodide source self-filling ability is reported for the synthesis of the CsPbI3 PQDs with high optoelectronic properties. Systematically experimental characterizations and theoretical calculations are conducted to fundamentally understand the effects of the I/Pb input molar ratio on the crystallographic and optoelectronic properties of PQDs. The results reveal that increasing the I/Pb input molar ratio can obtain ideal cubic structure PQDs with iodine-rich surfaces, which can significantly reduce the surface defects of PQDs and realize high orientation of PQD solids, facilitating charge carrier transport in the PQD solids with diminished nonradiative recombination. Consequently, the PQD solar cells exhibit an impressive efficiency of 15.16%, which is largely improved compared with that of 12.83% for the control solar cell. This work provides a feasible strategy for synthesizing high-quality PQDs for high-performance optoelectronic devices.

Rapid and inexpensive synthesis of liter-scale SiC aerogels

Ceramic aerogels are promising materials for thermal insulation and protection under harsh environments. Yet current synthesis methods fail to provide an energy-, time-, and cost-effective route for high-throughput production and large-scale applications, especially for non-oxide ceramic aerogels. Here we reported a way to synthesize SiC aerogels within seconds and over liter scale, with a demonstrated throughput of ~16 L min−1 in a typical lab experiment. The key lies in renovated combustion synthesis and a fast expansion from powder reactants to aerogel products over 1000% in volume. The synthesis process is self-sustainable and requires minimal energy input. The product is very cheap, with an estimated price of ~$0.7 L−1 (~$7 kg−1). The obtained SiC aerogels have excellent thermo-mechanical properties, including low thermal conductivity, high elasticity, and damage tolerance. Our invention not only offers a practical pathway for large-scale applications of ceramic aerogels, but also calls for rethinking of combustion synthesis in one-step conversion from raw chemicals to bulk products ready for practical applications.

Hydrothermal Synthesis of β-NiS Nanoparticles and Their Applications in High-Performance Hybrid Supercapacitors.

In this work, β-NiS nanoparticles (NPs) were efficiently prepared by a straightforward hydrothermal process. The difference in morphology between these NiS NPs was produced by adding different amounts of thiourea, and the corresponding products were denoted as NiS-15 and NiS-5. Through electrochemical tests, the specific capacity (Cs) of NiS-15 was determined to be 638.34 C g-1 at 1 A g-1, compared to 558.17 C g-1 for NiS-5. To explore the practical application potential of such β-NiS NPs in supercapacitors, a hybrid supercapacitor (HSC) device was assembled with activated carbon (AC) as an anode. Benefitting from the high capacity of the NiS cathode and the large voltage window of the device, the NiS-15//AC HSC showed a high energy density (Ed) of 43.57 W h kg-1 at 936.92 W kg-1, and the NiS-5//AC HSC provided an inferior Ed of 37.89 W h kg-1 at 954.79 W kg-1. Both HSCs showed excellent cycling performance over 6000 cycles at 10 A g-1. The experimental findings suggest that both NiS-15 and NiS-5 in this study can serve as potential cathodes for high-performance supercapacitors. This current synthesis method is simple and can be extended to the preparation of other transition metal sulfide (TMS)-based electrode materials with exceptional electrochemical properties.

Advance of Near-Infrared Emissive Carbon Dots in Diagnosis and Therapy: Synthesis, Luminescence, and Application.

Carbon dots (CDs) with good optical properties, biocompatibility, easy functionalization, and small size have attracted more and more attention and laid a good foundation for their applications in the biomedicine field. CDs emitted in near-infrared regions (NIR-CDs) can achieve high penetration depth imaging and produce high cytotoxic substance for disease treatment. Therefore, NIR-CDs are promising materials to realize high-quality imaging-guided diagnostic and therapeutic integration. This review first introduces the current mainstream synthesis methods of NIR-CDs by "top-down" and "bottom-up". Second, the luminescence modes of NIR-CDs are introduced, and the luminescence mechanisms based on carbon core state, surface state, molecular state, and crosslinking enhanced emission are summarized. Third, the applications and principles of NIR-CDs in imaging, drug delivery, and non-invasive therapeutics are introduced from a view of diagnosis and therapy. Finally, their prospects and challenges in biomedical and biotechnological applications are outlined.

Synthesis of flower-like covalent organic frameworks for photocatalytic selective oxidation of sulfide

BackgroundCovalent organic frameworks (COFs)-based photocatalysts have garnered significant attention for their potential in highly efficient and selective sulfide oxidation. However, the current synthesis methods of COF-based catalysts involve complex multi-step procedures, and better methods need to be upgraded for synthesis. MethodsIn this study, a flower-like COF-based photocatalyst (f-COFs) was synthesized by one-pot method at room temperature using zinc chloride (ZnCl2) as catalyst. The photocatalytic performance of f-COFs was investigated using methyl phenyl sulfide as substrate. Significant FindingsZinc ions remain on the f-COFs synthesized by this method. EDX analysis and XPS techniques were used to confirm the presence of zinc ions. The presence of zinc ions controls the self-assembly of COFs to form unique flower-like microstructure. Its flower-like microstructure provides a strong light absorption capacity. At the same time, the recombination of charge is inhibited, thus promoting the energy and electron transfer during the photocatalytic reaction. These properties allow reactive oxygen species to be prevalent in the reaction process of f-COFs as a photocatalyst, driving the conversion of methyl phenyl sulfide to sulfoxide within 5 h with excellent performance of 95 % conversion and 99 % selectivity.

New Method for Obtaining Carboxylic Derivatives of Oxazolo[5,4-b]pyridine Based on 3-Aminopyridine-2(1H)-ones

Current methods for synthesis of oxazolo[5,4-b]- and oxazolo[4,5-b]pyridines have several limitations, such as severe reaction conditions, lengthy reaction times, low yields and concurrent formation of side reaction products. This article presents the results of study focused on a one-step method for the synthesis of new derivatives of oxazolo[5,4-b]pyridine incorporating an aliphatic carboxylic group as a linker. During the investigation of acylation reactions of 3-aminopyridine-2(1H)-ones with cyclic anhydrides of dicarboxylic acids (succinic, maleic and glutaric), it was found that the monoamides formed at the initial stage undergo intramolecular cyclization yielding derivatives of oxazolo[5,4-b]pyridine. Subsequently, the reaction conditions were studied and optimized to achieve the target compounds with high yield and purity. The potential anti-inflammatory activity of the obtained derivatives of oxazolo[5,4-b]pyridine was evaluated by molecular docking method using AutoDock Vina software. Compounds 11-14b exhibited higher binding affinity with the selected target protein Prostaglandin synthase-2 (1CX2) compared to the reference anti-inflammatory drug diclofenac. Thus, taking into account the results of in silico analyses, the newly synthesized oxazolo[5,4-b]pyridine derivatives based on 3-aminopyridine-2(1H)-ones are promising candidates for further investigation of their potential anti-inflammatory activity through in vivo methods.

A highly sensitive and selective colorimetric aptasensor for detecting sulfadiazine in river waters based on gold nanoparticles synthesized from discarded Longan seed extract.

Gold nanoparticles (AuNPs) were extensively employed for in-situ detection sulfadiazine (SDZ) residues, yet current synthesis methods suffer from complex procedures, reagent pollution of the environment, and low particle quality. This study presents a novel synthesis method using discarded longan seed extract as a reducing agent to synthesized high-quality AuNPs, and then can be used for in-situ SDZ detection. Response surface methodology (RSM) was employed to optimize synthesis parameters, which resulted in five optimal combinations that enhanced the flexibility of synthesis. These AuNPs, ranging in size from 18.26nm to 33.8nm with zeta potentials from - 29.5mV to - 14.3mV, were successfully loaded with functional groups from longan seed extract. In the detection of SDZ, the colorimetric aptasensor demonstrated excellent sensitivity and selectivity over other antibiotics with a limit of detection and quantification at 70.98ng·mL-1 and 236.59ng·mL-1 in the concentration range of 200-800ng·mL-1. Recoveries of spiked SDZ samples ranged from 97.90% to 106.7%, with RSD values below 9.25%. Meanwhile, the aptasensor exhibited exceptional diagnostic efficacy (AUC: 0.976) compared to UV absorption methods in the ROC evaluation. In conclusion, this study highlights the potential of using AuNPs synthesized from longan seed extract coupled with aptamer technology as a straightforward detection method for SDZ in river water, offering promising applications in environmental monitoring.

Exploring undiscovered public knowledge in neuroscience.

In this essay, I argue that the combination of research synthesis and philosophical methods can fill an important methodological gap in neuroscience. While experimental research and formal modelling have seen their methods progressively increase in rigour and sophistication over the years, the task of analysing and synthesizing the vast literature reporting new results and models has lagged behind. The problem is aggravated because neuroscience has grown and expanded into a vast mosaic of related but partially independent subfields, each with their own literatures. This fragmentation not only makes it difficult to see the full picture emerging from neuroscience research but also limits progress in individual subfields. The current neuroscience literature has the perfect conditions to create what the information scientist Don Swanson called "undiscovered public knowledge"-knowledge that exists in the mutual implications of different published pieces of information but that is nonetheless undiscovered because those pieces have not been explicitly connected. Current methods for rigorous research synthesis, such as systematic reviews and meta-analyses, mostly focus on combining similar studies and are not suited for exploring undiscovered public knowledge. To that aim, they need to be adapted and supplemented. I argue that successful exploration of the hidden implications in the neuroscience literature will require the combination of these adapted research synthesis methods with philosophical methods for rigorous (and creative) analysis and synthesis.

A Uni-Micelle Approach for the Controlled Synthesis of Monodisperse Gold Nanocrystals.

Small-size gold nanoparticles (AuNPs) are showing large potential in various fields, such as photothermal conversion, sensing, and medicine. However, current synthesis methods generally yield lower, resulting in a high cost. Here, we report a novel uni-micelle method for the controlled synthesis of monodisperse gold nanocrystals, in which there is only one kind micelle containing aqueous solution of reductant while the dual soluble Au (III) precursor is dissolved in oil phase. Our synthesis includes the reversible phase transfer of Au (III) and "uni-micelle" synthesis, employing a Au (III)-OA complex as an oil-soluble precursor. Size-controlled monodisperse AuNPs with a size of 4-11 nm are synthesized by tuning the size of the micelles, in which oleylamine (OA) is adsorbed on the shell of micelles and enhances the rigidity of the micelles, depressing micellar coalescence. Monodisperse AuNPs can be obtained through a one-time separation process with a higher yield of 61%. This method also offers a promising way for the controlled synthesis of small-size alloy nanoparticles and semiconductor heterojunction quantum dots.

Tandem Electrooxidation - Reductive Amination of Biobased Isohexides Towards Bicyclic Diamines.

Isohexide-derived diamines are considered preferred precursors for the production of biobased polyurethanes and polyamides. However, current synthesis methods from isohexides suffer from serious issues concerning selectivity and the recyclability of the process auxiliaries (e. g. homogeneous catalysts), which renders a translation to the industry highly unlikely. Here, we report on the production of such diamine building blocks, via a tandem electrooxidation - reductive amination process in which the process auxiliaries can be easily recycled. The application of (immobilized) TEMPO in combination with simple halides (e. g. NaBr) in the electrochemical step even enables the oxidation of the sterically hindered exo-OHs of the isohexides to the corresponding diketones (yield up to 99 %). In the subsequent reductive amination, the produced ketones are atom-efficiently converted to isohexide diamines utilizing NH3, H2, and Ru/C and an acid resin cocatalyst.

Tris(2-hydroxyethyl)ammonium-Based Protic "Ionic Liquids": Synthesis and Characterization.

The proton transfer associated with the synthesis of protic ionic liquids (PILs) is often incomplete, meaning that the parent compounds may coexist with the ionic species. However, PILs are proposed for many applications as pure compounds without analysis of their ionicity. This work focuses on tris(2-hydroxyethyl)ammonium-based PILs with lactate, hydrogen succinate, hydrogen malate, and dihydrogen citrate anions. The interest of these anions lies in their low toxicity and capacity to disrupt the hydrogen-bonding network inherent to biopolymers. To improve current synthesis methods of this kind of PILs, which frequently lead to impurities derived from decomposition of reactants, working in the absence of solvents and at moderate temperatures is proposed. Through NMR studies, the ionicity of these systems was found to be low, from 20% to 86%, so the widely used term "ionic liquid" is not rigorous and must be used with caution. The un-ionized acid and base species coexist with the corresponding ionic forms, and this has to be considered in the studies involving these chemicals. The thermal characterization of the PILs was carried out. The influence of the anion on the thermal stability was found to be low. Isothermal thermogravimetric analysis showed that mass loss of these PILs starts at temperatures close to 350 K.