Liquid-phase Synthesis Research Articles

Seedless and non-thermal liquid-phase reduction synthesis of gold nanotriangles

Seedless and non-thermal liquid-phase reduction synthesis of gold nanotriangles

2. Formation and Production of Powder and Particles 2.2 Particle Synthesis in Liquid Phase 2.2.2 Inorganic Particle Synthesis by using Hydro- and Solvo-thermal Reactions

2. Formation and Production of Powder and Particles 2.2 Particle Synthesis in Liquid Phase 2.2.2 Inorganic Particle Synthesis by using Hydro- and Solvo-thermal Reactions

Graphene Oxide: Key to Efficient Charge Extraction and Suppression of Polaronic Transport in Hybrids with Poly (3-hexylthiophene) Nanoparticles.

Nanoparticles (NPs) of conjugated polymers in intimate contact with sheets of graphene oxide (GO) constitute a promising class of water-dispersible nanohybrid materials of increased interest for the design of sustainable and improved optoelectronic thin-film devices, revealing properties exclusively pre-established upon their liquid-phase synthesis. In this context, we report for the first time the preparation of a P3HTNPs-GO nanohybrid employing a miniemulsion synthesis approach, whereby GO sheets dispersed in the aqueous phase serve as a surfactant. We show that this process uniquely favors a quinoid-like conformation of the P3HT chains of the resulting NPs well located onto individual GO sheets. The accompanied change in the electronic behavior of these P3HTNPs, consistently confirmed by the photoluminescence and Raman response of the hybrid in the liquid and solid states, respectively, as well as by the properties of the surface potential of isolated individual P3HTNPs-GO nano-objects, facilitates unprecedented charge transfer interactions between the two constituents. While the electrochemical performance of nanohybrid films is featured by fast charge transfer processes, compared to those taking place in pure P3HTNPs films, the loss of electrochromic effects in P3HTNPs-GO films additionally indicates the unusual suppression of polaronic charge transport processes typically encountered in P3HT. Thus, the established interface interactions in the P3HTNPs-GO hybrid enable a direct and highly efficient charge extraction channel via GO sheets. These findings are of relevance for the sustainable design of novel high-performance optoelectronic device structures based on water-dispersible conjugated polymer nanoparticles.

Design, synthesis, and biological evaluation of a potential long-acting glucagon-like peptide-1 (GLP-1) analog

By binding to its receptor, glucagon-like peptide-1 (GLP-1) plays various physiological roles, including activating glucose-dependent insulin secretion, inhibiting gastric emptying, and reducing appetite. This suite of activities makes GLP-1 and its analogs an attractive choice for treating type 2 diabetes mellitus in the context of overweight or obesity. This study used different types and lengths of fatty acids to design dual fatty acid side chains for GLP-1 receptor agonists including decanoic, dodecanoic, tetradecanoic, hexadecanoic, dodecanedioic, tetradecanedioic, hexadecanedioic, and octadecanedioic acids. Sixteen GLP-1 receptor agonists (conjugates 13–28) with dual fatty acid side chains were obtained by liquid-phase synthesis. After structural confirmation using high-resolution mass spectrometry, peptide mapping, and circular dichroism, the biological activities of the conjugates were screened. First, the conjugates were screened for albumin binding and activity in GLP-1R-CRE-bla CHO-K1 cells. Albumin binding results suggested a synergistic effect between the two fatty acids in the conjugates. Next, conjugates 18, 19, and 21 selected after primary screening were assessed for receptor affinity, activity in INS-1 cells, plasma stability across different species, and efficacy and pharmacokinetics in normal and db/db mice. One candidate (conjugate 19) was found to have albumin binding of >99 %, good receptor affinity, activities of INS-1 cells, and plasma stability. We found that cellular activities in GLP-1R-CRE-bla CHO-K1 cells and pharmacodynamics and pharmacokinetics in normal and db/db mice for conjugate 19 were superior to those of semaglutide.

PVDF/PLA electrospun fiber membrane impregnated with metal nanoparticles for emulsion separation, surface antimicrobial, and antifouling activities.

Although many superwetting materials have been designed for the treatment of oil-containing wastewater, separation strategies for oil-in-water systems containing bacteria have rarely been reported. Herein, poly(vinylidene difluoride)- and poly(lactic acid)-blended fibrous membranes loaded with silver and copper oxide nanoparticles were successfully prepared by a two-step method of electrostatic spinning and liquid-phase synthesis. The product membrane showed excellent super-oleophilic properties in air and hydrophobicity under oil. It could separate water-in-oil emulsion systems containing surfactants with an efficiency above 90%. More importantly, the nanoparticle-loaded fibers were characterized by material degradability and slowly released ions. The fibers exhibited excellent antibacterial activities against both gram-positive and -negative bacteria. This work provides a feasible strategy for water-in-oil emulsion separation and bacterial treatment of wastewater.

Macro-superlubricity in sputtered MoS2-based films by decreasing edge pinning effect

AbstractTo date, MoS2 can only be achieved at microscale. Edge pinning effect caused by structure defects is the most obvious barrier to expand the size of structural superlubricity to macroscale. Herein, we plan to pin edge planes of MoS2 with nanospheres, and then the incommensurate structure can be formed between adjacent rolling nanoparticles to reduce friction. The sputtered MoS2 film was prepared by the physical vapor deposition (PVD) in advance. Then enough Cu2O nanospheres (∼40 nm) were generated in situ at the edge plane of MoS2 layers by liquid phase synthesis. An incommensurate structure (mismatch angle (θ) = 8°) caused by MoS2 layers was formed before friction. The friction coefficient of the films (5 N, 1,000 r/min) was ∼6.0×10−3 at the most. During friction, MoS2 layers pinned on numerous of Cu2O nanoparticles reduced its edge pinning effect and decreased friction. Moreover, much more incommensurate was formed, developing macro-superlubricity.

2. Formation and Production of Powder and Particles2.2 Particle Synthesis in Liquid Phase

2. Formation and Production of Powder and Particles2.2 Particle Synthesis in Liquid Phase

Obtaining of Metal-Matrix Alloys Based on Ni-Al for ESD Coatings Formation

The experimental results of obtaining complex-alloyed intermetallic alloys by the method of liquid-phase self-propagating high-temperature synthesis (SHS) and their subsequent use for the formation of wear-resistant coatings by the method of electrospark deposition (ESD) are submitted. Metal oxides Cr2O3, NiO, CoO and mineral concentrate containing a larger part of ZrO2 in its composition were used as a melt charge for the SHS experiments. Alloys based on Ni-Al system dopped with Cr, Zr, Co, and C were obtained. It was established that extra addition of C led to the refinement of the alloys microstructure (3-5 times). ESD coatings were formed on steel 45 using the obtained alloys as anode material. The coatings formed by using the alloys doped by Co, Zr, Cr and extra addition of C (0.4 wt%) proved to be maximum wear resistant.

Sn-Substituted Argyrodite Li6PS5Cl Solid Electrolyte for Improving Interfacial and Atmospheric Stability.

Sulfide-based solid electrolytes exhibit good formability and superior ionic conductivity. However, these electrolytes can react with atmospheric moisture to generate H2S gas, resulting in performance degradation. In this study, we attempted to improve the stability of the interface between Li metal and an argyrodite Li6Ps5Cl solid electrolyte by partially substituting P with Sn to form an Sn-S bond. The solid electrolyte was synthesized via liquid synthesis instead of the conventional mechanical milling method. X-ray diffraction analyses confirmed that solid electrolytes have an argyrodite structure and peak shift occurs as substitution increases. Scanning electron microscopy and energy-dispersive X-ray spectroscopy analyses confirmed that the particle size gradually increased, and the components were evenly distributed. Moreover, electrochemical impedance spectroscopy and DC cycling confirmed that the ionic conductivity decreased slightly but that the cycling behavior was stable for about 500 h at X = 0.05. The amount of H2S gas generated when the solid electrolyte is exposed to moisture was measured using a gas sensor. Stability against atmospheric moisture was improved. In conclusion, liquid-phase synthesis could be applied for the large-scale production of argyrodite-based Li6PS5Cl solid electrolytes. Moreover, Sn substitution improved the electrochemical stability of the solid electrolyte.

Rapid and Direct Liquid-Phase Synthesis of Luminescent Metal Halide Superlattices.

The crystallization of nanocrystal building blocks into artificial superlattices has emerged as an efficient approach for tailoring the nanoscale properties and functionalities of novel devices. To date, ordered arrays of colloidal metal halide nanocrystals have mainly been achieved by using post-synthetic strategies. Here, a rapid and direct liquid-phase synthesis is presented to achieve a highly robust crystallization of luminescent metal halide nanocrystals into perfect face-centered-cubic (FCC) superlattices on the micrometer scale. The continuous growth of individual nanocrystals is observed within the superlattice, followed by the disassembly of the superlattices into individually dispersed nanocrystals owing to the highly repulsive interparticle interactions induced by large nanocrystals. Transmission electron microscopy characterization reveals that owing to an increase in solvent entropy, the structure of the superlattices transforms from FCC to hexagonal close-packed (HCP) and the nanocrystals disassemble. The FCC superlattice exhibits a single and slightly redshifted emission, due to the reabsorption-free property of the building block units. Compared to individual nanocrystals, the superlattices have three times higher quantum yield with improved environmental stability, making them ideal for use as ultrabright blue-light emitters. This study is expected to facilitate the creation of metamaterials with ordered nanocrystal structures and their practical applications.

Chemically Understanding the Liquid-Phase Synthesis of Argyrodite Solid Electrolyte Li6PS5Cl with the Highest Ionic Conductivity for All-Solid-State Batteries

Solid electrolytes (SEs), which essentially act as both the electron separator and ion conductor, play an important role in all-solid-state lithium-ion batteries. Liquid-phase synthesis is one of the promising methods as the synthesis of SEs is easily scalable and consumes lower energy. However, due to the complexity of the SEs prepared by liquid-phase synthesis, many problems such as impurities arise, making the liquid electrolytes irreplaceable. This study examines and solves the question why Li3PO4 is produced as an impurity upon preparing Li6PS5Cl argyrodite by approaching the chemical factors. This is accomplished by replacing the hydroxide-based solvent with a thiol-based solvent through liquid-phase synthesis. As a result, the absence of Li3PO4 from the Li6PS5Cl SEs in this study resulted in Li6PS5Cl attaining the highest ionic conductivity value (>2 mS·cm–1) ever obtained through liquid-phase synthesis. Furthermore, the absence of Li3PO4 in the argyrodite SE could magnificently increase the cell’s capacity with remarkable stability.

The effect of a gas atmosphere on the formation of colloidal platinum nanoparticles in liquid phase synthesis

The effect of a gas atmosphere on the formation of colloidal platinum nanoparticles in liquid phase synthesis

Sodium-potassium co-doped layered manganese dioxide cathode material for high performance aqueous zinc-ion batteries

Manganese dioxide with high operating voltage and satisfactory energy density have been identified as the promising cathode materials for aqueous zinc-ion batteries (AZIBs). However, the structural instability of manganese-based materials during the (dis)charging process limits their further development. Herein, sodium-potassium co-doped layered K0.37Na0.18MnO2·xH2O (KNMOH) are synthesized by a liquid-phase synthesis method at room temperature. The co-doping of Na+ and K+ stabilizes the layered structure, widens the layer spacing and has the effect of electrostatic shielding to facilitate the (de)intercalation of Zn2+. Benefiting from the stable structure and nanoscale size, the flower-like KNMOH cathode maintained a high specific capacity of 239.1 mAh·g−1 after 700 cycles at 500 mA·g−1. Simultaneously, this work firstly reveals that the presence of K8(SO4)(SO3OH)6 suppressed the generation of Zn4SO4(OH)6·0.5H2O, resulting in more free Zn2+ and high reversibility. This co-doped design of bimetallic ions insertion enhances the electrochemical performance and provides a new idea for the improvement of the manganese-based cathode materials for AZIBs.

Morphological and structural modification of CaGe2 by annealing with MgCl2/Mg

Ge-based nanosheets and GeH phases were synthesized in the vapor phase using CaGe2 crystals as templates. Ge-based nanosheets have been synthesized in the liquid-phase, but not in the vapor-phase. Compared with liquid-phase synthesis, vapor-phase synthesis is more useful for nanostructure control and impurity addition technologies. These technologies will increase the future popularity of nanosheets. And it is important to apply these technologies after clarifying the effects of certain parameters, such as annealing temperature and changes in the mole fractions. As an introduction to the future development of vapor-phase synthesized Ge-based nanosheets, this study proposes the thermal annealing of CaGe2 powders with MgCl2. Furthermore, the effects of changing the molar fraction containing Mg atoms and the behavior of HCl were investigated from 100 °C–600 °C.

Simple Synthesis of Monodisperse Ultrasmall Au Icosahedral Nanoparticles

Ultrasmall metal nanoparticles (NPs) with a mean diameter below 2 nm are being intensively studied due to their unique structural and chemical properties. At such small sizes, metal particles can appear as various polyhedra with different atomic structures depending on whether electronic effects, surface energy, or the nucleation mechanism govern their crystallization. Therefore, the synthesis of monodisperse nanoparticles of a very small size and well-defined structure requires a good understanding of the different steps of the crystallization process, which can be achieved by conducting and coupling in situ studies at different length and time scales. In this article, we describe the synthesis of ultrasmall gold NPs by reduction of HAuCl4 in solution of oleylamine (OY) in hexane using trialkylsilanes as reducing agents. Thanks to time-resolved in situ small-angle X-ray scattering and X-ray absorption spectroscopy kinetic studies, a competition between nucleation of Au NPs from a solution containing Au(III) clusters and crystallization of a lamellar phase of composition OY-Au(I)-Cl was revealed. In situ X-ray diffraction and pair distribution function (PDF) analysis showed that the first chemical pathway leads to icosahedral NPs while the reduction of OY-Au(I)-Cl leads to fcc NPs. Increasing the reaction rate, achieved by adjusting the silane concentration, changing the nature of the silane (triethylsilane instead of triisopropylsilane), and/or increasing the temperature of reaction, avoided the formation of the Au(I) lamellar phase as the intermediate, leading to monodisperse Au NPs with an icosahedral structure. This fairly simple liquid-phase synthesis method yields highly concentrated suspensions of icosahedral gold NPs, paving the way for their future use in practical applications such as catalysis.

Multistep sequence-controlled supramolecular polymerization by the combination of multiple self-assembly motifs

The precise sequence control of polymer chain is an important research topic of polymer chemistry. Although some methods such as iterative synthesis and supramolecular polymerization have been developed to fabricate sequence-controllable polymer, it is still a great challenge to consecutively prepare multiple supramolecular polymers with different sequence structures. In this work, through the reasonable utilization of assembly motifs, we integrated multiple host-guest recognitions and metal coordination interactions to prepare different sequence-controlled supramolecular polymers by a multistep assembly strategy. This research provides inspiration for the design and preparation of supramolecular polymers with different sequence structures.

ZnO Particles Stabilized in Polymeric Matrix for Liquid-Phase Methanol Synthesis

ZnO supported on hypercrosslinked polystyrene was developed for liquid-phase methanol synthesis. The synthesized catalyst was characterized using the low-temperature nitrogen physisorption, TEM, XPS, XAS, and CO DRIFT methods. The analysis showed that the catalyst has a high specific surface area (720 m2/g) and is characterized by the micro-mesoporous structure typical of the polymer used. The active phase is represented by ZnO species with a hexagonal wurtzite structure. ZnO-HPS showed high activity, selectivity, and stability in liquid-phase methanol synthesis in comparison with the industrial catalyst. The activity of the proposed catalyst was found to be 1.64 times higher than that of the conventional Cu/ZnO/Al2O3.

Synthesis, Composition, Structure, and Electrochemical Behavior of Platinum–Ruthenium Catalysts

The bimetallic PtRu nanoparticles deposited on the carbon support with the metals’ atomic ratio of 1:1 have been obtained by different liquid-phase synthesis methods. The metals’ mass fraction in the obtained PtRu/C catalysts is about 27%. The average size of the bimetallic nanoparticles ranges from 1.9 to 3.9 nm. The activity of the obtained PtRu/C catalysts in the methanol electrooxidation reaction as well as their tolerance to intermediate products of its oxidation have been studied. The sample synthesized by the polyol method has proved to be the most active material. The values of its electrochemical surface area and activity in the methanol electrooxidation reaction are 1.5–1.7 times higher than those of the commercial PtRu/C analogue. Nevertheless, the use of the polyol method leads to losses of the metals during the synthesis. Therefore, this method needs further optimization.

Super silyl-based stable protecting groups for both the C- and N-terminals of peptides: applied as effective hydrophobic tags in liquid-phase peptide synthesis.

Tag-assisted liquid-phase peptide synthesis (LPPS) is one of the important processes in peptide synthesis in pharmaceutical discovery. Simple silyl groups have positive effects when incorporated in the tags due to their hydrophobic properties. Super silyl groups contain several simple silyl groups and play an important role in modern aldol reactions. In view of the unique structural architecture and hydrophobic properties of the super silyl groups, herein, two new types of stable super silyl-based groups (tris(trihexylsilyl)silyl group and propargyl super silyl group) were developed as hydrophobic tags to increase the solubility in organic solvents and the reactivity of peptides during LPPS. The tris(trihexylsilyl)silyl group can be installed at the C-terminal of the peptides in ester form and N-terminal in carbamate form for peptide synthesis and it is compatible with hydrogenation conditions (Cbz chemistry) and Fmoc-deprotection conditions (Fmoc chemistry). The propargyl super silyl group is acid-resistant, which is compatible with Boc chemistry. Both tags are complementary to each other. The preparation of these tags requires less steps than previously reported tags. Nelipepimut-S was synthesized successfully with different strategies using these two types of super silyl tags.

Rapid and column-chromatography-free peptide chain elongation via a one-flow, three-component coupling approach.

Short peptides are extremely important as drugs and building blocks for the syntheses of longer peptides. Both solid- and liquid-phase peptide syntheses suffer from a large number of synthetic steps, high cost, and/or tedious purification. Here, we developed a rapid, mild, inexpensive, and column-chromatography-free peptide chain elongation via a one-flow, three-component coupling (3CC) approach that is the first to use α-amino acid N-carboxy anhydrides (α-NCAs) both as electrophiles and nucleophiles. We demonstrated the high-yielding and column-chromatography-free syntheses of 17 tripeptides, as well as a gram-scale synthesis of a tripeptide. The total synthesis of beefy meaty peptide was achieved by repeating the 3CC approach with the addition of only one column chromatographic purification. We also demonstrated a one-flow tripeptide synthesis via in situ preparation of α-NCA starting from three readily available protected amino acids. With this study, we achieved dramatic reductions in both time and cost compared with typical solid-phase synthesis.