Unconventional Synthesis Research Articles

UNLEASH: Ultralow Nanocluster Loading of Pt via Electro-Acoustic Seasoning of Heterocatalysts.

The shift toward sustainable energy has fueled the development of advanced electrocatalysts to enable green fuel production and chemical synthesis. To date, no material outperforms Pt-group catalysts for key electrocatalytic reactions, necessitating advanced catalysts that minimize use of these rare and expensive constituents (i.e., Pt) to reduce cost without sacrificing activity. Whilst a myriad of routes involving co-synthesis of Pt with other elements have been reported, the Pt is often buried within the bulk of the composite, rendering a large proportion of it inaccessible to the interfacial electrocatalytic reaction. Surface decoration of Pt on arbitrary substrates is therefore desirable to maximize catalytic activity; nevertheless, Pt electrodeposition suffers from clustering and ripening effects that result in large ( ) aggregates that hinder electrocatalytic activity. Herein, an unconventional synthesis method is reported that utilizes high-frequency (10 MHz) acoustic waves to electrochemically 'season' a gold working electrode with an ultralow loading of Pt nanoclusters. The UNLEASH platform is shown to facilitate high-density dispersion of nanometer-order clusters at the bimetallic interface to enable superior atomic utilization of Pt. This is exemplified by its utility for methanol oxidation reaction (MOR), wherein a mass activity of 5.28 A is obtained, outperforming all other Au/Pt bimetallic electrocatalysts reported todate.

INFLUENCE OF TIME AND TEMPERATURE IN THE MICROWAVE-ASSISTED HYDROTHERMAL TREATMENT OF MAGNETITE NANOPARTICLES

Magnetite is an iron oxide that has been extensively investigated for its utilization in the development of drug delivery nanocarriers. Generally, magnetite nanoparticles are obtained through the chemical route of co-precipitation. However, since the outcome properties of the resulted nanoparticles are limited in terms of possibility to control the size and size distribution and to ensure the reproducibility of the synthesis process, unconventional synthesis routes are constantly investigated. Specifically, the microwave-assisted hydrothermal method represents an alternative with tremendous potential owing to the possibility of varying the treatment parameters, i.e., pressure, temperature, time. Thus, the present study aimed to investigate the influence of time and temperature upon the structural and physico-chemical properties of magnetite nanoparticles.

Subverting the Canon: Novel Cancer-Promoting Functions and Mechanisms for snoRNAs.

Small nucleolar RNAs (snoRNAs) constitute a class of intron-derived non-coding RNAs ranging from 60 to 300 nucleotides. Canonically localized in the nucleolus, snoRNAs play a pivotal role in RNA modifications and pre-ribosomal RNA processing. Based on the types of modifications they involve, such as methylation and pseudouridylation, they are classified into two main families-box C/D and H/ACA snoRNAs. Recent investigations have revealed the unconventional synthesis and biogenesis strategies of snoRNAs, indicating their more profound roles in pathogenesis than previously envisioned. This review consolidates recent discoveries surrounding snoRNAs and provides insights into their mechanistic roles in cancer. It explores the intricate interactions of snoRNAs within signaling pathways and speculates on potential therapeutic solutions emerging from snoRNA research. In addition, it presents recent findings on the long non-coding small nucleolar RNA host gene (lncSNHG), a subset of long non-coding RNAs (lncRNAs), which are the transcripts of parental SNHGs that generate snoRNA. The nucleolus, the functional epicenter of snoRNAs, is also discussed. Through a deconstruction of the pathways driving snoRNA-induced oncogenesis, this review aims to serve as a roadmap to guide future research in the nuanced field of snoRNA-cancer interactions and inspire potential snoRNA-related cancer therapies.

Inexpensive Fabrication of Sn-Ag- Cu/Cu:ZnO/Al/PET Memristive Devices through Unconventional Synthesis Techniques

In the last few decades there has been rapidly growing research interest in resistive switching devices which led to tremendous technological advancements. In this work, copper (Cu) doped zinc oxide (ZnO) thin film was deposited on Aluminum coated PET conductive sheets having a sheet resistance of 20 Ω. Soldering balls of 2 mm diameter consisting of 96.5% Sn, 3% Ag and 0.5% Cu alloy were dropped into this thin film to form the Sn-Ag- Cu/Cu:ZnO/Al/PET memristive devices. No additional annealing temperature was required as the heat transfer from 350 C hot soldering ball onto the Cu:ZnO thin film was sufficient to anneal the thin film. The electronic characteristics of the device were obtained by employing a function generator and an oscilloscope instead of an expensive source meter. The elimination of redundant hot furnace (for annealing) and source meter (for I-V characterization) resulted in the improvement of total equipment expenses by ~96%.

Unconventional Synthesis of Hierarchically Twinned Copper as Efficient Electrocatalyst for Nitrate-Ammonia Conversion.

Twin boundary (TB) engineering provides exciting opportunities to tune the performance levels of metal-based electrocatalysts. However, the controllable construction of TB greatly relies on surfactants, blocking active sites, and electron transfer by surfactants. Here, a surfactant-free and facile strategy is proposed for synthesizing copper (Cu) nanocatalysts with dense hierarchical TB networks (HTBs) by the rapid thermal reductions in metastable CuO nanosheets in H2 . As revealed by in situ transmission electron microscopy, the formation of HTBs is associated with the fragmentation of nanosheets in different directions to generate abundant crystal nuclei and subsequently unconventional crystal growth through the collision and coalescence of nuclei. Impressively, the HTBs endow Cu with excellent electrocatalytic performance for direct nitrate-ammonia conversion, superior to that of Cu with a single-oriented TB and without TB. It is discovered that the HTBs induce the formation of compressive strains, thereby creating a synergistic effect of TBs and strains to efficiently tune the binding energies of Cu with nitrogen intermediates (i.e., NO2 *) and thus promote the tandem reaction process of NO3 - -to-NO2 - and subsequent NO2 - -to-NH3 electrocatalysis. This work demonstrates the crucial role of HTBs for boosting electrocatalysis via the synergistic effect of TBs and strains.

Synthesis and Characterization Conducting Polymer Supported CDS-ZNS Nano Composites Used for Various Applications

Keys include undertaking polymer synthesis and physical property research. Conductive is polyaniline. The presence of pristine nano CdS particles in the matrix was demonstrated by X-ray diffraction (XRD).
 In this study, four sol-gel techniques are used to prepare nanostructured polyaniline (PANI). PANI molecular structure was characterized using X-ray diffraction to assess the morphology of PANI samples.
 The results of the prepared PANI's characterization reveal that the unconventional synthesis methods utilized to create it drastically changed its morphology, chemical composition, crystallinity, conductivity, and surface area. The outcomes of the characterization supported this. The manufacturing and properties of polyaniline conducting polymers are examined in this research. The classic and grafted techniques of polyaniline synthesis have been examined. The relationship between structure and properties is established by this high-accuracy development procedure. In the future, polyaniline with altered structure may be employed.
 PANI/CdS nanocomposites have higher DC conductivity than PANI, according to observations.
 In situ production of conducting polyaniline nanocomposites with CdS nanoparticles was achieved by oxidizing aniline with cadmium sulphate at 3.5 pH. Electrical conductivity of polyaniline is influenced by CdS-nanoparticles. In contrast to pure polyaniline, the electrical conductivity of polyaniline nano-composite is increased by the homogenous intercalation of CdS nanoparticles, which results in a cooperative phenomenon between polyaniline and the nanoparticles.

Intramolecular Through-Space Double-Electron Transfer Between A Pair of Redox-Active Guanidine Units Aligned by Dithiolate Bridges.

Using unconventional synthesis protocols, two redox-active triguanidine units are connected by a dithiolate bridge, aligning the two redox-active units in close proximity. The reduced, neutral and the tetracationic redox states with two dicationic triguanidine units are isolated and fully characterized. Then, the dicationic redox states are prepared by mixing the neutral and tetracationic molecules. At low temperatures, the dications are diamagnetic (singlet ground state) with two different triguanidine units (neutral and dicationic). At room temperature, the triplet state with two radical monocationic triguanidine units is populated. At low temperature (210 K), chemical exchange by intramolecular through-space electron-transfer between the two triguanidine units is evidenced by EXSY NMR spectroscopy. Intramolecular through-space transfer of two electrons from the neutral to the dicationic triguanidine unit is accompanied by migration of the counterions in opposite direction. The rate of double-electron transfer critically depends on the bridge. No electron-transfer is measured in the absence of a bridge (in a mixture of one dicationic and one neutral triguanidine), and relatively slow electron transfer if the bridge does not allow the two triguanidine units to approach each other close enough. The results give detailed, quantitative insight into the factors that influence intramolecular through-space double-electron-transfer processes.

Quantum Tunneling Mediated Low-Temperature Synthesis of Interstellar Hemiacetals.

Sugars and sugar-related molecules are ubiquitous in carbonaceous meteorites and in star-forming regions, but the underlying mechanisms of their formation have remained largely elusive. Herein, we report an unconventional synthesis of the hemiacetal, (R/S)-1-methoxyethanol (CH3OCH(OH)CH3), through quantum tunneling mediated reactions in low-temperature interstellar model ices composed of acetaldehyde (CH3CHO) and methanol (CH3OH). The detection of racemic 1-methoxyethanol through a bottom-up synthesis from simple, abundant precursor molecules within interstellar ices represents a vital starting point to the formation of complex interstellar hemiacetals. Once synthesized, hemiacetals may act as possible precursors to interstellar sugars and sugar-related molecules in deep space.

Effectiveness of the 3D-printing procedure in the synthesis of hybrid catalysts for the direct hydrogenation of CO2 into dimethyl ether

This work highlights the effectiveness of an unconventional synthesis of hybrid systems for the direct hydrogenation of carbon dioxide into dimethyl ether (DME), based on micro-extrusion of a ink-like catalytic paste by a robocasting procedure. Due to the possibility to exert a fine control over the structure, surface and geometric architecture, the adopted printing technique really ensures a superior management of heat and mass constraints in respect of the conventional powdered catalysts, the catalyst functionality resulting to be tightly dependent on the cooperation between metal-oxide and acidic phase. Additionally, the accessibility both of the CO2 activation and methanol (MeOH) dehydration sites over the hybrid micro-extruded catalyst most importantly affects the catalytic performance, as suggested by the values of turnover frequency of CO2 conversion and DME formation pointing out the need for a favorable exposure of chemisorption sites of different nature to enhance the specific reactivity.

Synthesis of poly(pyrazolopyridine)s by Hantzsch multicomponent polymerization

This work concerns the synthesis of poly(pyrazolopyridine)s via a three-component Hantzsch reaction. The first part of this study was intended to determine adequate experimental conditions for the synthesis of an analytically pure pyrazolopyridine heterocycle model compound in quantitative yield, which can be further used for polymer synthesis. For this purpose, the effect of different parameters (solvent, temperature, additive) on the selectivity of the reaction has been investigated. Some specific difunctional precursors (bisaminopyrazoles and dialdehydes) have been then designed and synthesized. From these reagents, poly(pyrazolopyridine)s were successfully synthesized by multicomponent polycondensation reaction. Some physico-chemical characterizations of these new macromolecular structures are described. • Multi-component reactions broaden the scope of conventional polycondensation. • Unconventional synthesis of aromatic and heterocyclic polymers by Hantzsch reaction. • Poly(pyrazolopyridine)s can be synthesized by multi-component polycondensation.

Ionic liquids and deep eutectics as a transformative platform for the synthesis of nanomaterials.

Ionic liquids (ILs) are becoming a revolutionary synthesis medium for inorganic nanomaterials, permitting more efficient, safer and environmentally benign preparation of high quality products. A smart combination of ILs and unconventional synthesis methods allows added value to be drawn from the broad matrix of available property combinations. Mixed systems such as Deep Eutectic Solvents (DES) offer a similarly broad combinatorial playground, which is also beginning to translate into applications. Approached holistically, these liquids therefore enable new universal manufacturing techniques that provide solutions to the existing problems of nanomanufacturing, and beyond that will open completely new horizons and possibilities for controlling the growth and assembly of nanostructures. Examples that illustrate the power of ILs in the improved manufacturing of nanomaterials are explored, such as the synthesis of light phosphors with exceptional quantum yields, record-figure-of merit thermoelectrics, and efficient photocatalysts, alongside developments in DES nanostructure and deep eutectic-solvothermal and ionothermal techniques.

Growth Study of Hierarchical Pore SSZ-13 Molecular Sieves with Improved CO2 Adsorption Performance.

SSZ-13, with a unique pore structure and excellent thermal stability, showed a potential application in the adsorption and catalysis industry. In this work, Al(NO3)3 was used as an Al source to study the performance and morphology of the zeolite. The zeolite was prepared with an unconventional process by adding an Al source before the structure-directing agent and base. When inorganic oxygen-containing anions were introduced into the unconventional synthesis system, the crystals of the zeolite conform to the unconventional growth mode. The zeolites with large crystals were assembled from small unit nanocrystals. Extending the reaction time, aging time and adding fluoride ions introduced a multistage pore structure on the surface of the molecular sieve, which improved the CO2 adsorption performance. When aging for 24 h, reaction for 96 h, and the amount of fluorine added was 0.05 (F/Si), the sample had the best hierarchical pore structure. The SSZ-13 molecular sieve with an added amount of 0.1 (F/Si) has the highest CO2 adsorption performance. The adsorption amount was 4.55 mmol/g at 1 bar, which is 20.4% higher than that of zeolite SSZ-13 prepared by the conventional process.

Unexpected Reaction Products of Uracil and Its Methyl Derivatives with Acetic Anhydride and Methylene Chloride.

New acetyl derivatives of uracil, 6-methyluracil, and thymine were obtained in the course of an unconventional synthesis in methylene chloride. It was shown that products with the acetyloxymethyl fragment are formed according to a mechanism different from that for products with the acetyloxyethyl group. In particular, for uracil it was proven that the reaction with Ac2O, TEA, and CH2Cl2 leads to 1-acetyloxymethyluracil, where the N1 substituent is composed of the -CH2- fragment that originated from CH2Cl2 and the 1-acetyloxy moiety from Ac2O. The reaction of uracil with Ac2O, TEA, CH2Cl2, and DMAP leads to an acetyloxyethyl derivative in which the -CH2-CH2- fragment originates from TEA and the 1-acetyloxy moiety from Ac2O. A possible mechanism for the formation of new compounds was suggested and supported by the density functional theory/B3LYP quantum mechanical calculations. New compounds (39 in total, including seven deuterated) were fully characterized by nuclear magnetic resonance and high-resolution mass spectrometry techniques.

New Trends in Diaziridine Formation and Transformation (a Review).

This review focuses on diaziridine, a high strained three-membered heterocycle with two nitrogen atoms that plays an important role as one of the most important precursors of diazirine photoaffinity probes, as well as their formation and transformation. Recent research trends can be grouped into three categories, based on whether they have examined non-substituted, N-monosubstituted, or N,N-disubstituted diaziridines. The discussion expands on the conventional methods for recent applications, the current spread of studies, and the unconventional synthesis approaches arising over the last decade of publications.

Catalyst-Controlled Site-Selective Acylation and its Application to Unconventional Total Synthesis of Natural Glycosides

Catalyst-Controlled Site-Selective Acylation and its Application to Unconventional Total Synthesis of Natural Glycosides

Green Synthesis of Gold and Silver Nanoparticles from Plant Extracts and Their Possible Applications as Antimicrobial Agents in the Agricultural Area

Currently, metal nanoparticles have varied uses for different medical, pharmaceutical, and agricultural applications. Nanobiotechnology, combined with green chemistry, has great potential for the development of novel and necessary products that benefit human health, environment, and industries. Green chemistry has an important role due to its contribution to unconventional synthesis methods of gold and silver nanoparticles from plant extracts, which have exhibited antimicrobial potential, among other outstanding properties. Biodiversity-rich countries need to collect and convert knowledge from biological resources into processes, compounds, methods, and tools, which need to be achieved along with sustainable use and exploitation of biological diversity. Therefore, this paper describes the relevant reported green synthesis of gold and silver nanoparticles from plant extracts and their capacity as antimicrobial agents within the agricultural field for fighting against bacterial and fungal pathogens that can cause plant, waterborne, and foodborne diseases. Moreover, this work makes a brief review of nanoparticles’ contribution to water treatment and the development of “environmentally-friendly” nanofertilizers, nanopesticides, and nanoherbicides, as well as presenting the harmful effects of nanoparticles accumulation in plants and soils.

Yield dimensionless magnetic effect and shear thinning for magnetorheological grease

The effects of silicone oil viscosity (SOV), carbonyl iron particles (CIPs) weight fraction and size on the yield dimensionless magnetic effect (DME) and shear-thinning behavior for magnetorheological (MR) grease were experimentally investigated in this study. Nine MR greases were prepared using Taguchi L9 orthogonal array based on an unconventional synthesis technique. The yield DME, namely the controllability of magnetic effect relative to viscous effect under the on-state magnetic fields and zero shear rate, was observed to be closely related to CIPs fraction based upon significance assessment and percent contribution (PC) comparison, whereas the shear-thinning behavior of suspension was dependent on the CIPs fraction and SOV. According to the analysis of discrepancy direction at the presence of magnetic fields, there was a negative linear correlation between yield DME and CIPs fraction, but the shear thinning had positive linear correlation with the CIPs fraction and SOV. Furthermore, the PC and the corresponding actual contribution values (ACV) of SOV and CIPs fraction towards the shear thinning showed distinct characteristics which were relevant to the critical magnetic fields. This study presented a hypothesis in which the difference of relative evolution rate between fiber structures and magnetic constructions under shearing and different magnetic fields caused the differences of PC and ACV of SOV and CIPs fraction to suspensions-viscosity attenuation.

Recovery of motor function after traumatic spinal cord injury by using plasma-synthesized polypyrrole/iodine application in combination with a mixed rehabilitation scheme.

Traumatic spinal cord injury (TSCI) can cause paralysis and permanent disability. Rehabilitation (RB) is currently the only accepted treatment, although its beneficial effect is limited. The development of biomaterials has provided therapeutic possibilities for TSCI, where our research group previously showed that the plasma-synthesized polypyrrole/iodine (PPy/I), a biopolymer with different physicochemical characteristics than those of the PPy synthesized by conventional methods, promotes recovery of motor function after TSCI. The present study evaluated if the plasma-synthesized PPy/I applied in combination with RB could increase its beneficial effects and the mechanisms involved. Adult rats with TSCI were divided into no treatment (control); biopolymer (PPy/I); mixed RB by swimming and enriched environment (SW/EE); and combined treatment (PPy/I + SW/EE) groups. Eight weeks after TSCI, the general health of the animals that received any of the treatments was better than the control animals. Functional recovery evaluated by two scales was better and was achieved in less time with the PPy/I + SW/EE combination. All treatments significantly increased βIII-tubulin (nerve plasticity) expression, but only PPy/I increased GAP-43 (nerve regeneration) and MBP (myelination) expression when were analyzed by immunohistochemistry. The expression of GFAP (glial scar) decreased in treated groups when determined by histochemistry, while morphometric analysis showed that tissue was better preserved when PPy/I and PPy/I + SW/EE were administered. The application of PPy/I + SW/EE, promotes the preservation of nervous tissue, and the expression of molecules related to plasticity as βIII-tubulin, reduces the glial scar, improves general health and allows the recovery of motor function after TSCI. The implant of the biomaterial polypyrrole/iodine (PPy/I) synthesized by plasma (an unconventional synthesis method), in combination with a mixed rehabilitation scheme with swimming and enriched environment applied after a traumatic spinal cord injury, promotes expression of GAP-43 and βIII-tubulin (molecules related to plasticity and nerve regeneration) and reduces the expression of GFAP (molecule related to the formation of the glial scar). Both effects together allow the formation of nerve fibers, the reconnection of the spinal cord in the area of injury and the recovery of lost motor function. The figure shows the colocalization (yellow) of βIII-tubilin (red) and GAP-43 (green) in fibers crossing the epicenter of the injury (arrowheads) that reconnect the rostral and caudal ends of the injured spinal cord and allowed recovery of motor function.

Unconventional Synthesis of Large Pore Ordered Mesoporous Carbon Nanospheres for Ionic Liquid-Based Supercapacitors

Ordered carbon spheres with enlarged mesopores have been considered to be desirable carbon electrodes for ionic liquid-based supercapacitors. New synthesis of these materials to use commercially available soft templates is yet to be developed. In this study, we demonstrate that by silica encapsulation of self-assembled polymer nanospheres prepared using commercially available Pluronic F127, mesopore sizes of obtained carbon nanospheres can be enlarged from micropores to large mesopores up to 10.7 nm in size. A linear relationship between the mesopore size and the thicknesses of silica nanocages has been established, which enables us to alter the mesopore sizes in a controlled manner. The two-electrode test in EMI-BF4 electrolyte demonstrates that mesoporous carbon nanospheres show a capacitance of up to 113 F g–1 at 10 A g–1. They also exhibit an excellent energy density (E) of 56 W h kg–1 (working voltage of 4.0 V). Such high capacitance, outstanding rate capability, and excellent power density (P) are o...

Investigation on Unconventional Synthesis of Astroinformatic Data Classifier Powered by Irregular Dynamics

This paper discusses the mutual combination of the unconventional algorithm (in this case evolutionary algorithms), deterministic chaos and modeling on real data from astrophysics. Analytical programming with selected evolutionary algorithm is used to synthesize suitable models. The main attention in this paper is focused on various chaotic generators, which are used instead of classical pseudo-random number generators. Chaotic generators are used in conjunction with a special case - a generator based on a strange non-chaotic attractor. The performance of all chaotic and non-chaotic based generators is then mutually compared at the end.