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The incorporation of artificial intelligence into agriculture presents challenges, particularly due to hardware limitations, especially in sensors. Currently, pest detection relies heavily on manual scouting by humans. Therefore, the objective of this study is to create a chemoresistive sensor that enables early identification of the characteristic volatile compound, viz., methyl jasmonate, released during pest infestations. Given the lower reactivity of esters, we have fine-tuned a composite consisting of SnO2 nanoparticles and 2D-MXene sheets to enhance adsorption and selective oxidation, resulting in heightened sensitivity. The optimized composite demonstrated a notable response even at concentrations as low as 120 ppb, successfully confirming pest infestations in tomato crops.
Assuntos
Acetatos , Ciclopentanos , Oxilipinas , Compostos de Estanho , Ciclopentanos/química , Oxilipinas/metabolismo , Oxilipinas/química , Compostos de Estanho/química , Acetatos/química , Animais , Solanum lycopersicum/química , Solanum lycopersicum/metabolismo , Insetos , Estresse Fisiológico/efeitos dos fármacosRESUMO
In agriculture, pest management is a major challenge. Crop releases volatiles in response to the pest; hence, sensing these volatile signals at a very early stage will ease pest management. Here, binary catalyst-loaded SnO2 nanoparticles of <5 nm were synthesized for the repeated capture and oxidation of the signature volatile and its products to amplify the chemoresistive signal to detect concentrations as low as ≈120 ppb. The sensitivity may be due to the presence of the elements in the Sn-Fe-Pt bond evidenced by extended X-ray absorption fine-structure spectroscopy (EXAFS) that captures and oxidize the volatile without escaping. This strong catalyst may oxidize nontarget volatiles and can cause false signals; hence, a molecular sieve filter has been coupled to ensure high selectivity for the detection ofTuta absolutainfestation in tomato. Finally, with the support of a mobile power bank, the optimized sensor has been assembled into a lightweight handheld device.
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Nanopartículas , Oxirredução , Agricultura , Estresse OxidativoRESUMO
Quick leaching of urea fertilizer encourages different coatings, but achieving a stable coating without toxic linkers is still challenging. Here, the naturally abundant bio-polymer, i.e., starch, has been groomed to form a stable coating through phosphate modification and the support of eggshell nanoparticles (ESN) as a reinforcement agent. The ESN offers a calcium ion binding site for the phosphate to cause bio-mimetic folding. This coating retains hydrophilic ends in the core and gives an excellent hydrophobic surface (water contact angle 123°). Further, the phosphorylated starch+ESN led the coating to release only â¼30 % of the nutrient in the initial ten days and sustained for up to 60 days to show â¼90 % release. The stability of the coating has been attributed to its resistance to major soil factors viz., acidity and amylase degradation. The ESN also increases elasticity, cracking control, and self-repairing capacity by serving as buffer micro-bots. The coated urea enhanced the yield of rice grain by â¼10%.
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Amido , Ureia , Preparações de Ação Retardada/química , Ureia/química , Amido/química , Solo , Fertilizantes/análise , FosfatosRESUMO
Fruit peels are rich source of bioactive compounds such as polyphenols, flavonoids, and antioxidants but are often discarded as waste due to limited pharmaceutical and nutraceutical applications. This study aimed to valorise pomegranate and citrus fruit peel into green synthesised silver nanoparticles (AgNPs) in order to modify cellulose-based wrapping material for prospective food packaging applications and propose an alternate and sustainable approach to replace polyethene based food packaging material. Four different concentrations of AgNO3 (0.5 mM, 1 mM, 2 mM, and 3 mM) were used for green synthesis of AgNPs from fruit peel bioactive, which were characterised followed by phytochemical analysis. Ultraviolet-Visible spectroscopy showed surface plasmon resonance at 420 nm, XRD analysis showed 2θ peak at 27.8°, 32.16°, 38.5°, 44.31°, 46.09°, 54.76°, 57.47°, 64.61° and 77.50° corresponding to (210), (122), (111), (200), (231), (142), (241), (220) and (311) plane of face centred cubic crystal structure of AgNPs. Fourier-transform infrared spectroscopy analysis of AgNPs green synthesised from pomegranate and kinnow peel extract showed a major peak at 3277, 1640 and 1250-1020 1/cm while a small peak at 2786 1/cm was observed in case of pomegranate peel extract which was negligible in AgNPs synthesized from kinnow peel extract. Particle sizes of AgNPs showed no statistically significant variance with p > 0.10 and thus, 2 mM was chosen for further experimentation and modification of cellulose based packaging material as it showed smallest average particle size. Zeta potential was observed to be nearly neutral with a partial negative strength due to presence of various phenolic compounds such as presence of gallic acid which was confirmed by ultrahigh performance liquid chromatography-photodiode array(UHPLC-PDA) detector. Thermal stability analysis of green synthesised AgNPs qualified the sterilisation conditions up to 100 °C. AgNPs green synthesized from both the peel extracts had higher polyphenolic content, antioxidant and radical scavenging activity as compared to peel extracts without treatment (p < 0.05). The cellulose based food grade packaging material was enrobed by green synthesised AgNPs. The characterisation of modified cellulose wrappers showed no significant difference in thickness of modified cellulose wrappers as compared with untreated cellulose wrapper (p > 0.42) while weight and grammage increased significantly in modified cellulose wrapper (p < 0.05). The colour values on CIE scale (L*, a* and b*) showed statistically significant increase in yellow and green colour (p < 0.05) for modified cellulose wrappers as compared to control wrapper. The oxygen permeability coefficient, water vapour permeability coefficient, water absorption capacity and water behaviour characteristics (water content, swelling degree and solubility) showed significant decrease (p < 0.05) for modified cellulose wrapper as compared to control wrapper. A uniform distribution and density of green synthesised AgNPs across cellulose wrapper matrix was observed through scanning electron microscopy (SEM) images with no significant aggregation, confirming successful enrobing and stable immobilisation of nanoparticles from cellulose matrix. A seven-day storage study of bread wrapped in modified and control cellulose wrappers showed delayed occurrence of microbial, yeast and mould count in bread packaged in modified cellulose wrappers and thus, resulting in shelf life extension of bread. The results are encouraging for the potential applications of modified cellulose wrappers to replace polyethene based food packaging.
Assuntos
Frutas , Nanopartículas Metálicas , Frutas/química , Prata/análise , Pão , Nanopartículas Metálicas/química , Extratos Vegetais/química , Antioxidantes/análise , Celulose/análise , Expectativa de Vida , Polietilenos/análiseRESUMO
The current review aims to gain knowledge on the biosynthesis and characterization of nanoparticles (NPs), their multifactorial role, and emerging trends of NPs utilization in modern science, particularly in sustainable agriculture, for increased yield to solve the food problem in the coming era. However, it is well known that an environment-friendly resource is in excessive demand, and green chemistry is an advanced and rising resource in exploring eco-friendly processes. Plant extracts or other resources can be utilized to synthesize different types of NPS. Hence NPs can be synthesized by organic or inorganic molecules. Inorganic molecules are hydrophilic, biocompatible, and highly steady compared to organic types. NPs occur in numerous chemical conformations ranging from amphiphilic molecules to metal oxides, from artificial polymers to bulky biomolecules. NPs structures can be examined by different approaches, i.e., Raman spectroscopy, optical spectroscopy, X-ray fluorescence, and solid-state NMR. Nano-agrochemical is a unification of nanotechnology and agro-chemicals, which has brought about the manufacture of nano-fertilizers, nano-pesticides, nano-herbicides, nano-insecticides, and nano-fungicides. NPs can also be utilized as an antimicrobial solution, but the mode of action for antibacterial NPs is poorly understood. Presently known mechanisms comprise the induction of oxidative stress, the release of metal ions, and non-oxidative stress. Multiple modes of action towards microbes would be needed in a similar bacterial cell for antibacterial resistance to develop. Finally, we visualize multidisciplinary cooperative methods will be essential to fill the information gap in nano-agrochemicals and drive toward the usage of green NPs in agriculture and plant science study.
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Nanopartículas Metálicas , Nanopartículas , Nanopartículas/química , Agricultura/métodos , Nanotecnologia , Antibacterianos , Medição de Risco , Nanopartículas Metálicas/químicaRESUMO
Crop diseases cause the release of volatiles. Here, the use of an SnO2-based chemoresistive sensor for early diagnosis has been attempted. Ionone is one of the signature volatiles released by the enzymatic and nonenzymatic cleavage of carotene at the latent stage of some biotic stresses. To our knowledge, this is the first attempt at sensing volatiles with multiple oxidation sites, i.e., ionone (4 oxidation sites), from the phytovolatile library, to derive stronger signals at minimum concentrations. Further, the sensitivity was enhanced on an interdigitated electrode by the addition of platinum as the dopant for a favorable space charge layer and for surface island formation for reactive interface sites. The mechanistic influence of oxygen vacancy formation was studied through detailed density functional theory (DFT) calculations and reactive oxygen-assisted enhanced binding through X-ray photoelectron spectroscopy (XPS) analysis.
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Idioma , Norisoprenoides , Eletrodos , Fazendas , OxigênioRESUMO
Lycopene, a natural colorant and antioxidant with a huge growing market, is highly susceptible to photo/thermal degradation, which demands real-time sensors. Hence, here a transparent upconversion nanoparticles (UCNPs) strip having 30 mol % Yb, 0.1 mol % Tm, and ß-NaYF4 UCNPs, which shows an intense emission at 475 nm, has been developed. This strip has been found to be sensitive to lycopene with a detection limit as low as 10 nM using a smartphone camera, which is due to static quenching that is confirmed by the lifetime study. In comparison to previous paper strips, here the transparent strip has minimal scattering with maximum sensitivity in spite of not using any metal quenchers. An increase in strip hydrophobicity during the fabrication process complements the strip to selectively permeate and present an extraction-free substitute analysis for chromatography. Hydrophobicity endows the strip with the capability to reuse the strip with â¼100% luminescence recovery.
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Nitrogen fertilizers, namely urea, are prone to leaching that causes inefficiency in crop production and environmental pollution; hence porous particles were explored for slow release. Nevertheless, discrete particles add cost; therefore, jute cellulose has been tested as twine to tether silica together for reusability. On the other hand, silica serves as an exoskeleton to give pore memory property to cellulose, which otherwise is susceptible to loss of porosity during irrigation. The composite shows â¼70% more absorption capacity in the fifth cycle than the fiber without silica coating. The urea release kinetics shows only <1/3 and 3/4 of urea release from the jute-silica composite compared to naked porous silica and cellulose, respectively. The slow and sustained release of fertilizer from the composite results in a continuous increase in the chlorophyll content in rice crops.
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The indiscriminate use of pesticides leads to irreparable damage to the ecosystem, which motivates for sustainable alternatives like pheromone-assisted pest management. The tomato pinworm Tuta absoluta is a major threat to tomato cultivation. Moreover, its green management technology uses a pheromone trap that has a short field life. To overcome this problem, a pheromone composite with graphene oxide (GO) and amine-modified graphene oxide (AGO) that can extend the diffusion path has been developed. The composite stimulates an effective electrophysiological response in the antenna, which results in trapping of a significantly higher number of insects as compared to the commercial septa, thus qualifying it for field evaluation. Compared to AGO, the GO composite has pheromones assembled into a multilayer, which increases the pheromone diffusion path. This in turn resulted in the extension of the pheromone life that proportionally increased the pest trapped. This technique will be beneficial to farmers as they have longer field efficacy to keep the pest damage low in an environmentally friendly manner.
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Acetatos/farmacologia , Preparações de Ação Retardada/química , Álcoois Graxos/farmacologia , Grafite/química , Controle de Insetos/métodos , Nanocompostos/química , Feromônios/farmacologia , Animais , Masculino , Mariposas/efeitos dos fármacosRESUMO
To daze conventional pesticide release limitations, nanotechnology-mediated pesticide delivery using natural polymers has been actively investigated. However, the lack of information on what are the beneficial/non-beneficial aspects of using hybrid- and organic-nanoparticles (NP) and among the polysaccharides which are better suited concerning pesticide loading efficiency (PLE wt%), entrapment efficiency, and sustained pesticide release (SPR %) has prompted us to investigate this study. In this report, we systematically investigated a series of polysaccharides such as starch (S), cellulose (C), aminocellulose (AC), and sodium carboxymethylcellulose (NaCMC) coated on magnetite NP (MNP, Fe3O4) and complete organic nanocarrier systems (starch and cellulose) that have no MNP part were compared for the PLE wt% and SPR % efficiencies for chlorpyrifos (ChP) insecticide. Overall, all nanocarriers (NCs) have shown good to excellent PLE wt% due to the smaller-sized NP obtained through optimal conditions. However, among the hybrid polysaccharides studied, starch MNP has shown a maximum PLE of 111 wt% in comparison with other polysaccharides (80-94 wt%) coated hybrid-NCs as well as with organic-NCs (81-87 wt%). The use of inorganic support does improve the PLE wt% markedly for starch but not for cellulose derivatives. Similarly, the SPR results of S-NP showed a remarkably better sustained release profile for ChP of 88% in 14 d. In contrast, other unfunctionalized and functionalized celluloses exhibited poor release profiles of 60%-20% for the same period. This study may help the researchers choose the right system for designing and achieving enhanced pesticide efficiency.
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Pesticide leaching and soil contamination are major issues in the present agriculture formulations. Hence, here 2D graphene oxide in combination with cationic, anionic, or nonionic polymers were tested for runoff resistance and targeted release behavior. Cationic polymer supplemented the binding of rGO on leaf surface by 30% more than control and reduced off-target leaching in soil by 45% more than control. Further, to enhance the fruit rot control caused by Colletotrichum capsici in chili crop, the rGO was decorated with Cu2-xSe nanocrystals, which provided combined disease control with captan. The chitosan coating in the nanocomposite added targeted pH-responsive fungal inhibition behavior and could reduce the C. capsici growth by â¼1/2 times compared to captan control.
Assuntos
Captana/farmacologia , Quitosana/farmacologia , Colletotrichum/efeitos dos fármacos , Fungicidas Industriais/farmacologia , Grafite/farmacologia , Doenças das Plantas/prevenção & controle , Captana/química , Quitosana/química , Colletotrichum/crescimento & desenvolvimento , Frutas/química , Fungicidas Industriais/química , Grafite/química , Concentração de Íons de Hidrogênio , Testes de Sensibilidade Microbiana , Nanocompostos/química , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Mushrooms are rich in ergosterol, a precursor of ergocalciferol, which is a type of vitamin D2. The conversion of ergosterol to ergocalciferol takes place in the presence of UV radiation by the cleavage of the "B-ring" in the ergosterol. As the UV radiation cannot penetrate deep into the tissue, only minimal increase occurs in sunlight. In this study, upconversion nanoparticles with the property to convert deep-penetrating near-infrared radiation to UV radiation have been cast into a disk to use sunlight and emit UV radiation for vitamin D conversion. An engineered upconversion nanoparticle (UCNP) disk with maximum particles and limited clusters demonstrates â¼2.5 times enhanced vitamin D2 conversion.
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Luz Solar , Raios Ultravioleta , Ergosterol , Raios Ultravioleta/efeitos adversos , Vitamina D , VitaminasRESUMO
Classical plant uptake is limited to hydrophilic or water-dispersible material. Therefore, in order to test the uptake behaviour of hydrophobic particles, here, we tested the fate of hydrophobic particles (oleylamine coated Cu2-xSe NPs (CS@OA)) in comparison to hydrophilic particles (chitosan-coated Cu2-xSe NPs (CS@CH)) by treatment on the plant roots. Surprisingly, hydrophobic CS@OA NPs have been found to be ~ 1.3 times more efficient than hydrophilic CS@CH NPs in tomato plant root penetration. An atomic force microscopy (AFM) adhesion force experiment confirms that hydrophobic NPs experience non-spontaneous yet energetically favorable root trapping and penetration. Further, a relative difference in the hydrophobic vs. hydrophilic NPs movement from roots to shoots has been observed and found related to the change in protein corona as identified by two dimensional-polyacrylamide gel electrophoresis (2D-PAGE) analysis. Finally, the toxicity assays at the give concentration showed that Cu2-xSe NPs lead to non-significant toxicity as compared to control. This technology may find an advantage in fertilizer application.
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Corantes Fluorescentes/química , Nanopartículas/química , Raízes de Plantas/metabolismo , Corantes Fluorescentes/farmacologia , Microscopia de Força Atômica , Raízes de Plantas/química , Raízes de Plantas/ultraestruturaRESUMO
Leishmania is an obligate intracellular protozoan parasite, which resides in human macrophage vacuoles that are referred to as parasitophorus vacuoles. Amphotericin B (AmB) is the first-line drug with 99% cure rates; however, overdose-induced toxic side effects are a major limitation. To improve the efficacy at lower dose and subsequently to avoid toxicity and to further investigate the role of charge dynamics on the efficacy, a graphene oxide (GO)-based composite of AmB was developed with native negatively charged GO and amine-conjugated positively charged AGO. The AGO composite resulted in enhanced uptake as confirmed by confocal and FACS analysis. Thus, AGO caused a strong inhibition of amastigotes, with IC50 values 5-fold lower than free AmB. The parasitophorus vacuoles harbour a hydrolytic and acidic environment, which is favourable for the parasites, as they don't attenuate this condition. AGO-AmB was able to modify the intracellular pH of the Leishmania donovani-infected macrophages, generating unfavourable conditions for the amastigote, and thus improving its efficacy.
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According to Food and Agriculture Organization 2015 report, post-harvest agricultural loss accounts for 20-50% annually; on the other hand, reports about preservatives toxicity are also increasing. Hence, preservative release with response to fruit requirement is desired. In this study, acid synthesized in the overripe fruits was envisaged to cleave acid labile hydrazone to release preservative salicylaldehyde from graphene oxide (GO). To maximize loading and to overcome the challenge of GO reduction by hydrazine, two-step activation with ethylenediamine and 4-nitrophenyl chloroformate respectively, are followed. The final composite shows efficient preservative release with the stimuli of the overripe fruit juice and improves the fruit shelf life. The composite shows less toxicity as compared to the free preservative along with the additional scope to reuse. The composite was vacuum-filtered through a 0.4 µm filter paper, to prepare a robust wrapper for the fruit storage.
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Grafite/química , Conservação de Alimentos , Frutas , VácuoRESUMO
Noninvasive techniques, such as breath tests (urea breath test), blood pressure measurements using a sphygmomanometer and electrocardiography, were employed by a physician to perform classical diagnosis. The use of state-of-the-art noninvasive therapies at the organ level in modern medicine has gradually become possible. However, cancer treatment demands spatially and temporally controlled noninvasive therapy at the cell level because nonspecific toxicity often causes complicated side effects. To increase survival in cancer patients further, combination therapy and combination drugs are explored which demand high specificity to avoid combined-drug side effects. We believe that high specificity could be obtained by implementing near-infrared (NIR) light-assisted nanoparticles in photothermal therapy, chemotherapy, and photodynamic therapy. To refine this therapy and subsequently achieve high efficiency, novel nanomaterials have been designed and modified either to enhance the uptake and drug delivery to the cancer site, or control treatment to administer therapy efficiently. These modifications and developments have been demonstrated to achieve spatial and temporal control when conducting an in vivo xenograft, because the NIR light penetrated effectively the biological tissue. The nanoplatforms discussed in this review are grouped under the following subheadings: Au nanorods (NRs), Au nanoshells, other Au-related nanomaterials, graphene oxide, upconversion nanoparticles, and other related materials (including materials such as CuS, Fe3O4-related systems, and carbon nanotubes (CNTs)).
Assuntos
Raios Infravermelhos , Nanoestruturas/uso terapêutico , Neoplasias/tratamento farmacológico , Fototerapia/métodos , Animais , Ouro/química , Ouro/uso terapêutico , Grafite/química , HumanosRESUMO
External stimuli responsive dual drugs carrier was synthesized with Au nanorods (NRs) as the platform. On Au NRs, single stranded DNAs were assembled using 5' thiol end. Following this, complementary DNA (cDNA) strands were hybridized. This hybridized double stranded DNA facilitated doxorubicin (Dox) intercalation into the duplexes. The cDNA designed with the 5' amine functional group assisted to tether platinum [Pt(IV)] prodrugs by establishing amide bond with the acid group at the axial ligand. The other axial acid group in Pt(IV) prodrugs was conjugated with the folic acid (FA) to target folate receptors overexpressed in the cancer cells. This targeting vehicle provided remote-controlled delivery of this high toxic cargo cocktail at the tumor site, ensuring extra specificity that can avoid acute toxicity, where release of Dox and Pt(IV) was achieved upon NIR 808 nm diode laser irradiation. The dehybridization set the Dox free to bind the cell nucleus and cellular reductants reduced Pt(IV) to yield toxic Pt(II), becoming an active drug. The in vitro and in vivo studies revealed that this external stimulus responsive combination drug delivery was significantly effective.
Assuntos
Antineoplásicos/administração & dosagem , Cisplatino/administração & dosagem , Doxorrubicina/administração & dosagem , Sistemas de Liberação de Medicamentos/instrumentação , Neoplasias/tratamento farmacológico , Oligonucleotídeos/química , Fototerapia , Pró-Fármacos/administração & dosagem , Animais , Antineoplásicos/química , Linhagem Celular Tumoral , Cisplatino/química , Doxorrubicina/química , Portadores de Fármacos/química , Sistemas de Liberação de Medicamentos/métodos , Receptores de Folato com Âncoras de GPI/antagonistas & inibidores , Receptores de Folato com Âncoras de GPI/metabolismo , Humanos , Masculino , Camundongos , Camundongos Nus , Nanotubos/química , Neoplasias/metabolismo , Pró-Fármacos/químicaRESUMO
Photothermal cancer therapy using near-infrared (NIR) laser radiation is an emerging treatment. In the NIR region, two biological transparency windows are located in 650-950 nm (first NIR window) and 1000-1350 nm (second NIR window) with optimal tissue transmission obtained from low scattering and energy absorption, thus providing maximum radiation penetration through tissue and minimizing autofluorescence. To date, intensive effort has resulted in the generation of various methods that can be used to shift the absorbance of nanomaterials to the 650-950 nm NIR regions for studying photoinduced therapy. However, NIR light absorbers smaller than 100 nm in the second NIR region have been scant. We report that a Au nanorod (NR) can be designed with a rod-in-shell (rattle-like) structure smaller than 100 nm that is tailored to be responsive to the first and second NIR windows, in which we can perform hyperthermia-based therapy. In vitro performance clearly displays high efficacy in the NIR photothermal destruction of cancer cells, showing large cell-damaged area beyond the laser-irradiated area. This marked phenomenon has made the rod-in-shell structure a promising hyperthermia agent for the in vivo photothermal ablation of solid tumors when activated using a continuous-wave 808 m (first NIR window) or a 1064 nm (second NIR window) diode laser. We tailored the UV-vis-NIR spectrum of the rod-in-shell structure by changing the gap distance between the Au NR core and the AuAg nanoshell, to evaluate the therapeutic effect of using a 1064 nm diode laser. Regarding the first NIR window with the use of an 808 nm diode laser, rod-in-shell particles exhibit a more effective anticancer efficacy in the laser ablation of solid tumors compared to Au NRs.
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Ouro/química , Raios Infravermelhos , Nanotubos/química , Radioterapia/métodos , Absorção , Animais , Linhagem Celular Tumoral , Lasers , Neoplasias Pulmonares/radioterapia , Masculino , Camundongos , Nanotubos/toxicidade , Polietilenoglicóis/química , Prata/químicaRESUMO
Based on the difference in the redox potentials between two metal species, the galvanic replacement reaction is known to create an irreversible process to generate hollow nanostructures in a wide range of shapes. In the context of galvanic replacement reaction, continuing etching leads to the general collapse of the hollow structures because of the excess amount of oxidizing agent. We demonstrate the growth of solid nanostructures from a hollow frame-like architecture in the course of a galvanic replacement reaction without any morphology destruction. We report the successful composition transformation of solid Ag with a wide range of shapes, such as plate, decahedron, rod, prism, sphere, and foil, from as thin as <10 nm up to 5 µm and with an area of â¼4 mm(2), to their solid Au counterparts using straightforward chemical reactions. The successful conversion process relies on a decrease in the reduction rate of the metallic precursor to initiate dissolution of Ag in the first stage (a galvanic replacement reaction), then a subsequent backfilling of Au into the hollowed-out structures. Cetyltrimethylammonium bromide (CTAB) surfactant, a key parameter, interacts with metal salt precursor to form a complex species that retards metal reduction. In addition, we demonstrate conversion of solid nano-Ag to solid nano-Pd as well as of Cu foil (10 µm thick) to shiny Au foil.
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The thermally induced cross-linked esterification occurs for the formation of eccentric inorganic-polymeric nanoparticles. By taking advantage of eccentricity, Ag-PSMA eccentric structure is converted to raspberry-like Au-based Janus nanoparticles.