Growth of Ag nanoparticles using plasma-modified multi-walled carbon nanotubes

This study presents a novel method for preparing multi-walled carbon nanotubes (MWNTs) grafted with a poly(2-hydroxyethyl methacrylate) (HEMA)-silver complex (CNTs-HEMA-Ag complex) through plasma-induced grafting polymerization. The characteristics of the MWNTs after being grafted with HEMA polymer are monitored by Fourier transform infrared (FT-IR) spectroscopy. The chelating groups in the HEMA polymer grafted on the surface of the CNTs-HEMA are the coordination sites for chelating silver ions, and are further used as nanotemplates for the growing of Ag nanoparticles (quantum dots). Transmission electron microscopy (TEM) reveals that the particle size of Ag nanoparticles on the CNT surfaces increases with the Ag(+) chelating concentration, reaction time, and reaction temperature. Moreover, the crystalline phase of Ag nanoparticles is identified by using x-ray diffraction (XRD). In addition, high-resolution x-ray photoelectron spectroscopy (XPS) is used to characterize the functional groups on the surface of the MWNTs after chemical modification through plasma treatment; it demonstrates that the growing amount of the Ag nanoparticles on the nanotubes increases with the Ag(+) chelating concentration due to the blocking effect of the Ag particles forming on the MWNTs.     

Synthesis and characterization of silver nanoparticles impregnated into bacterial cellulose

This article presents a study about the synthesis of colloidal silver (Ag)/biopolymer where Ag submicron particles were prepared in situ on bacterial cellulose (BC) produced by Gluconacetobacter xylinus. Different reducing agents were compared (hydrazine, hydroxylamine or ascorbic acid) together with the influence of gelatin or polyvinylpyrrolidone (PVP) employed as colloid protectors. Particle size distribution and morphology were investigated by scanning electron microscope (SEM). SEM images show silver nanoparticles (40–100 nm) size range attached on (BC) microfibrils. XRD analyses confirmed the Ag cubic phase deposited on to BC fibrils. The ash contents determined by thermogravimetric analyses have indicated high level of silver loading on the obtained composites.     

Study of mechanism of enhanced antibacterial activity by green synthesis of silver nanoparticles

The extensive use of silver nanoparticles needs a synthesis process that is greener without compromising their properties. The present study describes a novel green synthesis of silver nanoparticles using Guava (Psidium guajava) leaf extract. In order to compare with the conventionally synthesized ones, we also prepared Ag-NPs by chemical reduction. Their optical and morphological characteristics were thoroughly investigated and tested for their antibacterial properties on Escherichia coli. The green synthesized silver nanoparticles showed better antibacterial properties than their chemical counterparts even though there was not much difference between their morphologies. Fourier transform infrared (FTIR) spectroscopic analysis of the used extract and as-synthesized silver nanoparticles suggests the possible reduction of Ag(+) by the water-soluble ingredients of the guava leaf like tannins, eugenol and flavonoids. The possible reaction mechanism for the reduction of Ag(+) has been proposed and discussed. The time-dependent electron micrographs and the simulation studies indicated that a physical interaction between the silver nanoparticles and the bacterial cell membrane may be responsible for this effect. Based on the findings, it seems very reasonable to believe that this greener way of synthesizing silver nanoparticles is not just an environmentally viable technique but it also opens up scope to improve their antibacterial properties.     

Microwave-assisted rapid synthesis of anisotropic Ag nanoparticles by solid state transformation

Anisotropic silver nanoparticles (NPs) have been synthesized rapidly using microwave irradiation by the decomposition of silver oxalate in a glycol medium using polyvinyl pyrolidone (PVP) as the capping agent. The obtained Ag nanoparticles have been characterized by UV-visible spectroscopy, powder x-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) studies. Anisotropic Ag nanoparticles of average size around 30?nm have been observed in the case of microwave irradiation for 75?s whereas spherical particles of a size around 5-6?nm are formed for 60?s of irradiation. The texture coefficient and particle size calculated from XRD patterns of anisotropic nanoparticles reveal the preferential orientation of (111) facets in the Ag sample. Ethylene glycol is found to be a more suitable medium than diethylene glycol. A plausible mechanism has been proposed for the formation of anisotropic Ag nanoparticles from silver oxalate.     

Speciation analysis of silver nanoparticles and silver ions in antibacterial products and environmental waters via cloud point extraction-based separation

The rapid growth in commercial use of silver nanoparticles (AgNPs) will inevitably increase silver exposure in the environment and the general population. As the fate and toxic effects of AgNPs is related to the Ag(+) released from AgNPs and the transformation of Ag(+) into AgNPs, it is of great importance to develop methods for speciation analysis of AgNPs and Ag(+). This study reports the use of Triton X-114-based cloud point extraction as an efficient separation approach for the speciation analysis of AgNPs and Ag(+) in antibacterial products and environmental waters. AgNPs were quantified by determining the Ag content in the Triton X-114-rich phase with inductively coupled plasma mass spectrometry (ICPMS) after microwave digestion. The concentration of total Ag(+), which consists of the AgNP adsorbed, the matrix associated, and the freely dissolved, was obtained by subtracting the AgNP content from the total silver content that was determined by ICPMS after digestion. The limits of quantification (S/N = 10) for antibacterial products were 0.4 μg/kg and 0.2 μg/kg for AgNPs and total silver, respectively. The reliable quantification limit was 3 μg/kg for total Ag(+). The presence of Ag(+) at concentrations up to 2-fold that of AgNPs caused no effects on the determination of AgNPs. In the cloud point extraction of AgNPs in antibacterial products, the spiked recoveries of AgNPs were in the range of 71.7-103% while the extraction efficiencies of Ag(+) were in the range of 1.2-10%. The possible coextracted other silver containing nanoparticles in the cloud point extraction of AgNPs were distinguished by transmission electron microscopy (TEM), scanning electron microscopy (SEM)- energy dispersive spectroscopy (EDS), and UV-vis spectrum. Real sample analysis indicated that even though the manufacturers claimed nanosilver products, AgNPs were detected only in three of the six tested antibacterial products.     

Rapid biologically one-step synthesis of stable bioactive silver nanoparticles using Osage orange (Maclura pomifera) leaf extract and their antimicrobial activities

Synthesis of nanoparticles by using natural products as reducing and stabilizing agents have been widely used in various fields especially medicine, primarily because of its lower cost, simplicity, and less toxic byproducts. In the present work, silver nanoparticles (Ag NPs) were rapidly synthesized from silver nitrate in a green one-step synthesis by the aqueous extracts of Osage orange (Maclura pomifera) leaf as a reducing and stabilizing agent simultaneously. The effects of pH, extract quantity, and silver salt concentration were investigated to determine the optimum conditions of green synthesis of Ag NPs. The synthesized Ag NPs were characterized by different techniques including UV–Visible (UV–Vis) absorption spectroscopy, X-ray diffraction (XRD), Fourier transform Infrared (FT-IR) Spectroscopy, and Transmission Electron Microscopy (TEM). The Ag NPs showed surface plasmon resonance centered at 415?nm. The XRD pattern and TEM analysis revealed spherical, stable, and uniform Ag NPs with the average particle size of about 12?nm. The FT-IR spectroscopy showed that mainly hydroxyl functional groups, as both the reducing and stabilizing agent are responsible for silver nanoparticles synthesis. The antimicrobial activity of the synthesized Ag NPs showed a significant microbicidal effect on all clinical isolates especially, Gram-negative bacteria and fungi. These results suggest that such stable and uniform Ag NPs can be synthesized rapidly and simply for clinical as well as pharmaceutical applications.     

Preparation of silver nanocomposites stabilized by an amphiphilic block copolymer under ultrasonic irradiation

Silver nanoparticles were synthesized by using amphiphilic block copolymer Polyacrylonitrile-block-poly(ethylene glycol)-blcok-Polyacrylonitrile (PAN-b-PEG-b-PAN, PEA) based on the flexibility of the copolymer chains and the complex effect of –CN in the polyacrylonitrile with Ag⁺ ion and Ag under ultrasonic irradiation. The product was characterized by X-ray Diffraction (XRD), Fourier Transfer Infrared Spectrometer (FTIR), Transmission Electron Microscope (TEM), UV–Vis spectrum and Thermal Gravity Analysis (TGA). The results revealed that the size and size distribution of the resulting silver nanoparticles prepared basing on the copolymer were strongly dependent on the initial concentration of the silver ion solution and the irradiation conditions. Low initial silver ion concentration allowed for yielding silver nanoparticles with a small size and the size of the silver nanoparticles increased with increasing of silver ion concentration. The silver crystal was polycrystalline with a cubic structure, as confirmed by XRD. This work provides a simple route for the in situ synthesis of Ag nanoparticles.     

Ag/GaP nanoparticles with photooxidation property under visible light

This article reports the use of Gallium phosphide (GaP) and Ag/GaP nanoparticles, which can harness visible light to decompose organic dye in aqueous solution. The Ag(1.139 wt%)/GaP and Ag(5.225 wt%)/GaP nanoparticles were prepared by the liquid phase reduction of silver nitrate with hydrazine hydrate. The application of X-ray fluorescence and high-resolution transmission electron micrograph morphology has provided direct evidence of the presence of silver on the GaP nanoparticles. Under visible light, the experiments on the photocatalytic degradation of crystal violet in solution over the GaP and Ag/GaP nanoparticles were carried out. The results reveal that small size and number density of Ag domains deposited on GaP nanoparticles have enhanced photocatalytic efficiencies, as compared to large size and number density of Ag domains. This study suggests the potential of both GaP and Ag/GaP nanoparticles as photofunctional materials for waste-water cleaning.     

Catalytic properties of silica/silver nanocomposites

The catalytic properties of silver nanoparticles supported on silica and the relation between catalytic activity of silver particles and the support (silica) size are investigated in the present article. The silver nanoparticles with 4 nm diameters were synthesized and were attached to silica spheres with sizes of 40, 78, 105 nm, respectively. The reduction of Rhodamine 6G (R6G) by NaBH4 was designed by using the SiO2/Ag core-shell nanocomposites as catalysts. The experimental results demonstrated that the catalytic activity of silica/silver nanoparticles depends on not only the concentration of catalysts (silver) but also the support silica size. Silver particles supported on small SiO2 spheres (approximately 40 nm) show high catalytic activity. Moreover, by making a comparison between the UV-vis spectra of the catalyst before and after the catalytic reaction, we found that the position of surface plasma resonance (SPR) peak of Ag nanoparticles changes little. The above results suggested that the size and morphology of silver particles were probably kept unchanged after the reduction of R6G and also implied that the catalytic activity of silver particles was hardly lost during the catalytic reaction.     

醇辅助还原法可控制备Cu@Ag核壳颗粒及其抗氧化性能

研究了一种Ag包裹量可控制备Cu@Ag核壳颗粒的方法,其中利用乙二醇(EG)作为还原剂,AgNO3作为Ag源。探讨了不同分散剂,明胶、十六烷基三甲基溴化铵(CTAB)、聚乙烯吡咯烷酮(PVP)对Cu@Ag核壳颗粒形貌的影响,其中明胶作为分散剂时的包覆效果最佳。以明胶作为分散剂,当AgNO3浓度为0.93mol/L时,制得了包裹均匀的Cu@Ag核壳颗粒,其压实薄膜电阻仅为1.6Ω/sq,具有良好的导电性。通过表面Ag的包裹,Cu@Ag核壳颗粒在空气中放置4个月后,压实薄膜电阻为12.6Ω/sq,表现出持久的抗氧化性能。醇还原法可以实现在Cu颗粒表面快捷可控地制备Ag包裹层,包覆率高,且Cu@Ag复合颗粒抗氧化性能持久,适用于工业生产。     

A nanoparticle autocatalytic sensor for Ag+ and Cu2+ ions in aqueous solution with high sensitivity and selectivity and its application in test paper

A novel nanoparticle autocatalytic sensor for the detection of Ag(+) and Cu(2+) has been constructed based on the oxidative ability of Ag(+) and Cu(2+) toward o-phenylenediamine (OPDA). Ag(+) and Cu(2+) can be reduced to zerovalent silver and copper, respectively, and then such zerovalent Ag and Cu species form silver and copper nanoparticles that can catalyze the reaction between OPDA and Ag(+) and Cu(2+). In the reaction, OPDA is oxidized to 2,3-diaminophenazine (OPDAox), which has a fluorescence emission at 568 nm. Under the optimal conditions, Ag(+) and Cu(2+) can be detected in the concentration ranges from 60 nM to 60 μM and from 2.5 nM to 25 μM, respectively. Through this facile approach, Ag(+) and Cu(2+) can be detected down to 60 nM and 2.5 nM, respectively. In addition, the sensor is utilized for the detection of Ag(+) and Cu(2+) in sewage, and we have obtained very good results that are consistent with those of inductively coupled plasma-mass spectroscopy (ICP-MS). Moreover, such a nanoparticle autocatalytic sensor is applied to test paper for the detection of Ag(+) and Cu(2+) with the naked eye. With such test paper, Ag(+) and Cu(2+) could be detected at levels as low as 0.06 nmol and 0.3 nmol, respectively, with detection ranges of 0.06-60 nmol for Ag(+) and 0.3-60 nmol for Cu(2+), under the irradiation of UV light (365 nm). The test paper could be potentially used in the rapid detection of Ag(+) and Cu(2+) in real samples.     

Biosynthesis of gold and silver nanoparticles using Emblica Officinalis fruit extract, their phase transfer and transmetallation in an organic solution

The design, synthesis and characterization of biologically synthesized nanomaterials have become an area of significant interest. In this paper, we report the extracellular synthesis of gold and silver nanoparticles using Emblica Officinalis (amla, Indian Gooseberry) fruit extract as the reducing agent to synthesize Ag and Au nanoparticles, their subsequent phase transfer to an organic solution and the transmetallation reaction of hydrophobized silver nanoparticles with hydrophobized chloroaurate ions. On treating aqueous silver sulfate and chloroauric acid solutions with Emblica Officinalis fruit extract, rapid reduction of the silver and chloroaurate ions is observed leading to the formation of highly stable silver and gold nanoparticles in solution. Transmission Electron Microscopy analysis of the silver and gold nanoparticles indicated that they ranged in size from 10 to 20 nm and 15 to 25 nm respectively. Ag and Au nanoparticles thus synthesized were then phase transferred into an organic solution using a cationic surfactant octadecylamine. Transmetallation reaction between hydrophobized silver nanoparticles and hydrophobized chloroaurate ions in chloroform resulted in the formation of gold nanoparticles.     

Structural analysis of graphene oxide/silver nanocomposites: optical properties,electrochemical sensing and photocatalytic activity

In the present study, graphene oxide/silver (GO/Ag) nanocomposites were synthesized via a facile simple one pot chemical reduction method using ethylene glycol/sodium borohydrate (EG/NaBH₄) as solvent and reducing agent. GO was selected as a substrate and stabilizer to prepare GO/Ag nanocomposites. The synthesized GO/Ag nanocomposites were characterized by a series of techniques. Highly monodispersed stable crystalline silver nanoparticles having a face-centered cubic (fcc) phase were confirmed by X-ray powder diffraction (XRD) on GO signature. Scanning electron microscopy images showed that Ag nanoparticles are deposited on the GO sheet with a narrow size distribution. Transmission electron microscopy observations revealed that large numbers of Ag nanoparticles were uniformly distributed on GO sheet and well separated with an average size of 18 nm. Ultraviolet–visible (UV–Vis) spectroscopic results showed the peak of GO and surface plasmon resonance (SPR) of Ag nanoparticles. The SPR property of GO/Ag nanocomposites showed that there was an interaction between Ag nanoparticles and GO sheet. The intensities of the Raman signal of GO/Ag nanocomposites are gradually increased with attachment of Ag nanoparticles i.e. there is surface-enhanced Raman scattering activity. Electrochemical investigations indicated that the nanocomposites possessed an excellent performance for detecting towards 4-nitrophenol. An application of the obtained GO/Ag nanocomposites as a catalyst in the reduction of 4-nitrophenol to 4-aminophenol by NaBH₄ was demonstrated. The GO/Ag nanocomposites exhibited high activity and stability for the catalytic reduction of 4-nitrophenol. The prepared GO/Ag nanocomposites act as photo-catalysts.     

Preparation,characterisation and kinetics of corn-shaped Ag nanoparticles

Conventional UV-vis spectroscopic and transmission electron microscopy methods were used to monitor the kinetics, formation and characterisation of silver nanoparticles in the methionine-promoted reduction of silver(I). The silver nanoparticles (purple colour; λ _max?=?550?nm) are corn-shaped and aggregated, and the average particle size is about 23?nm. The kinetics of silver nanoparticles formation has been studied as a function of [Ag(I)], [methionine] and [CTAB]. We see that [Ag(I)] has no effect on the rate of silver nanoparticles formation. At higher [CTAB]?≥?40.0?×?10^?4?mol?dm^?3, silver nanoparticles were not observed. Methionine is responsible for interparticle interaction, increase in aggregate size and cross-linking between the particles, and it acts as complexing, reducing, adsorbing and capping agents. A mechanism consistent with the observed kinetics has been proposed and discussed.     

Synthesis of silver nanorods by low energy excitation of spherical plasmonic seeds

Plasmon excitation of Ag seed particles with 600-750 nm light in the presence of Ag(+) and trisodium citrate was used to synthesize penta-twinned nanorods. Importantly, the excitation wavelength can be used to control the reaction rate and, consequently, the aspect ratio of the nanorods. When the excitation wavelength is red-shifted from the surface plasmon resonance of the spherical seed particles, the rate of Ag(+) reduction becomes slower and more kinetically controlled. Such conditions favor the deposition of silver onto the tips of the growing nanorods as compared to their sides, resulting in the generation of higher aspect ratio rods. However, control experiments reveal that there is only a range of low energy excitation wavelengths (between 600 and 750 nm) that yields monodisperse nanorods. This study further highlights the utility of using wavelength to control the size and shape of growing nanoparticles using plasmon-mediated methods.     

Real-time monitoring of plasmonic evolution in thick Ag:SiO(2) films: nanocomposite optical tuning

An in situ optical microspectroscopy study of the surface plasmon resonance (SPR) evolution of Ag nanoparticles (NPs) embedded in thick SiO(2) films deposited on soda-lime glass has been conducted during thermal processing in air. The temperature and time dependences of the SPR were analyzed in the context of Mie extinction and crystal growth theories and were discussed along with consideration of oxidation processes and film/substrate physicochemical interactions. At relatively high temperatures, Ag NPs were indicated to grow first through a diffusion-based process and subsequently via Ostwald ripening. At lower temperatures, an initial decrease in Ag particle size was indicated due to oxidation, followed by NP diffusion-based growth. The growth and oxidation stages appeared temperature and time dependent, allowing for the tuning of material properties. The product of Ag NP oxidation was revealed by photoluminescence spectroscopy performed ex situ as single Ag(+) ions. The oxidative effect of the air atmosphere on Ag NPs was shown to be ultimately circumvented by the thick nanocomposite film. The phenomenon was explained on the basis of the displacement of the Ag/Ag(+) redox equilibrium toward Ag NP stability after ion migration toward the substrate being self-constrained. In addition, the current spectroscopic approach has been proposed for estimating the activation energy for silver diffusion in the SiO(2) matrix.     

Silver nanoparticles/montmorillonite composites prepared using nitrating reagent at water and glycerol

Three procedures (P) were applied to prepare silver nanoparticles on natural Ca-montmorillonite (MT). The intercalation of the montmorillonite with silver nitrate in aqueous solution (P1), the intercalation of the montmorillonite with silver nitrate in glycerol (P2) and the successive combination of both P1 and P2 methods resulted to P3 method. X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and Fourier Transform Infrared (FTIR) spectroscopy and the molecular modeling were employed to characterize silver nanoparticles and montmorillonite nanocomposite. The P1 produced MT-1 composite with 2.3 wt% Ag and the partially collapsed layered structure. Nanoparticles of silver larger than 20 nm with a lot of planar defects were randomly distributed on the MT-1 surface; nanoparticles smaller than 20 nm were oriented to the montmorillonite substrate. The MT-2 composite from P2 contained only 1 wt% of Ag. The molecular simulation model of MT-2 showed the interlayer space with the exchangeable cations and metallic silver atoms arrangement within the glycerol bilayer. The P3 produced composite MT-3 that contained 2.4 wt% Ag. The nanoparticles > 20 nm size had a well-defined geometry, very small nanoparticles were amorphous. The modeled structure showed the exchangeable cations, Ag+ and Ag0 located close to the silicate layers and monolayer of glycerol molecules in the interlayer space.     

Well-defined nanoclusters as fluorescent nanosensors: a case study on Au(25) (SG)(18)

The fluorescence of nanoparticles has attracted much attention in recent research, but in many cases the underlying mechanisms are difficult to evaluate due to the polydispersity of nanoparticles and their unknown structures, in particular the surface structures. Recent breakthroughs in the syntheses and structure determinations of well-defined gold nanoclusters provide opportunities to conduct in-depth investigations. Devising well-defined nanocluster sensors based on fluorescence change is of particular interest not only for scientific studies but also for practical applications. Herein, the potential of the glutathionate (SG)-capped Au(25) nanocluster as a silver ion sensor is evaluated. The Ag(+) detection limit of approximately 200 nM, based on the fluorescence enhancement and good linear fluorescence response in the silver ion concentration range from 20 nM to 11 μM, in combination with the good selectivity among 20 types of metal cations, makes Au(25) (SG)(18) a good candidate for fluorescent sensors for silver ions. Further experiments reveal three important factors responsible for the unique fluorescence enhancement caused by silver ions: 1) the oxidation state change of Au(25) (SG)(18) ; 2) the interaction of neutral silver species (Ag(0) , reduced by Au(25) (SG)(18) (-) ) with Au(25) (SG)(18) ; and 3) the interaction of Ag(+) with Au(25) (SG)(18.) Experiments demonstrate the very different chemistry of hydrophobic Au(25) (SC(2) H(4) Ph)(18) and hydrophilic Au(25) (SG)(18) in the reaction with silver ions. This work indicates another potential application of gold nanoclusters, offers new strategies for nanocluster-based chemical sensing, and reveals a new way to influence nanocluster chemistry for potential applications.     

Synthesis of silver-integrated silica nanostructures using rice hulls and their electrochemical performance for supercapacitor application

We report the synthesis of silver-integrated silica nanostructures using rice hulls and silver chloride through a facile thermal combustion process. The formation of mesoporous silica nanomatrix embedded with silver nanoparticles (SiO₂:Ag 5 wt% and SiO₂:Ag 10 wt%) was confirmed by XRD, FTIR, EDX, BET, and TEM analysis. Also, the obtained results from the above studies revealed that the concentration of silver ions significantly increases the particle size and number of silver nanoparticles formed in the silica matrix. The electrochemical performance was studied using silver-integrated silica nanostructures as a working electrode in KOH electrolyte. The maximum specific capacitance of SiO₂:Ag 5 wt%- and SiO₂:Ag 10 wt%-coated electrode was found to be 517 and 580 F/g at current density of 1 A/g. It was also found that SiO₂:Ag 10 wt% electrode exhibit an excellent stability with the capacitance retention of 94% than SiO₂:Ag 5 wt% (capacitance retention of 85%) after 1000 cycles at a current density of 1 A/g. These results may be attributed to the inherent characteristic of more silver nanoparticles present in the silica nanomatrix in SiO₂:Ag 10 wt%. The intrinsic characteristic of rice hull-derived silica nanostructures such as high surface area and mesoporous structure along with the advantage of silver nanoparticles (conductivity) can facilitate the Faradic redox processes at electrode surface which are responsible for the supercapacitive behavior of the prepared silver-integrated silica nanostructures.

     

In-situ preparation of binary-phase silver nanoparticles at a high Ag+ concentration

Stable and monodisperse silver nanoparticles (NPs) have been synthesized using high metal salt concentration (up to 0.735 M) through a simple but novel technique. It is based on one-step procedure that uses glycerol for reducing Ag+ in the presence of o-phenylenediamine (o-PDA) resulting the nanoparticles are in two forms (one water-soluble, the other a precipitated). The water-soluble phase contains NPs that have a bimodal size distribution (2-3 and 5-6 nm); the other comprises precipitated NPs, having a unimodal size distribution (2-3 nm). The water-soluble NPs are covalently bonded to the aromatic amine molecules to form isolated units, while the precipitated nanoparticles are embedded in the networks formed by cross-linking between COOH groups of hydroxypyruvic acid (oxidized form of glycerol) and NH2 groups of o-PDA molecules. We used transmission electron microscopy (TEM), UV-Vis spectroscopy, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) to characterize the silver products obtained.