Search results for: gold catalysts

Authors: Marius Sebastian Secula, Mihaela Darie, Gabriela Carja

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Persistent organic pollutant discharged by various industries or urban regions into the aquatic ecosystems represent a serious threat to fauna and human health. The endocrine disrupting compounds are known to have toxic effects even at very low values of concentration. The anti-inflammatory agent Ibuprofen is an endocrine disrupting compound and is considered as model pollutant in the present study. The use of light energy to accomplish the latest requirements concerning wastewater discharge demands highly-performant and robust photo-catalysts. Many efforts have been paid to obtain efficient photo-responsive materials. Among the promising photo-catalysts, layered double hydroxides (LDHs) attracted significant consideration especially due to their composition flexibility, high surface area and tailored redox features. This work presents Fe(II) self-supported on ZnMeLDHs (Me =Al3+, Fe3+) as novel efficient photo-catalysts for Fenton-like catalysis. The co-precipitation method was used to prepare ZnAlLDH, ZnFeAlLDH and ZnCrLDH (Zn2+/Me3+ = 2 molar ratio). Fe(II) was self-supported on the LDHs matrices by using the reconstruction method, at two different values of weight concentration. X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), Fourier transform infrared (FTIR) and transmission electron microscopy (TEM) were used to investigate the structural, textural, and micromorphology of the catalysts. The Fe(II)/ZnMeLDHs nano-hybrids were tested for the degradation of a model pharmaceutical agent, the anti-inflammatory agent ibuprofen, by photocatalysis and photo-Fenton catalysis, respectively. The results point out that the embedment Fe(II) into ZnFeAlLDH and ZnCrLDH lead to a slight enhancement of ibuprofen degradation by light irradiation, whereas in case of ZnAlLDH, the degradation process is relatively low. A remarkable enhancement of ibuprofen degradation was found in the case of Fe(II)/ZnMeLDHs by photo-Fenton process. Acknowledgements: This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS - UEFISCDI, project number PN-II-RU-TE-2014-4-0405.

Keywords: layered double hydroxide, heterogeneous Fenton, micropollutant, photocatalysis

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Authors: Chetna Tyagi. G. B. V. S. Lakshmi, Ambuj Tripathi, D. K. Avasthi

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Graphene oxide provides a good host matrix for preparing nanocomposites due to the different functional groups attached to its edges and planes. Being biocompatible, it is used in therapeutic applications. As enzyme-based biosensor requires complicated enzyme purification procedure, high fabrication cost and special storage conditions, we need enzyme-less biosensors for use even in a harsh environment like high temperature, varying pH, etc. In this work, we have prepared both enzyme-based and enzyme-less graphene oxide-based biosensors for glucose detection using glucose-oxidase as enzyme and gold nanoparticles, respectively. These samples were characterized using X-ray diffraction, UV-visible spectroscopy, scanning electron microscopy, and transmission electron microscopy to confirm the successful synthesis of the working electrodes. Electrochemical measurements were performed for both the working electrodes using a 3-electrode electrochemical cell. Cyclic voltammetry curves showed the homogeneous transfer of electron on the electrodes in the scan range between -0.2V to 0.6V. The sensing measurements were performed using differential pulse voltammetry for the glucose concentration varying from 0.01 mM to 20 mM, and sensing was improved towards glucose in the presence of gold nanoparticles. Gold nanoparticles in graphene oxide nanocomposite played an important role in sensing glucose in the absence of enzyme, glucose oxidase, as evident from these measurements. The selectivity was tested by measuring the current response of the working electrode towards glucose in the presence of the other common interfering agents like cholesterol, ascorbic acid, citric acid, and urea. The enzyme-less working electrode also showed storage stability for up to 15 weeks, making it a suitable glucose biosensor.

Keywords: electrochemical, enzyme-less, glucose, gold nanoparticles, graphene oxide, nanocomposite

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Authors: Nihel Dib, Redouane Bachir, Ghezlane Berrahou, Chaima Zoulikha Tabet Zatla, Sumeya Bedrane, Ginessa Blanco Montilla, Jose Juan Calvino Gamez

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In recent decades, the world’s population has rapidly increased annually, resulting in the consumption of huge amounts of conventional non-renewable petroleum-based resources at an alarming rate. The scarcity of such resources will shut down the corresponding industries and consequently have negative effects on the well-being of humanity. Accordingly, to combat the forthcoming crises and to serve the ever-growing demands, seeking potentially sustainable resources such as geothermal, wind, solar, and biomass has become an active field of study. Currently, lignocellulosic biomass, one of the world’s most plentiful resources, is acknowledged as a cost-effective material that has drawn great interest from many researchers since it has substantial energy potential as well as containing useful C5 and C6 sugars. These C5 and C6 sugars are the key reactants for the production of the valuable 16-platform chemicals such as 5-hydroxymethyl furfural, furfural, levulinic acid, succinic acid, and fumaric acid, all of which are crucial intermediates for synthesizing high-value bio-based chemicals and polymers. Succinic acid (SA) has been predicted to make a significant contribution to the global bio-based economy soon since it serves as a C4 building block that is used in a wide spectrum of industries, including biopolymers, solvents, and pharmaceuticals. In the present work, we modify the HDL MgAl with Zr to try to create acid sites on the supports and deposit gold by deposition precipitation with urea with a low gold content (0.25%). The catalyst was used to produce succinic acid by selective oxidation of furfuraldehyde with hydrogen peroxide under mild reaction conditions.

Keywords: hydrotalcite, catalysis, gold, biomass, furfural, oxidation

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Authors: Sunitha Sampathi, Pankaj Kumar Tiriya, Sonia Gera, Sravanthi Reddy Pailla, V. Likhitha, A. J. Maruthi

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Surgical site infections (SSIs) are the most common nosocomial infections localized at the incision site. With an estimated 27 million surgical procedures each year in USA, approximately 2-5% rate of SSIs are predicted to occur annually. SSIs are treated with antibiotic medication. Current trend suggest that the direct drug delivery from the suture to the scared tissue can improve patient comfort and wound recovery. For that reason coating the surface of the medical device such as suture and catguts with broad spectrum antibiotics can prevent the formation of bactierial colonies with out comprimising the mechanical properties of the sutures.Hence, the present study was aimed to develop and evaluate a surgical suture coated with an antibiotic Ciprofloxacin hydrochloride loaded on gold nanoparticles. Gold nanoparticles were synthesized by chemical reduction method and conjugated with ciprofloxacin using Polyvinylpyrolidone as stabilizer and gold as carrier. Ciprofloxacin conjugated gold nanoparticles were coated over an absorbable surgical suture made of Polyglactan using sodium alginate as an immobilising agent by slurry dipping technique. The average particle size and Polydispersity Index of drug conjugated gold NPs were found to be 129±2.35 nm and 0.243±0.36 respectively. Gold nanoparticles are characterized by UV-Vis absorption spectroscopy, Fourier Transform Infrared Spectroscopy (FT-IR), Scanning electron microscopy and Transmission electron microscopy. FT-IR revealed that there is no chemical interaction between drug and polymer. Antimicrobial activity for coated sutures was evaluated by disc diffusion method on culture plates of both gram negative (E-coli) and gram positive bacteria (Staphylococcus aureus) and results found to be satisfactory. In vivo studies for coated sutures was performed on Swiss albino mice and histological evaluation of intestinal wound healing parameters such as wound edges in mucosa, muscularis, presence of necrosis, exudates, granulation tissue, granulocytes, macrophages, restoration, and repair of mucosal epithelium and muscularis propria on day 7 after surgery were studied. The control animal group, sutured with plain suture (uncoated suture) showed signs of restoration and repair, but presence of necrosis, heamorraghic infiltration and granulation tissue was still noticed. Whereas the animal group treated with ciprofloxacin and ciprofloxacin gold nanoparticle coated sutures has shown promising decrease in terms of haemorraghic infiltration, granulation tissue, necrosis and better repaired muscularis layers on comparision with plain coated sutures indicating faster rate of repair and less chance of sepsis. Hence coating of sutures with broad spectrum antibiotics can be an alternate technique to reduce SSIs.

Keywords: ciprofloxacin hydrochloride, gold nanoparticles, surgical site infections, sutures

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Authors: A. Abdelnasser, M. Kumral, B. Zoheir, P. Weihed, M. Budakoglu, L. Gumus

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Atud gold deposits located at the central part of the Egyptian Eastern Desert of Egypt. It represents the vein-type gold mineralization at the Arabian-Nubian Shield in North Africa. Furthermore, this Au mineralization was closely associated with intense hydrothermal alteration haloes along the NW-SE brittle-ductile shear zone at the mined area. This study reports new data about the mineral chemistry of the hydrothermal and metamorphic minerals as well as the geothermobarometry of the metamorphism and determines the paragenetic interrelationship between Au-bearing sulfides and gangue minerals in Atud gold mine by using the electron microprobe analyses (EMPA). These analyses revealed that the ore minerals associated with gold mineralization are arsenopyrite, pyrite, chalcopyrite, sphalerite, pyrrhotite, tetrahedrite and gersdorffite-cobaltite. Also, the gold is highly associated with arsenopyrite and As-bearing pyrite as well as sphalerite with an average ~70 wt.% Au (+26 wt.% Ag) whereas it occurred either as disseminated grains or along microfractures of arsenopyrite and pyrite in altered wallrocks and mineralized quartz veins. Arsenopyrite occurs as individual rhombic or prismatic zoned grains disseminated in the quartz veins and wallrock and is intergrown with euhedral arsenian pyrite (with ~2 atom % As). Pyrite is As-bearing pyrite that occurs as disseminated subhedral or anhedral zoned grains replacing by chalcopyrite in some samples. Inclusions of sphalerite and pyrrhotite are common in the large pyrite grains. Secondary minerals such as sericite, calcite, chlorite and albite are disseminated either in altered wallrocks or in quartz veins. Sericite is the main secondary and alteration mineral associated with Au-bearing sulfides and calcite. Electron microprobe data of the sericite show that its muscovite component is high in all analyzed flakes (XMs= an average 0.89) and the phengite content (Mg+Fe a.p.f.u.) varies from 0.10 to 0.55 and from 0.13 to 0.29 in wallrocks and mineralized veins respectively. Carbonate occurs either as thin veinlets or disseminated grains in the mineralized quartz vein and/or the wallrocks. It has higher amount of calcite (CaCO3) and low amount of MgCO3 as well as FeCO3 in the wallrocks relative to the quartz veins. Chlorite flakes are associated with arsenopyrite and their electron probe data revealed that they are generally Fe-rich composition (FeOt 20.64–20.10 wt.%) and their composition is clinochlore either pycnochlorite or ripidolite with Al (iv) = 2.30-2.36 pfu and 2.41-2.51 pfu and with narrow range of estimated formation temperatures are (289–295°C) and (301-312°C) for pycnochlorite and ripidolite respectively. Albite is accompanied with chlorite with an Ab content is high in all analyzed samples (Ab= 95.08-99.20).

Keywords: micro-analytical data, mineral chemistry, EMPA, Atud gold deposit, Egypt

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Authors: Chang, Ya-Ju, Hsieh, Pei-Hsin, Wu, Jui-Chuang, Chen-Yang, Yui Whei

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A mesoporous silica material was prepared to apply to the lateral-flow immunochromatography for detecting a model biosample. The probe antibody is immobilized on the silica surface as the test line to capture its affinity antigen, which laterally flows through the chromatography strips. The antigen is labeled with nano-gold particles, such that the detection can be visually read out from the test line without instrument aids. The result reveals that the mesoporous material provides a vast area for immobilizing the detection probes. Biosening surfaces corresponding with a positive proportion of detection signals is obtained with the biosample loading.

Keywords: mesoporous silica, immunochromatography, lateral-flow strips, biosensors, nano-gold particles

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Authors: Nayana T. Nivangune, Vivek V. Ranade, Ashutosh A. Kelkar

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Organic carbamates are versatile compounds widely employed as pesticides, fungicides, herbicides, dyes, pharmaceuticals, cosmetics and in the synthesis of polyurethanes. Carbamates can be easily transformed into isocyanates by thermal cracking. Isocyantes are used as precursors for manufacturing agrochemicals, adhesives and polyurethane elastomers. Manufacture of polyurethane foams is a major application of aromatic ioscyanates and in 2007 the global consumption of polyurethane was about 12 million metric tons/year and the average annual growth rate was about 5%. Presently Isocyanates/carbamates are manufactured by phosgene based process. However, because of high toxicity of phoegene and formation of waste products in large quantity; there is a need to develop alternative and safer process for the synthesis of isocyanates/carbamates. Recently many alternative processes have been investigated and carbamate synthesis by methoxycarbonylation of aromatic amines using dimethyl carbonate (DMC) as a green reagent has emerged as promising alternative route. In this reaction methanol is formed as a by-product, which can be converted to DMC either by oxidative carbonylation of methanol or by reacting with urea. Thus, the route based on DMC has a potential to provide atom efficient and safer route for the synthesis of carbamates from DMC and amines. Lot of work is being carried out on the development of catalysts for this reaction and homogeneous zinc salts were found to be good catalysts for the reaction. However, catalyst/product separation is challenging with these catalysts. There are few reports on the use of supported Zn catalysts; however, deactivation of the catalyst is the major problem with these catalysts. We wish to report here methoxycarbonylation of aniline to methylphenylcarbamate (MPC) using amino acid complexes of Zn as highly active and selective catalysts. The catalysts were characterized by XRD, IR, solid state NMR and XPS analysis. Methoxycarbonylation of aniline was carried out at 170 °C using 2.5 wt% of the catalyst to achieve >98% conversion of aniline with 97-99% selectivity to MPC as the product. Formation of N-methylated products in small quantity (1-2%) was also observed. Optimization of the reaction conditions was carried out using zinc-proline complex as the catalyst. Selectivity was strongly dependent on the temperature and aniline:DMC ratio used. At lower aniline:DMC ratio and at higher temperature, selectivity to MPC decreased (85-89% respectively) with the formation of N-methylaniline (NMA), N-methyl methylphenylcarbamate (MMPC) and N,N-dimethyl aniline (NNDMA) as by-products. Best results (98% aniline conversion with 99% selectivity to MPC in 4 h) were observed at 170oC and aniline:DMC ratio of 1:20. Catalyst stability was verified by carrying out recycle experiment. Methoxycarbonylation preceded smoothly with various amine derivatives indicating versatility of the catalyst. The catalyst is inexpensive and can be easily prepared from zinc salt and naturally occurring amino acids. The results are important and provide environmentally benign route for MPC synthesis with high activity and selectivity.

Keywords: aniline, heterogeneous catalyst, methoxycarbonylation, methylphenyl carbamate

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Authors: Manal M. Kame, Hanan G. El-Baz, Zeinab A.Demerdash, Engy M. Abd El-Moneem, Mohamed A. Hendawy, Ibrahim R. Bayoumi

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There is a constant need to improve the performance of current diagnostic assays of schistosomiasis as well as develop innovative testing strategies to meet new testing challenges. This study aims at increasing the diagnostic efficiency of monoclonal antibody (MAb)-based antigen detection assays through gold nanoparticles conjugated with specific anti-Schistosoma mansoni monoclonal antibodies. In this study, several hybidoma cell lines secreting MAbs against adult worm tegumental Schistosoma antigen (AWTA) were produced at Immunology Department of Theodor Bilharz Research Institute and preserved in liquid nitrogen. One MAb (6D/6F) was chosen for this study due to its high reactivity to schistosome antigens with highest optical density (OD) values. Gold nanoparticles (AuNPs) were functionalized and conjugated with MAb (6D/6F). The study was conducted on serum samples of 116 subjects: 71 patients with S. mansoni eggs in their stool samples group (gp 1), 25 with other parasites (gp2) and 20 negative healthy controls (gp3). Patients in gp1 were further subdivided according to egg count in their stool samples into Light infection {≤ 50 egg per gram(epg) (n= 17)}, moderate {51-100 epg (n= 33)} and severe infection {>100 epg(n= 21)}. Sandwich ELISA was performed using (AuNPs -MAb) for detection of circulating schistosomal antigen (CSA) levels in serum samples of all groups and the results were compared with that after using MAb/ sandwich ELISA system. Results Gold- MAb/ ELISA system reached a lower detection limit of 10 ng/ml compared to 85 ng/ml on using MAb/ ELISA and the optimal concentrations of AuNPs -MAb were found to be 12 folds less than that of MAb/ ELISA system for detection of CSA. The sensitivity and specificity of sandwich ELISA for detection of CSA levels using AuNPs -MAb were 100% & 97.8 % respectively compared to 87.3% &93.38% respectively on using MAb/ ELISA system. It was found that CSA was detected in 9 out of 71 S.mansoni infected patients on using AuNPs - MAb/ ELISA system and was not detected by MAb/ ELISA system. All those patients (9) was found to have an egg count below 50 epg feces (patients with light infections). ROC curve analyses revealed that sandwich ELISA using gold-MAb was an excellent diagnostic investigator that could differentiate Schistosoma patients from healthy controls, on the other hand it revealed that sandwich ELISA using MAb was not accurate enough as it could not recognize nine out of 71 patients with light infections. Conclusion Our data demonstrated that: Loading gold nanoparticles with MAb (6D/6F) increases the sensitivity and specificity of sandwich ELISA for detection of CSA, thus active (early) and light infections could be easily detected. Moreover this binding will decrease the amount of MAb consumed in the assay and lower the coast. The significant positive correlation that was detected between ova count (intensity of infection) and OD reading in sandwich ELISA using gold- MAb enables its use to detect the severity of infections and follow up patients after treatment for monitoring of cure.

Keywords: Schistosomiasis, nanoparticles, gold, monoclonal antibodies, ELISA

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Authors: M. Shemis, O. Maher, G. Casterou, F. Gauffre

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Hepatitis C virus (HCV) is a major cause of chronic liver disease with a global 170 million chronic carriers at risk of developing liver cirrhosis and/or liver cancer. Egypt reports the highest prevalence of HCV worldwide. Currently, two classes of assays are used in the diagnosis and management of HCV infection. Despite the high sensitivity and specificity of the available diagnostic assays, they are time-consuming, labor-intensive, expensive, and require specialized equipment and highly qualified personal. It is therefore important for clinical and economic terms to develop a low-tech assay for the direct detection of HCV RNA with acceptable sensitivity and specificity, short turnaround time, and cost-effectiveness. Such an assay would be critical to control HCV in developing countries with limited resources and high infection rates, such as Egypt. The unique optical and physical properties of gold nanoparticles (AuNPs) have allowed the use of these nanoparticles in developing simple and rapid colorimetric assays for clinical diagnosis offering higher sensitivity and specificity than current detection techniques. The current research aims to develop a detection assay for HCV RNA using gold nanoparticles (AuNPs). Methods: 200 anti-HCV positive samples and 50 anti-HCV negative plasma samples were collected from Egyptian patients. HCV viral load was quantified using m2000rt (Abbott Molecular Inc., Des Plaines, IL). HCV genotypes were determined using multiplex nested RT- PCR. The assay is based on the aggregation of AuNPs in presence of the target RNA. Aggregation of AuNPs causes a color shift from red to blue. AuNPs were synthesized using citrate reduction method. Different sets of probes within the 5’ UTR conserved region of the HCV genome were designed, grafted on AuNPs and optimized for the efficient detection of HCV RNA. Results: The nano-gold assay could colorimetrically detect HCV RNA down to 125 IU/ml with sensitivity and specificity of 91.1% and 93.8% respectively. The turnaround time of the assay is < 30 min. Conclusions: The assay allows sensitive and rapid detection of HCV RNA and represents an inexpensive and simple point-of-care assay for resource-limited settings.

Keywords: HCV, gold nanoparticles, point of care, viral load

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Authors: Brahim Merdas, Abdelhak Boutaleb

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Polymetallic mineralizations with Zn, Sb, Pb boxed in miopliocene limestones of Hammam N’bails’s basin are regarded as the youngest mineralizations of North East of Algeria and are characterized by the presence of rather rare mineral phases throughout the world such as nadorite and flajolotite. Mineralization seems to have a bond with thermal springs emergent within the basin and with the faults which limit the basin. The comparison between mineralizations and similar ore deposits known in the world and which are characterized by the presence of the noble metals such as gold and the discovery of traces of this metal (1.4g/t) enables us to start again the problems of the noble metals of the type “low sulfidation” related to the thermal springs in the area in particular and in all Algerian North generally.

Keywords: Nadorite, galana, gold, dolomitisation, epigenétic, hot springs, , miopliocene, Hammam N’bails, algeria

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Authors: Srinivas Nerella

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A series of new heterodentate N, O-donor ligands derived from condensing 3-amino Coumarins with hydroxy benzaldehydes and acetophenones were used to afford new mononuclear Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Pd(II) coordination compounds. All the complexes were characterized by IR, 1H-NMR, 13C-NMR, Mass, ESR, Electronic spectra, Conductance, Magnetic and Thermal studies. The ligands show hexa coordination in Mn(II), Co(II), Ni(II), and Pd(II) complexes resulting octahedral geometries, while the ligands in Zn(II) and Cu(II) complexes show tetra coordination resulting tetrahedral and square planar geometries respectively. These mononuclear complexes were investigated as catalysts in the hydrothiolation of aromatic and aliphatic alkynes with thiols. These metal complexes were acted as versatile catalysts and gave good yields.

Keywords: schiff bases, divalent metal complexes of schiff bases, Catalytic activity, hydrothiolation

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Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman

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Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However, the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol-gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The as-prepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve

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Authors: Shimayali Kaushal, Nitesh Priyadarshi, Nitin Kumar Singhal

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Food borne bacterial species have been identified as major pathogens in most of the severe pathogen-related diseases among humans which result in great loss to human health and food industry. Conventional methods like plating and enzyme-linked immune sorbent assay (ELISA) are time-consuming, laborious and require specialized instruments. Nanotechnology has emerged as a great field in case of rapid detection of pathogens in recent years. The AuNRs material has good electro-optical properties due to its larger light absorption band and scattering in surface plasmon resonance wavelength regions. By exploiting the sugar-based adhesion properties of microorganism, we can use the glycoconjugates capped gold nanorods as a potential nanobiosensor to detect the foodborne pathogen. In the present study, polyethylene glycol (PEG) coated gold nanorods (AuNRs) were prepared and functionalized with different types of carbohydrates and further characterized by UV-Visible spectrophotometry, dynamic light scattering (DLS), transmission electron microscopy (TEM). The reactivity of above said nano-biosensor was probed by lectin binding assay and also by different strains of foodborne bacteria by using spectrophotometric and microscopic techniques. Due to the specific interaction of probe with foodborne bacteria (Escherichia coli, Pseudomonas aeruginosa), our nanoprobe has shown significant and selective ablation of targeted bacteria. Our findings suggest that our nanoprobe can be an ideal candidate for selective optical detection of food pathogens and can reduce loss to the food industry.

Keywords: glyco-conjugates, gold nanorods, nanobiosensor, nanoprobe

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Authors: Alessio Varotto, Lorenzo Freschi, Umberto Pasqual Laverdura, Anastasia Moschovi, Davide Pumiglia, Iakovos Yakoumis, Marta Feroci, Maria Luisa Grilli

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Dry reforming of Methane (DRM) is considered one of the most valuable technologies for green-house gas valorization thanks to the fact that through this reaction, it is possible to obtain syngas, a mixture of H₂ and CO in an H₂/CO ratio suitable for utilization in the Fischer-Tropsch process of high value-added chemicals and fuels. Challenges of the DRM process are the reduction of costs due to the high temperature of the process and the high cost of precious metals of the catalyst, the metal particles sintering, and carbon deposition on the catalysts’ surface. The aim of this study is to demonstrate the feasibility of the synthesis of catalysts using a leachate solution containing Pt coming directly from the recovery of spent diesel oxidation catalysts (DOCs) without further purification. An unusual perovskite support for DRM, the BaCe₁₋ₓ₋ᵧZrₓGdᵧO₃ (BCZG) perovskite, has been chosen as the catalyst support because of its high thermal stability and capability to produce oxygen vacancies, which suppress the carbon deposition and enhance the catalytic activity of the catalyst. BCZG perovskite has been synthesized by a sol-gel modified Pechini process and calcinated in air at 1100 °C. BCZG supports have been impregnated with a Pt-containing leachate solution of DOC, obtained by a mild hydrometallurgical recovery process, as reported elsewhere by some of the authors of this manuscript. For comparison reasons, a synthetic solution obtained by digesting commercial Pt-black powder in aqua regia was used for BCZG support impregnation. Pt nominal content was 2% in both BCZG-based catalysts formed by real and synthetic solutions. The structure and morphology of catalysts were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Thermogravimetric Analysis (TGA) was used to study the thermal stability of the catalyst’s samples. Brunauer-Emmett-Teller (BET) analysis provided a high surface area of the catalysts. H₂-TPR (Temperature Programmed Reduction) analysis was used to study the consumption of hydrogen for reducibility, and it was associated with H₂-TPD characterization to study the dispersion of Pt on the surface of the support and calculate the number of active sites used by the precious metal. Dry reforming of methane (DRM) reaction, carried out in a fixed bed reactor, showed a high conversion efficiency of CO₂ and CH4. At 850°C, CO₂ and CH₄ conversion were close to 100% for the catalyst obtained with the aqua regia-based solution of commercial Pt-black, and ~70% (for CH₄) and ~80 % (for CO₂) in the case of real HCl-based leachate solution. H₂/CO ratios were ~0.9 and ~0.70 in the first and latter cases, respectively. As far as we know, this is the first pioneering work in which a BCGZ catalyst and a real Pt-containing leachate solution were successfully employed for DRM reaction.

Keywords: dry reforming of methane, perovskite, PGM, recycled Pt, syngas

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Authors: O. P. Yadav

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Nano-size Ag-N co-doped ZnO/CuO composite photo-catalyst has been synthesized by chemical method and characterized using XRD, TEM, FTIR, AAS and UV-Vis spectroscopic techniques. Photo-catalytic activity of as-synthesized nanomaterial has been studied using degradation of methyl orange as a probe under UV as well as visible radiations. Ag-N co-doped ZnO/CuO composite showed higher photo-catalytic activity than Ag- or N-doped ZnO and undoped ZnO-CuO composite photo-catalysts. The observed highest activity of Ag-N co-doped ZnO-CuO among the studied photo-catalysts is attributed to the cumulative effects of lowering of band-gap energy and decrease of recombination rate of photo-generated electrons and holes owing to doped N and Ag, respectively. Effects of photo-catalyst load, pH and substrate initial concentration on degradation of methyl orange have also been studied. Photo-catalytic degradation of methyl orange follows pseudo first order kinetics.

Keywords: degradation, nanocomposite, photocatalyst, spectroscopy, XRD

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Authors: Esther Acha, Jose Cambra, De Chen

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Hydrogen is considered an important energy vector for the 21st century. Nowadays there are some difficulties for hydrogen economy implantation, and one of them is the high purity required for hydrogen. This energy vector is still being mainly produced from fuels, from wich hydrogen is produced as a component of a mixture containing other gases, such as CO, CO2 and H2O. A forthcoming sustainable pathway for hydrogen is steam-reforming of bio-oils derived from biomass, e.g. via fast pyrolysis. Bio-oils are a mixture of acids, alcohols, aldehydes, esters, ketones, sugars phenols, guaiacols, syringols, furans, multi-functional compounds and also up to a 30 wt% of water. The sorption enhanced steam reforming (SESR) process is attracting a great deal of attention due to the fact that it combines both hydrogen production and CO2 separation. In the SESR process, carbon dioxide is captured by an in situ sorbent, which shifts the reversible reforming and water gas shift reactions to the product side, beyond their conventional thermodynamic limits, giving rise to a higher hydrogen production and lower cost. The hydrogen containing mixture has been obtained from the SESR of bio-oil type compounds. Different types of catalysts have been tested. All of them contain Ni at around a 30 wt %. Two samples have been prepared with the wet impregnation technique over conventional (gamma alumina) and non-conventional (olivine) supports. And a third catalysts has been prepared over a hydrotalcite-like material (HT). The employed sorbent is a commercial dolomite. The activity tests were performed in a bench-scale plant (PID Eng&Tech), using a stainless steel fixed bed reactor. The catalysts were reduced in situ in the reactor, before the activity tests. The effluent stream was cooled down, thus condensed liquid was collected and weighed, and the gas phase was analysed online by a microGC. The hydrogen yield, and process behavior was analysed without the sorbent (the traditional SR where a second purification step will be needed but that operates in steady state) and the SESR (where the purification step could be avoided but that operates in batch state). The influence of the support type and preparation method will be observed in the produced hydrogen yield. Additionally, the stability of the catalysts is critical, due to the fact that in SESR process sorption-desorption steps are required. The produced hydrogen yield and hydrogen purity has to be high and also stable, even after several sorption-desorption cycles. The prepared catalysts were characterized employing different techniques to determine the physicochemical properties of the fresh-reduced and used (after the activity tests) materials. The characterization results, together with the activity results show the influence of the catalysts preparation method, calcination temperature, or can even explain the observed yield and conversion.

Keywords: CO2 sorbent, enhanced steam reforming, hydrogen

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Authors: Andrea Dragu, Solen Kinayyigit, Valerie Colliere, Karin Karin Philippot, Camelia Bala, Vasile I. Parvulescu

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The production of transportation fuels from biomass has gained a growing attention due to diminishing fossil fuel reserves, rising petroleum prices and increasing concern about global warming. In recent years, renewable hydrocarbons that are completely fungible with fossil fuels have been suggested to be efficiently produced by catalytic deoxygenation of fatty acids and their derivatives viadecarboxylation / decarbonylation. Several triglycerides (tall oil fatty acids) and saturated/unsaturated fatty acids and their corresponding esters were used as feedstocks. Their impact together with the influence of the reaction conditions and the catalyst composition on the nature of the reaction pathways of the deoxygenation of vegetable oils and their derivatives were recently reviewed. Following this state of the art the aim of the present study was the investigation of Pd NPs deposited onto mesoporous carbon supports as active and stable catalysts for the deoxygenation of oleic acid. The catalysts were prepared by the deposition of Pd NPs synthesised following an organometallic route on mesoporous carbons with different characteristics. Experiments were carried out under both batch and flow conditions. They demonstrated that under batch conditions (200 atm; 573K), the extent of the reaction depended, firstly, on the Pd loading and then on the metal dispersion and the oxidation state of palladium, both influenced by the way the support has been treated before the NPs deposition and by the preparation/stabilization methodology of Pd NPs. No aromatic compounds were detected in the reaction products but octadecanol and octadecane were observed in large extents. Under flow conditions (4 atm; 573 K), the conversion of stearic acid was superior to that observed in batch conditions. The product mixture contained over 20% heptadecane. No octadecanol, octadecane, and aromatic compounds were detected. The maxima in performances are obtained after only 0.5 h. After that, the yields in heptadecane suffer from a severe decrease until 3h reaction time. However, at that time, stopping feeding the reactor with oleic acid and flushing the catalyst only with mesitylene recovered the activity and the selectivity of the catalysts. With the complete removal of H2, the analysis revealed the presence of heptadecene in high excess compared to heptadecane (almost 7 to 1), thus suggesting decarbonylation as the main route. ICP-OES measurements indicated no leaching of palladium and simple washing of catalysts with mesitylene allowed recycling without any change in conversion or product distribution. Noteworthy, mesitylene as solvent exhibited no effect in this reaction. In conclusion, this study demonstrates the feasibility of such catalysts for the green production of fuels from biomass.

Keywords: fuels from biomass, green catalyst, Pd nano-particles , recycble catalyst

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Authors: Xinyi Zhao, Furong Tian

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Mycotoxins are secondary metabolic products of fungi. These are poisonous, carcinogens and mutagens in nature and pose a serious health threat to both humans and animals, causing severe illnesses and even deaths. The rapid, simple and cheap detection methods of mycotoxins are of immense importance and in great demand in the food and beverage industry as well as in agriculture and environmental monitoring. Lateral flow immunochromatographic strips (ICSTs) have been widely used in food safety, environment monitoring. Forty-six papers were identified and reviewed on Google Scholar and Scopus for their limit of detection and nanomaterial on Lateral flow immunochromatographic strips on different types of mycotoxins. The papers were dated 2001-2021. Twenty five papers were compared to identify the lowest limit of detection of among different mycotoxins (Aflatoxin B1: 10, Zearalenone:5, Fumonisin B1: 5, Trichothecene-A: 5). Most of these highly sensitive strips are competitive. Sandwich structure are usually used in large scale detection. In conclusion, the mycotoxin receives that most researches is aflatoxin B1 and its limit of detection is the lowest. Gold-nanopaticle based immunochromatographic test strips has the lowest limit of detection. Five papers involve smartphone detection and they all detect aflatoxin B1 with gold nanoparticles. In these papers, quantitative concentration results can be obtained when the user uploads the photograph of test lines using the smartphone application.

Keywords: aflatoxin B1, limit of detection, gold nanoparticle, lateral flow immunochromatographic strips, mycotoxins

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Authors: Rameez Ahmad, Aqib Mehmood, Imran Khan

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Self-directed car (SDC) that can drive itself from one fact to another without support from a driver. Certain trust that self-directed car obligate the probable to transform the transportation manufacturing while essentially removing coincidences, and cleaning up the environment. This study realizes the effects that SDC (also called a self-driving, driver or robotic) vehicle travel demands and ride scheme is likely to have. Without the typical obstacles that allows detection of a audio vision based hardware and software construction (It (SDC) and cost benefits, the vehicle technologies, Gold (Generic Obstacle and Lane Detection) to a knowledge-based system to predict their potential and consider the shape, color, or balance) and an organized environment with colored lane patterns, lane position ban. Discovery the problematic consequence of (SDC) on GT (grand trunk road) road and brand the car further effectual.

Keywords: SDC, gold, GT, knowledge-based system

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Authors: Mohammad Ali Karimi, Hossein Tavallali, Abdolhamid Hatefi-Mehrjardi

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In this study, an electrochemical sensor based on gold nanoparticles (AuNPs) functionalized improved graphene (AuNPs-IGE) was fabricated for selective determination of L-dopa in the presence of ascorbic acid by a novel self-assembly method. The AuNP IGE modified carbon paste electrode (AuNPs-IGE/CPE) utilized for investigation of the electrochemical behavior of L-dopa in phosphate buffer solution. Compared to bare CPE, AuNPs-IGE/CPE shows novel properties towards the electrochemical redox of levodopa (L-dopa) in phosphate buffer solution at pH 4.0. The oxidation potential of L-dopa shows a significant decrease at the AuNPs-IGE/CPE. The oxidation current of L-dopa is higher than that of the unmodified CPE. AuNPs-IG/CPE shows excellent electrocatalytic activity for the oxidation of ascorbic acid (AA). Using differential pulse voltammetry (DPV) method, the oxidation current is well linear with L-dopa concentration in the range of 0.4–50 µmol L-1, with a detection limit of about 1.41 nmol L-1 (S/N = 3). Therefore, it was applied to measure L-dopa from real samples that recoveries are 94.6-106.2%. The proposed electrode can also effectively avoid the interference of ascorbic acid, making the proposed sensor suitable for the accurate determination of L-dopa in both pharmaceutical preparations and human body fluids.

Keywords: gold nanoparticles, improved graphene, L-dopa, self-assembly

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Authors: Yusif Habib

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The Volta River Basin (VRB) is a transboundary resource shared by Six (6) the West African States. It’s utilization spans across irrigation, hydropower generation, domestic/household water use, transportation, industrial processing, among others. Simultaneously, mineral resources such as gold are mined within the VRB catchment. Typically, the extraction/mining operation is earth-surface excavation; known as Artisanal and Small-scale mining. We developed a conceptual framework in the context of Water-Energy-Food (WEF) Nexus to delineate the trade-offs and synergies between the mineral extractive operation’s impact on Agricultural systems, specifically, cereal crops (e.g. Maize, Millet, and Rice) and the environment (water and soil quality, deforestation, etc.) on the VRB. Thus, the study examined the trade-offs and synergies through the WEF nexus lens to explore the extent of an eventual overarching mining preference for gold exploration with high economic returns as opposed to the presumably low yearly harvest and household income from food crops production to inform intervention prioritization. Field survey (household, expert, and stakeholder consultation), bibliometric analysis/literature review, scenario, and simulation models, including land-use land cover (LULC) analyses, were conducted. The selected study area(s) in Ghana was the location where the mineral extractive operation’s presence and impact are widespread co-exist with the Agricultural systems. Overall, the study proposes mechanisms of the virtuous cycle through FEW Nexus instead of the presumably existing vicious cycle to inform decision making and policy implementation.

Keywords: agriculture, environmental sustainability, gold Mining, synergies, trade-off, water-energy-food nexus

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Authors: Faezeh Aghazadeh

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The catalytic activity of Pt/γ-Al₂O₃ and Pt-Fe/γ-Al₂O₃ catalysts was investigated to bring about the complete oxidation of 2-Propanol. Among them, Pt-Fe/γ-Al₂O₃ was found to be the most promising catalyst based on activity. The catalysts were characterized by (XRD), (SEM), (TEM) and ICP-AES techniques. Iron loadings on Pt/γ-Al₂O₃ had a great effect on catalytic activity, and Pt-Fe/γ-Al₂O₃ (1.75 wt% Fe) catalyst at calcination temperature 300°C was observed to be the most active, which might be contributed to the favorable synergetic effects between Pt and Fe, high activity and the well-dispersed bimetallic phase. The combustion of 2-Propanol in the vapor phase was carried out in a conventional flow U-shape glass reactor used in the differential mode at atmospheric pressure. 2-Propanol was analyzed by a gas chromatograph VARIAN 3800 CX equipped with an FID. As observed, better performance and activity were observed for Pt-Fe/Al₂O₃ bimetallic catalyst. These results indicate that the high dispersion on support gives a positive effect on catalytic activity.

Keywords: volatile organic compounds, bimetallic catalyst, catalytic activity, low temperature

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Authors: Abrar Hussain, Kuen-Song Lin, Sayed Maeen Badshah, Jamshid Hussain

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The conversion of CO₂ into versatile, useful compounds such as fuels and other chemicals remains a challenging frontier in research, demanding the innovation of increasingly effective catalysts. In the present work, a catalyst-incorporating zirconium (Zr) modification within CuO–ZnO–Al₂O₃ (CZA) was synthesized via a co-precipitation method to convert CO₂ into methanol. Furthermore, bio-HZSM-5 was used to promote methanol dehydration to produce dimethyl ether (DME). We prepared the porous hierarchy bio-HZSM-5 with remarkable pore connectivity by utilizing an economical loofah sponge and rice husks as biotemplates. The synthesized catalysts were characterized using Field Emission Scanning Electron Microscopy (FE-SEM), X–ray diffraction (XRD), N₂ adsorption (BET), temperature-programmed desorption (NH₃-TPD) and thermogravimetric analysis (TGA). The Zr addition improved the performance of the CZZA catalyst as a structural promoter, leading to increased DME selectivity and total carbon conversion by enhancing active sites, surface area, and the synergistic interfaces between CuO and ZnO. The presence of silicon in the biomass, notably from the loofah sponge (0.016 wt %) and rice husks (8.3 wt %), also performed a pivotal role in the preparation of bio-HZSM-5. Furthermore, contrasted to the CZZA/com-ZSM-5 catalyst, the integration of CZZA with bio-HZSM-5-L bifunctional catalyst achieved the highest DME yield (12.1 %), DME selectivity (58.6%), CO₂ conversion (22.5%) at 280 °C and 30 bar. The payback time for 5 and 10-tons per day (5 and10-TPD) DME formation using the catalytic process of CO₂ from petrochemical refinery plant waste gas emissions was 2.98 and 2.44 years, respectively.

Keywords: Cost assessment, Dimethyl ether, low-cost bio-HZSM-5, CZZA catalyst, CO₂ hydrogenation

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Authors: Zahrah Thamer Althagafi, Mohamed I. Awad

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A simple method for the fabrication of Au (111)-like electrode via controlled reductive desorption of a pre-adsorbed cysteine monolayer onto polycrystalline gold (poly-Au) electrode is introduced. Then, the voltammetric behaviour of dopamine (DA) and ascorbic acid (AA) on the thus modified electrode is investigated. Electrochemical characterization of the modified electrode is achieved using cyclic voltammetry and square wave voltammetry. For the binary mixture of DA and AA, the results showed that Au (111)-like electrode exhibits excellent electrocatalytic activity towards the oxidation of DA and AA. This allows highly selective and simultaneous determination of DA and AA. The effect of various experimental parameters on the voltammetric responses of DA and AA was investigated. The enrichment of the Au (111) facet of the poly-Au electrode is thought to be behind the electrocatalytic activity.

Keywords: gold electrode, electroanalysis, electrocatalysis, monolayers, self-assembly, cysteine, dopamine, ascorbic acid

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Authors: Carla Palencia-Aguilar

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Calculations of Net Carbon Balance can be obtained by means of Net Biome Productivity (NBP), Net Ecosystem Productivity (NEP), and Net Primary Production (NPP). The latter is an important component of the biosphere carbon cycle and is easily obtained data from MODIS MOD17A3HGF; however, the results are only available yearly. To overcome data availability, bands 33 to 36 from MODIS MYD021KM (obtained on a daily basis) were analyzed and compared with NPP data from the years 2000 to 2021 in 7 sites where surface mining takes place in the Colombian territory. Coal, Gold, Iron, and Limestone were the minerals of interest. Scales and Units as well as thermal anomalies, were considered for net carbon balance per location. The NPP time series from the satellite images were filtered by using two Matlab filters: First order and Discrete Transfer. After filtering the NPP time series, comparing the graph results from the satellite’s image value, and running a linear regression, the results showed R2 from 0,72 to 0,85. To establish comparable units among NPP and bands 33 to 36, the Greenhouse Gas Equivalencies Calculator by EPA was used. The comparison was established in two ways: one by the sum of all the data per point per year and the other by the average of 46 weeks and finding the percentage that the value represented with respect to NPP. The former underestimated the total CO2 emissions. The results also showed that coal and gold mining in the last 22 years had less CO2 emissions than limestone, with an average per year of 143 kton CO2 eq for gold, 152 kton CO2 eq for coal, and 287 kton CO2 eq for iron. Limestone emissions varied from 206 to 441 kton CO2 eq. The maximum emission values from unfiltered data correspond to 165 kton CO2 eq. for gold, 188 kton CO2 eq. for coal, and 310 kton CO2 eq. for iron and limestone, varying from 231 to 490 kton CO2 eq. If the most pollutant limestone site improves its production technology, limestone could count with a maximum of 318 kton CO2 eq emissions per year, a value very similar respect to iron. The importance of gathering data is to establish benchmarks in order to attain 2050’s zero emissions goal.

Keywords: carbon dioxide, NPP, MODIS, MINING

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Authors: Yijin Kang

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Chemical-electrical energy conversion and storage are greatly attractive for the development of sustainable energy. Catalytic processes are heavily involved in such energy conversion and storage. Development of high-performance catalyst nanomaterials relies on tuning material structures at nanoscale. This is in particular manifested in the design of catalysts demanding both high activity and durability. Here, a research system will be presented that connects fundamental investigation on well-defined extended surfaces (e.g. single crystal surfaces), extrapolation onto nanocrystals with highly controlled shape and size, exploration of interfacial interaction using novel nanocrystal superlattices as platform, and finally design of high performance catalysts in which all the possible beneficial properties from complex functional structures are implemented. Using recently published results, it will be demonstrated that optimal and fine balanced activity and durability, as well as tunable functionality, can be achieved by carefully tailoring the nanostructure of catalytic nanomaterials.

Keywords: energy, nanomaterials, catalysis, electrocatalysis

Procedia PDF Downloads 239

Authors: Cristina Opris, Bogdan Cojocaru, Madalina Tudorache, Simona M. Coman, Vasile I. Parvulescu, Camelia Bala, Bahir Duraki, Jeroen A. Van Bokhoven

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The tremendous achievements in the development of the society concretized by more sophisticated materials and systems are merely based on non-renewable resources. Consequently, after more than two centuries of intensive development, among others, we are faced with the decrease of the fossil fuel reserves, an increased impact of the greenhouse gases on the environment, and economic effects caused by the fluctuations in oil and mineral resource prices. The use of biomass may solve part of these problems, and recent analyses demonstrated that from the perspective of the reduction of the emissions of carbon dioxide, its valorization may bring important advantages conditioned by the usage of genetic modified fast growing trees or wastes, as primary sources. In this context, the abundance and complex structure of lignin may offer various possibilities of exploitation. However, its transformation in fuels or chemicals supposes a complex chemistry involving the cleavage of C-O and C-C bonds and altering of the functional groups. Chemistry offered various solutions in this sense. However, despite the intense work, there are still many drawbacks limiting the industrial application. Thus, the proposed technologies considered mainly homogeneous catalysts meaning expensive noble metals based systems that are hard to be recovered at the end of the reaction. Also, the reactions were carried out in organic solvents that are not acceptable today from the environmental point of view. To avoid these problems, the concept of this work was to investigate the synthesis of superparamagnetic core shell catalysts for the fragmentation of lignin directly in the aqueous phase. The magnetic nanoparticles were covered with a nanoshell of an oxide (niobia) with a double role: to protect the magnetic nanoparticles and to generate a proper (acidic) catalytic function and, on this composite, cobalt nanoparticles were deposed in order to catalyze the C-C bond splitting. With this purpose, we developed a protocol to prepare multifunctional and magnetic separable nano-composite Co@Nb2O5@Fe3O4 catalysts. We have also established an analytic protocol for the identification and quantification of the fragments resulted from lignin depolymerization in both liquid and solid phase. The fragmentation of various lignins occurred on the prepared materials in high yields and with very good selectivity in the desired fragments. The optimization of the catalyst composition indicated a cobalt loading of 4wt% as optimal. Working at 180 oC and 10 atm H2 this catalyst allowed a conversion of lignin up to 60% leading to a mixture containing over 96% in C20-C28 and C29-C37 fragments that were then completely fragmented to C12-C16 in a second stage. The investigated catalysts were completely recyclable, and no leaching of the elements included in the composition was determined by inductively coupled plasma optical emission spectrometry (ICP-OES).

Keywords: superparamagnetic core-shell catalysts, environmental production of fuels, renewable lignin, recyclable catalysts

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Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

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Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H₂) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H₂, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO Hydrodeoxygenation, DFT, liquid fuels, XPS, XTL

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Authors: Ka Ho Yau, Jan Frederick Engels, Kwok Kei Lai, Reinhard Renneberg

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Lateral flow test is a prevalent technology in various sectors such as food, pharmacology and biomedical sciences. Colloidal gold (CG) is widely used as the signalling molecule because of the ease of synthesis, bimolecular conjugation and its red colour due to intrinsic SPRE. However, the production of colloidal gold is costly and requires vigorous conditions. The stability of colloidal gold are easily affected by environmental factors such as pH, high salt content etc. Silica nanoparticles are well known for its ease of production and stability over a wide range of solvents. Using reverse micro-emulsion (w/o), silica nanoparticles with different sizes can be produced precisely by controlling the amount of water. By incorporating different water-soluble dyes, a rainbow colour of the silica nanoparticles could be produced. Conjugation with biomolecules such as antibodies can be achieved after surface modification of the silica nanoparticles with organosilane. The optimum amount of the antibodies to be labelled was determined by Bradford Assay. In this work, we have demonstrated the ability of the dye-doped silica nanoparticles as a signalling molecule in lateral flow test, which showed a semi-quantitative measurement of the analyte. The image was further analysed for the LOD=10 ng of the analyte. The working range and the linear range of the test were from 0 to 2.15μg/mL and from 0 to 1.07 μg/mL (R2=0.988) respectively. The performance of the tests was comparable to those using colloidal gold with the advantages of lower cost, enhanced stability and having a wide spectrum of colours. The positives lines can be imaged by naked eye or by using a mobile phone camera for a better quantification. Further research has been carried out in multicolour detection of different biomarkers simultaneously. The preliminary results were promising as there was little cross-reactivity being observed for an optimized system. This approach provides a platform for multicolour detection for a set of biomarkers that enhances the accuracy of diseases diagnostics.

Keywords: colorimetric detection, immunosensor, paper-based biosensor, silica

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Authors: Mariia V. Efremova, Iana O. Tcareva, Anastasia D. Blokhina, Ivan S. Grebennikov, Anastasia S. Garanina, Maxim A. Abakumov, Yury I. Golovin, Alexander G. Savchenko, Alexander G. Majouga, Natalya L. Klyachko

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During last decades magnetite nanoparticles (NPs) attract a deep interest of scientists due to their potential application in therapy and diagnostics. However, magnetite nanoparticles are toxic and non-stable in physiological conditions. To solve these problems, we decided to create two types of hybrid systems based on magnetite and gold which is inert and biocompatible: gold as a shell material (first type) and gold as separate NPs interfacially bond to magnetite NPs (second type). The synthesis of the first type hybrid nanoparticles was carried out as follows: Magnetite nanoparticles with an average diameter of 9±2 nm were obtained by co-precipitation of iron (II, III) chlorides then they were covered with gold shell by iterative reduction of hydrogen tetrachloroaurate with hydroxylamine hydrochloride. According to the TEM, ICP MS and EDX data, final nanoparticles had an average diameter of 31±4 nm and contained iron even after hydrochloric acid treatment. However, iron signals (K-line, 7,1 keV) were not localized so we can’t speak about one single magnetic core. Described nanoparticles covered with mercapto-PEG acid were non-toxic for human prostate cancer PC-3/ LNCaP cell lines (more than 90% survived cells as compared to control) and had high R2-relaxivity rates (>190 mМ-1s-1) that exceed the transverse relaxation rate of commercial MRI-contrasting agents. These nanoparticles were also used for chymotrypsin enzyme immobilization. The effect of alternating magnetic field on catalytic properties of chymotrypsin immobilized on magnetite nanoparticles, notably the slowdown of catalyzed reaction at the level of 35-40 % was found. The synthesis of the second type hybrid nanoparticles also involved two steps. Firstly, spherical gold nanoparticles with an average diameter of 9±2 nm were synthesized by the reduction of hydrogen tetrachloroaurate with oleylamine; secondly, they were used as seeds during magnetite synthesis by thermal decomposition of iron pentacarbonyl in octadecene. As a result, so-called dumbbell-like structures were obtained where magnetite (cubes with 25±6 nm diagonal) and gold nanoparticles were connected together pairwise. By HRTEM method (first time for this type of structure) an epitaxial growth of magnetite nanoparticles on gold surface with co-orientation of (111) planes was discovered. These nanoparticles were transferred into water by means of block-copolymer Pluronic F127 then loaded with anti-cancer drug doxorubicin and also PSMA-vector specific for LNCaP cell line. Obtained nanoparticles were found to have moderate toxicity for human prostate cancer cells and got into the intracellular space after 45 minutes of incubation (according to fluorescence microscopy data). These materials are also perspective from MRI point of view (R2-relaxivity rates >70 mМ-1s-1). Thereby, in this work magnetite-gold hybrid nanoparticles, which have a strong potential for biomedical application, particularly in targeted drug delivery and magnetic resonance imaging, were synthesized and characterized. That paves the way to the development of special medicine types – theranostics. The authors knowledge financial support from Ministry of Education and Science of the Russian Federation (14.607.21.0132, RFMEFI60715X0132). This work was also supported by Grant of Ministry of Education and Science of the Russian Federation К1-2014-022, Grant of Russian Scientific Foundation 14-13-00731 and MSU development program 5.13.

Keywords: drug delivery, magnetite-gold, MRI contrast agents, nanoparticles, toxicity

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