An undergraduate level experiment on the synthesis of Au nanoparticles and their size-dependent optical and catalytic properties

The synthesis of gold nanoparticles (Au NPs) 15, 26, and 34 nm in diameter, followed by the investigation of their size-dependent optical and catalytic properties, is described herein as an undergraduate level experiment. The proposed experiment covers concepts on the synthesis, stabilization, and characterization of Au NPs, their size-dependent optical and catalytic properties at the nanoscale, chemical kinetics, and the role of a catalyst. The experiment should be performed by groups of two or three students in three lab sessions of 3 h each and organized as follows: i) synthesis of Au NPs of different sizes and investigation of their optical properties; ii) evaluation of their catalytic activity; and iii) data analysis and discussion. We believe that this activity enables students to integrate these multidisciplinary concepts in a single experiment as well as to become introduced/familiarized with an active research field and current literature in the areas of nanoparticle synthesis and catalysis.

Ni(II), Cu(II), AND Zn(II) COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z)-(3-METHYLPYRIDIN-2- YLEIMINO)METHYL)PHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II), Cu(II), and Zn(II) are described. All three compounds have the general formula [M(L)2(H2O)2], where L = deprotonated phenol in the Schiff base 2-((z)-(3-methylpyridin-2-yleimino)methyl)phenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD), and room temperature magnetic moments. The Cu(II) and Ni(II) complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II) sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature) showed a typical ΔMS = ± 1 transition. The complexes ([M(L)2(H2O)2]) were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.

Model studies on the synthesis of the natural meroterpenoid cordiaquinone A

Two main strategies for the synthesis of the natural meroterpenoid cordiaquinone A (1) - isolated of the roots of Cordia corymbosa G. Don (Boraginaceae) - were tested on model compounds. Whereas all attempts of alkylation of epsilon-caprolactone (10) were unsuccessful, the coupling of epoxycitronellol (17) with an appropriate organocuprate proceeded in the expected direction.

Synthesis of new disulfonamides from different substituted diamino pyridines

A series of novel disulfonamide derivatives were synthesized and characterized by FT-IR, ¹H NMR and MS techniques. In order to prepare new disulfonamides, at first we synthesized new diamines containing a pyridine ring. Then, they have been reacted with sulfonyl chlorides to give corresponding disulfonamides.

Synthesis of percarboxylic acids in microreactor

Percarboxylic acids are commonly used as disinfection and bleaching agents in textile, paper, and fine chemical industries. All of these applications are based on the oxidative potential of these compounds. In spite of high interest in these chemicals, they are unstable and explosive chemicals, which increase the risk of synthesis processes and transportation. Therefore, the safety criteria in the production process should be considered. Microreactors represent a technology that efficiently utilizes safety advantages resulting from small scale. Therefore, microreactor technology was used in the synthesis of peracetic acid and performic acid. These percarboxylic acids were produced at different temperatures, residence times and catalyst i.e. sulfuric acid concentrations. Both synthesis reactions seemed to be rather fast because with performic acid equilibrium was reached in 4 min at 313 K and with peracetic acid in 10 min at 343 K. In addition, the experimental results were used to study the kinetics of the formation of performic acid and peracetic acid. The advantages of the microreactors in this study were the efficient temperature control even in very exothermic reaction and good mixing due to the short diffusion distances. Therefore, reaction rates were determined with high accuracy. Three different models were considered in order to estimate the kinetic parameters such as reaction rate constants and activation energies. From these three models, the laminar flow model with radial velocity distribution gave most precise parameters. However, sulfuric acid creates many drawbacks in this synthesis process. Therefore, a ´´greener´´ way to use heterogeneous catalyst in the synthesis of performic acid in microreactor was studied. The cation exchange resin, Dowex 50 Wx8, presented very high activity and a long life time in this reaction. In the presence of this catalyst, the equilibrium was reached in 120 second at 313 K which indicates a rather fast reaction. In addition, the safety advantages of microreactors were investigated in this study. Four different conventional methods were used. Production of peracetic acid was used as a test case, and the safety of one conventional batch process was compared with an on-site continuous microprocess. It was found that the conventional methods for the analysis of process safety might not be reliable and adequate for radically novel technology, such as microreactors. This is understandable because the conventional methods are partly based on experience, which is very limited in connection with totally novel technology. Therefore, one checklist-based method was developed to study the safety of intensified and novel processes at the early stage of process development. The checklist was formulated using the concept of layers of protection for a chemical process. The traditional and three intensified processes of hydrogen peroxide synthesis were selected as test cases. With these real cases, it was shown that several positive and negative effects on safety can be detected in process intensification. The general claim that safety is always improved by process intensification was questioned.

Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Synthesis of stocks and phenotypic effects of dwarf and bantam sex-linked major genes in egg-type chickens

The present study describes the production of stocks segregating dwarf (dw), bantam (dwB) and normal (dw+) alleles, as well as the characters, shank length, adult body weight, age at sexual maturity and egg production. Heterozygous K dw+/k dwB sires were mated to normal (dw+) dams to produce stock D6.a, and mated to dwB females to produce stock D6.b. Stock D4.a came from mating F1 heterozygous dwB dw sires to dwarf Leghorns. In a third series of matings, 7/8 Sebright and 1/8 dw-Leghorn dwB dw sires were crossed to three groups of dams of different genotypes. The progeny of the normal (dw+), dwarf (dw), and bantam (dwB) dams were designated as stocks D4.b, D4.c and D4.d, respectively. The dw+ dams were White Leghorn strain cross females. The difference between the rate of laying of normal (69.7%) and their bantam sisters (68.6%) was not statistically significant when the average 32-week body weight of the dw+ sisters was 1,897 g. However, when the 32-week body weight of the normal daughters from the same sires and smaller dams was around 1,646 g, the difference between the rate of laying of the normal (78.1%) and their bantam sisters (75.9%) was significant (P < 0.05). The dwB gene may have a similar but smaller effect on the rate of egg laying than its dwarf allele. The difference between sexual maturity of normal and bantam daughters of either the largest or the smallest dams was not statistically significant, even though the smallest dwB pullets were in average 2.9 days older at first egg. The use of shank length combined with adult body weight allowed a precise discrimination between bantams and dwarfs

Synthesis of fructans by fructosyltransferase from the tuberous roots of Viguiera discolor (Asteraceae)

Sucrose:sucrose fructosyltransferase (SST) and fructan:fructan fructosyl-transferase (FFT) activities from crude extracts of tuberous roots of Viguiera discolor growing in a preserved area of cerrado were analyzed in 1995-1996. SST activity was characterized by the synthesis of 1-kestose from sucrose and FFT activity by the production of nystose from 1-kestose. The highest fructan-synthesizing activity was observed during early dormancy (autumn), when both (SST and FFT) activities were high. The increase in synthetic activity seemed to start during the fruiting phase in the summer, when SST activity was higher than in spring. During winter and at the beginning of sprouting, both activities declined. The in vitro synthesis of high molecular mass fructans from sucrose by enzymatic preparations from tuberous roots collected in summer showed that long incubations of up to 288 h produced consistently longer polymers which resembled those found in vivo with respect to chromatographic profiles.

Catalytic direct synthesis of hydrogen peroxide in a novel microstructured reactor

The direct synthesis from hydrogen and oxygen is a green alternative for production of hydrogen peroxide. However, this process suffers from two challenges. Firstly, mixtures of hydrogen and oxygen are explosive over a wide range of concentrations (4-94% H2 in O2). Secondly, the catalytic reaction of hydrogen and oxygen involves several reaction pathways, many of them resulting in water production and therfore decreasing selectivity. The present work deals with these two challenges. The safety problem was dealed by employing a novel microstructured reactor. Selectivity of the reaction was highly improved by development a set of new catalysts. The final goal was to develop an effective and safe continuous process for direct synthesis of hydrogen peroxide from H2 and O2. Activated carbon cloth and Sibunit were examined as the catalysts’ supports. Palladium and gold monometallic and palladium-gold bimetallic catalysts were thoroughly investigated by numerous kinetic experiments performed in a tailored batch reactor and several catalyst charachterization methods. A complete set of data for direct synthesis of H2O2 and its catalytic decomposition and hydrogenation was obtained. These data were used to assess factors influencing selectivity and activity of the catalysts in direct synthesis of H2O2 as well as its decomposition and hydrogenation. A novel microstructured reactor was developed based on hydrodynamics and mass transfer studies in prototype microstractural plates. The shape and the size of the structural elements in the microreactor plate were optimized in a way to get high gas-liquid interfacial area and gas-liquid mass transfer. Finally, empirical correlations for the volumetric mass transfer coefficient were derived. A bench-scale continuous process was developed by using the novel microstructral plate reactor. A series of kinetic experiments were performed to investigate the effects of the gas and the liquid feed rates and their ratio, the amount of the catalyst, the gas feed composition and pressure on the final rate of H2O2 production and selectivity.

Butyrate induces apoptosis in murine macrophages via caspase-3, but independent of autocrine synthesis of tumor necrosis factor and nitric oxide

We demonstrated that 4 mM butyrate induces apoptosis in murine peritoneal macrophages in a dose- and time-dependent manner as indicated by studies of cell viability, flow cytometric analysis of annexin-V binding, DNA ladder pattern and the determination of hypodiploid DNA content. The activity of caspase-3 was enhanced during macrophage apoptosis induced by butyrate and the caspase inhibitor z-VAD-FMK (100 µM) inhibited the butyrate effect, indicating the major role of the caspase cascade in the process. The levels of butyrate-induced apoptosis in macrophages were enhanced by co-treatment with 1 µg/ml bacterial lipopolysaccharide (LPS). However, our data indicate that apoptosis induced by butyrate and LPS involves different mechanisms. Thus, LPS-induced apoptosis was only observed when macrophages were primed with IFN-gamma and was partially dependent on iNOS, TNFR1 and IRF-1 functions as determined in experiments employing macrophages from various knockout mice. In contrast, butyrate-induced macrophage apoptosis was highly independent of IFN-gamma priming and of iNOS, TNFR1 and IRF-1 functions.

Gentamicin-induced preconditioning of proximal tubular LLC-PK1 cells stimulates nitric oxide production but not the synthesis of heat shock protein

Nephrotoxicity is the main side effect of antibiotics such as gentamicin. Preconditioning has been reported to protect against injuries as ischemia/reperfusion. The objective of the present study was to determine the effect of preconditioning with gentamicin on LLC-PK1 cells. Preconditioning was induced in LLC-PK1 cells by 24-h exposure to 2.0 mM gentamicin (G/IU). After 4 or 15 days of preconditioning, cells were again exposed to gentamicin (2.0 mM) and compared to untreated control or G/IU cells. Necrosis and apoptosis were assessed by acridine orange and HOESCHT 33346. Nitric oxide (NO) and endothelin-1 were assessed by the Griess method and available kit. Heat shock proteins were analyzed by Western blotting. After 15 days of preconditioning, LLC-PK1 cells exhibited a significant decrease in necrosis (23.5 ± 4.3 to 6.5 ± 0.3%) and apoptosis (23.5 ± 4.3 to 6.5 ± 2.1%) and an increase in cell proliferation compared to G/IU. NO (0.177 ± 0.05 to 0.368 ± 0.073 µg/mg protein) and endothelin-1 (1.88 ± 0.47 to 2.75 ± 0.53 pg/mL) production significantly increased after 15 days of preconditioning compared to G/IU. No difference in inducible HSP 70, constitutive HSC 70 or HSP 90 synthesis in tubular cells was observed after preconditioning with gentamicin. The present data suggest that preconditioning with gentamicin has protective effects on proximal tubular cells, that involved NO synthesis but not reduction of endothelin-1 or production of HSP 70, HSC 70, or HSP 90. We conclude that preconditioning could be a useful tool to prevent the nephrotoxicity induced by gentamicin.

Cotransfected human chondrocytes: over-expression of IGF-I and SOX9 enhances the synthesis of cartilage matrix components collagen-II and glycosaminoglycans

Damage to cartilage causes a loss of type II collagen (Col-II) and glycosaminoglycans (GAG). To restore the original cartilage architecture, cell factors that stimulate Col-II and GAG production are needed. Insulin-like growth factor I (IGF-I) and transcription factor SOX9are essential for the synthesis of cartilage matrix, chondrocyte proliferation, and phenotype maintenance. We evaluated the combined effect of IGF-I and SOX9 transgene expression on Col-II and GAG production by cultured human articular chondrocytes. Transient transfection and cotransfection were performed using two mammalian expression plasmids (pCMV-SPORT6), one for each transgene. At day 9 post-transfection, the chondrocytes that were over-expressing IGF-I/SOX9 showed 2-fold increased mRNA expression of the Col-II gene, as well as a 57% increase in Col-II protein, whereas type I collagen expression (Col-I) was decreased by 59.3% compared with controls. The production of GAG by these cells increased significantly compared with the controls at day 9 (3.3- vs 1.8-times, an increase of almost 83%). Thus, IGF-I/SOX9 cotransfected chondrocytes may be useful for cell-based articular cartilage therapies.

Synthesis of Short Oligonucleotides on a Soluble Support by the Phosphoramidite Method

In the last decades, the chemical synthesis of short oligonucleotides has become an important aspect of study due to the discovery of new functions for nucleic acids such as antisense oligonucleotides (ASOs), aptamers, DNAzymes, microRNA (miRNA) and small interfering RNA (siRNA). The applications in modern therapies and fundamental medicine on the treatment of different cancer diseases, viral infections and genetic disorders has established the necessity to develop scalable methods for their cheaper and easier industrial manufacture. While small scale solid-phase oligonucleotide synthesis is the method of choice in the field, various challenges still remain associated with the production of short DNA and RNA-oligomers in very large quantities. On the other hand, solution phase synthesis of oligonucleotides offers a more predictable scaling-up of the synthesis and is amenable to standard industrial manufacture techniques. In the present thesis, various protocols for the synthesis of short DNA and RNA oligomers have been studied on a peracetylated and methylated β-cyclodextrin, and also on a pentaerythritol-derived support. On using the peracetylated and methylated β-cyclodextrin soluble supports, the coupling cycle was simplified by replacement of the typical 5′-O-(4,4′-dimethoxytrityl) protecting group with an acid-labile acetal-protected 5′-O-(1-methoxy-1-methylethyl) group, which upon acid-catalyzed methanolysis released easily removable volatile products. For this reason monomeric building blocks 5′-O-(1-methoxy-1-methylethyl) 3′-(2-cyano-ethyl-N,N-diisopropylphosphoramidite) were synthesized. Alternatively, on using the precipitative pentaerythritol support, novel 2´-O-(2-cyanoethyl)-5´-O-(1-methoxy-1-methylethyl) protected phosphoramidite building blocks for RNA synthesis have been prepared and their applicability by the synthesis of a pentamer was demonstrated. Similarly, a method for the preparation of short RNAs from commercially available 5´-O-(4,4´-dimethoxytrityl)-2´-O-(tert-butyldimethyl-silyl)ribonucleoside 3´-(2-cyanoethyl-N,N-diisopropylphosphoramidite) building blocks has been developed

Genetic variability for synthesis of bioactive compounds in peppers (Capsicum annuum) from Brazil

AbstractThe objective of this study was to evaluate the genetic variability for synthesis of bioactive compounds in pepper (Capsicum annuum, Solanaceae). Total phenolics, anthocyanins, carotenoids and antioxidant activity were evaluated in 14 accessions of Capsicum annuum from the Capsicum Genebank of Embrapa Temperate Agriculture (Pelotas – RS, Brazil). Thirty plants of each accession were cultivated in the field during spring and summer. The experimental design was a complete randomized block with 14 treatments (accessions) and three replications. The laboratory evaluations followed the same experimental design to field, but with two repetitions more. Seeds were discarded and opposite longitudinal portions of fruits were manually prepared for chemical analyzes. The data obtained showed high genetic variability for phenolics, anthocyanins, carotenoids and antioxidant activity. The P39, P77, P119, P143 and P302 accessions exhibited the highest levels of antioxidants, which are strongly indicated to be used in breeding programs of Capsicum peppers.