Side reactions of 4-acetamido-TEMPO as the catalyst in cellulose oxidation systems

Holzforschung ◽  
2010 ◽  
Vol 64 (5) ◽  
Author(s):  
Ilabahen Patel ◽  
Martina Opietnik ◽  
Stefan Böhmdorfer ◽  
Manuel Becker ◽  
Antje Potthast ◽  
...  
Keyword(s):  
Ph Value ◽  
Cellulose Degradation ◽  
Water Soluble ◽  
Alkaline Media ◽  
Similar Process ◽  
Side Reactions ◽  
Cellulose Oxidation ◽  
Lower Reactivity ◽  
Acidic Conditions ◽  
Neutral Conditions

Abstract TEMPO/hypochlorite oxidation of cellulosics are frequently used to obtain water-soluble polyglucuronates or nano-disperse materials. The reaction under neutral conditions offers a big advantage over hitherto applied alkaline systems as base-induce β-elimination reactions causing severe cellulose degradation are suppressed. Although 4-acetamido-TEMPO seems to offer high initial activities in cellulose oxidation, the TEMPO derivative is irreversibly converted into species with much lower reactivity. The degradation pathways and the chemical structure of the 4-acetamido-TEMPO-derived (by)products have been clarified. Degradation is strongly dependent on the pH value of the reaction mixture. In acidic conditions (pH<5), 4-oxo-TEMPO is formed by an oxidative deamination process, the 4-oxo-derivative still being capable of performing cellulose oxidation. In alkaline media, a similar process proceeds, but is immediately followed by a Favorskij rearrangement to a pyrrolidine-3-carboxylic acid (PROXYL) derivative. In both cases, the released acetamido moiety is slowly converted into methylamine by a decarboxylative rearrangement (Hofmann degradation). The results suggest that the instability and the chemical fate of 4-acetamido-TEMPO needs to be considered when cellulose oxidations and their kinetics are addressed: the recyclability of the 4-acetamido-TEMPO catalyst is rather limited.

scholarly journals Photocatalytic Degradation of a Water Soluble Herbicide by Pure and Noble Metal DepositedTiO2Nanocrystalline Films

2008 ◽  
Vol 2008 ◽  
pp. 1-7 ◽  
Author(s):  
Katerina Pelentridou ◽  
Elias Stathatos ◽  
Helen Karasali ◽  
Dionysios D. Dionysiou ◽  
Panagiotis Lianos
Keyword(s):  
Photocatalytic Degradation ◽  
Noble Metals ◽  
Ph Value ◽  
Water Soluble ◽  
Alkaline Media ◽  
Nanocrystalline Films ◽  
First Order Kinetics ◽  
Photodegradation Rate ◽  
Valence States ◽  
Initial Ph

We present the photocatalytic degradation of a water soluble sulfonylurea herbicide: azimsulfuron in the presence of titania nanocrystalline films. Efficient photodegradation of herbicide was achieved by using low-intensity black light tubes emitting in the Near-UV. The degradation of the herbicide follows first-order kinetics according to the Langmuir-Hinshelwood model. Intermediate products were identified by the LC-MS-MS technique during photocatalytic degradation. In order to increase photodegradation rate of the herbicide, we examined the effect of titania modification by depositing noble metals at various quantities and valence states. The presence of platinum at neutral valence state and optimum concentration induced higher photodegradation rates while silver-modified titania exhibited similar photocatalytic rates with those obtained with pure nanocrystallineTiO2films. Finally, the effect of initial pH value was also examined. Acidic or alkaline media were unfavorable for azimsulfuron photodegradation.

Molecularly Imprinted Sensor for Ascorbic Acid Based on Gold Nanoparticles and Multiwalled Carbon Nanotubes

2020 ◽  
Vol 16 (7) ◽  
pp. 905-913
Author(s):  
Youyuan Peng ◽  
Qingshan Miao
Keyword(s):  
Carbon Nanotubes ◽  
Gold Nanoparticles ◽  
Ascorbic Acid ◽  
Multiwalled Carbon Nanotubes ◽  
Ph Value ◽  
Biological Fluids ◽  
Water Soluble ◽  
Multiwalled Carbon ◽  
Experimental Conditions ◽  
Molecularly Imprinted

Background: L-Ascorbic acid (AA) is a kind of water soluble vitamin, which is mainly present in fruits, vegetables and biological fluids. As a low cost antioxidant and effective scavenger of free radicals, AA may help to prevent diseases such as cancer and Parkinson’s disease. Owing to its role in the biological metabolism, AA has also been utilized for the therapy of mental illness, common cold and for improving the immunity. Therefore, it is very necessary and urgent to develop a simple, rapid and selective strategy for the detection of AA in various samples. Methods: The molecularly imprinted poly(o-phenylenediamine) (PoPD) film was prepared for the analysis of L-ascorbic acid (AA) on gold nanoparticles (AuNPs) - multiwalled carbon nanotubes (MWCNTs) modified glass carbon electrode (GCE) by electropolymerization of o-phenylenediamine (oPD) and AA. Experimental parameters including pH value of running buffer and scan rates were optimized. Scanning electron microscope (SEM), fourier-transform infrared (FTIR) spectra, cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were utilized for the characterization of the imprinted polymer film. Results: Under the selected experimental conditions, the DPV peak currents of AA exhibit two distinct linear responses ranging from 0.01 to 2 μmol L-1 and 2 to 100 μmol L-1 towards the concentrations of AA, and the detection limit was 2 nmol L-1 (S/N=3). Conclusion: The proposed electrochemical sensor possesses excellent selectivity for AA, along with good reproducibility and stability. The results obtained from the analysis of AA in real samples demonstrated the applicability of the proposed sensor to practical analysis.

scholarly journals Effects of Sugar Cane Molasses Addition on the Fermentation Quality, Microbial Community, and Tastes of Alfalfa Silage

Animals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 355
Author(s):  
Runbo Luo ◽  
Yangdong Zhang ◽  
Fengen Wang ◽  
Kaizhen Liu ◽  
Guoxin Huang ◽  
...  
Keyword(s):  
Sugar Cane ◽  
Ph Value ◽  
Electronic Tongue ◽  
Water Soluble ◽  
Soluble Carbohydrates ◽  
Cane Molasses ◽  
Fermentation Quality ◽  
Alfalfa Silage ◽  
Additive Control

The objective was to study the effects of sugar cane molasses addition on the fermentation quality and tastes of alfalfa silage. Fresh alfalfa was ensiled with no additive (Control), 1% molasses (M1), 2% molasses (M2), and 3% molasses (M3) for 206 days. The chemical composition and fermentation characteristics of the alfalfa silages were determined, the microbial communities were described by 16S rRNA sequencing, and the tastes were evaluated using an electronic tongue sensing system. With the amount of added molasses (M), most nutrition (dry matter and crude protein) was preserved and water-soluble carbohydrates (WSC) were sufficiently used to promote the fermentation, resulting in a pH reduction from 5.16 to 4.48. The lactic acid (LA) content and LA/acetic acid (AA) significantly increased, indicating that the fermentation had turned to homofermentation. After ensiling, Enterococcus and Lactobacillus were the dominant genus in all treatments and the undesirable microbes were inhibited, resulting in lower propionic acid (PA), butyric acid (BA), and NH3-N production. In addition, bitterness, astringency, and sourness reflected tastes of alfalfa silage, while umami and sourness changed with the amount of added molasses. Therefore, molasses additive had improved the fermentation quality and tastes of alfalfa silage, and the M3 group obtained the ideal pH value (below 4.5) and the best condition for long-term preservation.

Water soluble biguanide salts and their 1,3,5-triazine derivatives as inhibitors of acetylcholinesterase and α-glucosidase

2020 ◽  
Vol 235 (10) ◽  
pp. 465-475
Author(s):  
Ozge Gungor ◽  
Seda Nur Kertmen Kurtar ◽  
Muhammet Kose
Keyword(s):  
Spectroscopic Method ◽  
Substitute Aniline ◽  
Water Soluble ◽  
X Ray Diffraction ◽  
Nucleophilic Reaction ◽  
X Ray ◽  
Triazine Derivatives ◽  
Acidic Conditions ◽  
Approved Drugs ◽  
Solid State Structures

AbstractSeven biguanide derivatives were prepared by the nucleophilic reaction between dicyandiamide and p-substitute aniline derivatives or memantine or adamantine under acidic conditions. The cyclization of the biguanide compounds were also conducted via acetone to give 1,3,5-triazine derivatives. The structures of the synthesized compounds were characterized by analytical methods. The solid state structures of [HL5]Cl, [H2L7]Cl2, [HL1a]Cl and [HL5a]Cl were investigated by X-ray diffraction study. The acetylcholinesterase and α-glucosidase inhibitor properties of the compounds were then evaluated by the spectroscopic method. The compounds were found to show considerable acetylcholinesterase and α-glucosidase inhibitory activities compared to the approved drugs. The cyclization of biguanide derivatives with acetone did not affect inhibition of acetylcholinesterase, yet increased the α-glucosidase inhibition.

scholarly journals Sequential extraction and thermal desorption of mercury from contaminated soil and tailings from Mongolia

2012 ◽  
Vol 10 (5) ◽  
pp. 1565-1573 ◽  
Author(s):  
Pavel Coufalík ◽  
Pavel Krásenský ◽  
Marek Dosbaba ◽  
Josef Komárek
Keyword(s):  
Sequential Extraction ◽  
Thermal Desorption ◽  
Solid Phase ◽  
Extraction Procedure ◽  
Speciation Analysis ◽  
Water Soluble ◽  
Mercury Species ◽  
Different Temperatures ◽  
Acidic Conditions ◽  
Desorption Method

AbstractMercury forms in contaminated environmental samples were studied by means of sequential extraction and thermal desorption from the solid phase. The sequential extraction procedure involved the following fractions: water soluble mercury, mercury extracted in acidic conditions, mercury bound to humic substances, elemental Hg and mercury bound to complexes, HgS, and residual mercury. In addition to sequential extraction, the distribution of mercury species as a function of soil particles size was studied. The thermal desorption method is based on the thermal decomposition or desorption of Hg compounds at different temperatures. The following four species were observed: Hg0, HgCl2, HgS and Hg(II) bound to humic acids. The Hg release curves from artificial soils and real samples were obtained and their applicability to the speciation analysis was considered.

scholarly journals The effect of bacterial inoculant supplementation on the fermentation process of crushed maize ears in laboratory silos

2005 ◽  
Vol 53 (4) ◽  
pp. 33-42
Author(s):  
Petr Doležal ◽  
Dušan Kořínek ◽  
Jan Doležal ◽  
Václav Pyrochta
Keyword(s):  
Lactic Acid ◽  
Ph Value ◽  
Lactobacillus Rhamnosus ◽  
Lactobacillus Brevis ◽  
Water Soluble ◽  
Bacterial Strains ◽  
Total Acid ◽  
Ethanol Content ◽  
Fermentation Quality ◽  
Biological Additive

In the experiment was the effect of biological additive on the fermentation quality of crushed maize ears of two hybrids by comparing with the untreated control. The bacterial inoculant „A“ contained selected bacterial strains of Lactobacillus rhamnosus (NCIMB 30121) and Enterococcus faecium (NCIMB 30122). As effective substances of bacterial water–soluble inoculant „B“ were selected bacterial strains of Lactobacillus rhamnosus (NCIMB 30121), Lactobacillus plantarum (DSM 12836), Lactobacillus brevis (DSM 12835), Lactobacillus buchneri (DSM 12856), Pediococcus acidialactici (P. pentosaceus) (DSM 12834). The addition of inoculant „A“ in our experiment conditions increased statistically significantly (P<0.01) the pH value (4.09±0.01), resp. 4.02±0.02 in second trial with Pedro hybrid. The bacterial inoculant „B“ increased significantly (P<0.01) the contents of lactic acid (50.95±0.1.87 g/kg DM), acetic acid (18.61±0.34 g/kg DM), sum of acids (69.55±1.62 g/kg DM) and decreased (P<0.01) in the first trial the ethanol content (5.41±0.45 g/kg DM). The highest DM content (P<0.01) was in all experimental inoculated silages with additive „A“ (54.26±0.86%, and 53.56±0.54%, resp.). The bacterial inoculant „A“ increased significantly (P<0.01) in comparison with control silage in the second trial the content of lactic acid (34.66Ī2.81 g/kg DM), sum of acids (44.68±3.54 g/kg DM), the total acids content (32.87±2.88 g/kg DM), and ethanol content (17.33±0.79 g/kg DM). The inoculation positive effect was demonstrated in reduction of ethanol amount and of total acid production. The pH value of inoculated silages was not significantly lower than that in the control silage.

scholarly journals BAKERS YEAST CATALYZED AND ULTRASOUND ACCELERATED SYNTHESIS OF 2-AMINO-2-CHROMENES

2021 ◽  
Vol 9 (01) ◽  
pp. 189-195
Author(s):  
Balaji S. Londhe ◽  
◽  
Santosh L. Khillare ◽  
Avinash M. Nalawade ◽  
Ramrao A. Mane ◽  
...  
Keyword(s):  
Dual Role ◽  
Yeast Cells ◽  
Side Reactions ◽  
Efficient Synthesis ◽  
Neutral Conditions

In the present work, bakers yeast catalyzed efficient synthesis of 2-amino-2-chromenes in methanol is presented. Here the ultrasonication has dual role i.e. as a source of energy for the reaction and tool for the disruption of the yeast cells. The cyclocondensation has been essentially carried under neutral conditions, thus reducing the possibility of unwanted side reactions.

scholarly journals Kinetic insights into the peroxygenase activity of cellulose-active lytic polysaccharide monooxygenases (LPMOs)

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Riin Kont ◽  
Bastien Bissaro ◽  
Vincent G. H. Eijsink ◽  
Priit Väljamäe
Keyword(s):  
Catalytic Properties ◽  
Biomass Conversion ◽  
Side Reactions ◽  
Cellulose Oxidation ◽  
Multiple Substrates ◽  
Glycosidic Bonds ◽  
Lytic Polysaccharide Monooxygenases ◽  
Polysaccharide Monooxygenases ◽  
Global Carbon ◽  
Insight Into

AbstractLytic polysaccharide monooxygenases (LPMOs) are widely distributed in Nature, where they catalyze the hydroxylation of glycosidic bonds in polysaccharides. Despite the importance of LPMOs in the global carbon cycle and in industrial biomass conversion, the catalytic properties of these monocopper enzymes remain enigmatic. Strikingly, there is a remarkable lack of kinetic data, likely due to a multitude of experimental challenges related to the insoluble nature of LPMO substrates, like cellulose and chitin, and to the occurrence of multiple side reactions. Here, we employed competition between well characterized reference enzymes and LPMOs for the H2O2 co-substrate to kinetically characterize LPMO-catalyzed cellulose oxidation. LPMOs of both bacterial and fungal origin showed high peroxygenase efficiencies, with kcat/KmH2O2 values in the order of 105–106 M−1 s−1. Besides providing crucial insight into the cellulolytic peroxygenase reaction, these results show that LPMOs belonging to multiple families and active on multiple substrates are true peroxygenases.

Photodegradation of Cationic and Anioic Dyes by pH-Dependent Dispersion of Amphoteric g-C3N4 Nanosheets

2020 ◽  
Vol 20 (10) ◽  
pp. 6215-6221
Author(s):  
Qingmei Zhang ◽  
Aoli Wen ◽  
Guoliang Chen ◽  
Juan Huang ◽  
Xu Zhou ◽  
...  
Keyword(s):  
Ph Value ◽  
Cationic Dye ◽  
Amino Groups ◽  
Anionic Dye ◽  
Chromotrope 2R ◽  
Different Types ◽  
Acidic Conditions ◽  
Ph Dependent

g-C3N4 nanosheets (NSs) were prepared via H2SO4 exfoliation from the bulky g-C3N4 and the photocatalytic (PC) activities were investigated comprehensively using Rodamine B (RhB) and Chromotrope 2R (Ch2R) as candidate pollutants. The results showed that the pH value have important functions in the improvement of photodegradation performance of C3N4 NSs. RhB as cationic dye could be photodegraded more efficiently under acidic conditions while Ch2R as anionic dye was degraded easily in pH ≥ 11 solution. In particular, the Ch2R could be degraded completely within only 30 min in pH = 11 solution. It might be because the amphoteric C3N4 NSs surface with carboxyl and amino groups possessed negative and positive charges in alkaline and acidic conditions, respectively. These results presumably provided a new idea to enhance the pH-dependent photodegradation activity and degrade different types of pollutants selectively by adjusting the pH of amphoteric nanocatalyts.

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