scholarly journals Reductive methylation of proteins with sodium cyanoborohydride. Identification, suppression and possible uses of N-cyanomethyl by-products

1982 ◽  
Vol 203 (1) ◽  
pp. 331-334 ◽  
Author(s):  
M J Gidley ◽  
J K M Sanders
Keyword(s):  
Metal Ions ◽  
Good Yield ◽  
Product Formation ◽  
Free Cyanide ◽  
Amino Groups ◽  
Sodium Cyanoborohydride ◽  
Reductive Methylation ◽  
Cyanide Ion ◽  
Work Up ◽  
By Products

Reductive methylation of protein amino groups with formaldehyde and sodium cyanoborohydride is shown to give up to 25% yield of N-cyanomethyl (-CH2CN) product; on work up of the reaction this is hydrolysed back to starting amine, lowering the methylation yield. Addition of metal ions such as Ni2+, which complex with free cyanide ion, improve reductive methylation yields by suppressing by-product formation. The N-cyanomethyl group itself, produced in good yield when cyanide ion replaces cyanoborohydride, may have some value as a reversible modifier of amino groups in proteins.

Aldehyde gold clusters for molecular labeling

1995 ◽  
Vol 53 ◽  
pp. 858-859
Author(s):  
James F. Hainfeld ◽  
Frederic R. Furuya
Keyword(s):  
Covalent Bond ◽  
Aldehyde Group ◽  
Gold Clusters ◽  
Side Reactions ◽  
Amino Groups ◽  
Sodium Cyanoborohydride ◽  
Schiff’S Base ◽  
Protein Molecules ◽  
Hydroxysuccinimide Esters ◽  
Primary Amino

Glutaraldehyde is a useful tissue and molecular fixing reagents. The aldehyde moiety reacts mainly with primary amino groups to form a Schiff's base, which is reversible but reasonably stable at pH 7; a stable covalent bond may be formed by reduction with, e.g., sodium cyanoborohydride (Fig. 1). The bifunctional glutaraldehyde, (CHO-(CH2)3-CHO), successfully stabilizes protein molecules due to generally plentiful amines on their surface; bovine serum albumin has 60; 59 lysines + 1 α-amino. With some enzymes, catalytic activity after fixing is preserved; with respect to antigens, glutaraldehyde treatment can compromise their recognition by antibodies in some cases. Complicating the chemistry somewhat are the reported side reactions, where glutaraldehyde reacts with other amino acid side chains, cysteine, histidine, and tyrosine. It has also been reported that glutaraldehyde can polymerize in aqueous solution. Newer crosslinkers have been found that are more specific for the amino group, such as the N-hydroxysuccinimide esters, and are commonly preferred for forming conjugates. However, most of these linkers hydrolyze in solution, so that the activity is lost over several hours, whereas the aldehyde group is stable in solution, and may have an advantage of overall efficiency.

Nickel-Catalyzed Inter- and Intramolecular Carbon-Sulfur Bond Metathesis by Reversible Arylation

2019 ◽  
Author(s):  
Tristan Delcaillau ◽  
Alessandro Bismuto ◽  
Zhong Lian ◽  
Bill Morandi
Keyword(s):  
Good Yield ◽  
Functional Group ◽  
Product Formation ◽  
Single Bond ◽  
Ring Closing Metathesis ◽  
Catalytic Systems ◽  
Metathesis Reactions ◽  
New Applications ◽  
Further Development ◽  
Sulfur Bond

A nickel-catalyzed carbon-sulfur bond metathesis has been developed to access high-value thioethers. 1,2-bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional group tolerant reaction. Further, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis which does not involve alkene bonds. In-depth organometallic studies support a reversible Ni(0)-Ni(II) pathway to product formation. Overall, this work does not only disclose a more sustainable and more functional group tolerant alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information which are highly relevant to the further development and application of unusual single bond metathesis reactions.

Regioselective Synthesis of Potent 4,5,6,7-Tetrahydroindazole Derivatives via Microwave-assisted Vilsmeier-Haack Reaction and their Antioxidant Activity Evaluation

2019 ◽  
Vol 16 (3) ◽  
pp. 194-201 ◽  
Author(s):  
Renu Bala ◽  
Vandana Devi ◽  
Pratibha Singh ◽  
Navjot Kaur ◽  
Pawandeep Kaur ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Microwave Irradiation ◽  
Biological Activities ◽  
Reaction Times ◽  
Conventional Heating ◽  
High Chemical ◽  
Microwave Assisted ◽  
Work Up ◽  
Active Methylene ◽  
By Products

Background: Tetrahydroindazole, a member of the fused-pyrazole system, is a least studied class of heterocyclic compounds owing to its scarcity in nature. However, a large number of synthetically prepared tetrahydroindazoles are known to show a variety of biological activities such as interleukin- 2 inducible T-Cell kinase inhibitors, AMPA receptor positive allosteric modulators, antitumor, antituberculosis, anti-inflammatory and antimicrobial activities. Vilsmeier-Haack reaction is one of the most important chemical reactions used for formylation of electron rich arenes. Even though Vilsmeier- Haack reaction was studied on a wide variety of hydrazones derived from active methylene compounds, literature lacks the examples of the use of 4-substituted cyclohexanones as a substrate for the synthesis of 4,5,6,7-tetrahydroindazoles. The study of the reaction of Vilsmeier-Haack reagent with hydrazones derived from cyclic keto compounds having active methylene has been considered the interested topic of investigation. In the present study, ethyl cyclohexanone-4-carboxylate was treated with one equivalent of various hydrazines for two hours and the resulted hydrazones were further treated with an OPC-VH reagent (Vilsmeier-Haack reagent isolated from phthaloyl dichloride and N,Ndimethylformamide) afforded 4,5,6,7-tetrahydroindazoles in excellent yields. The synthesized compounds 4a-f and 5a-f were screened for their antioxidant activities using the DPPH radical scavenging assay. The target compounds were synthesized regioselectively using 4+1 approach in excellent yields. A number of experiments using both conventional heating as well as microwave irradiation methods were tried and on comparison, microwave irradiation method was found excellent in terms of easy work up, high chemical yields, shortened reaction times, clean and, no by-products formation. Some of the synthesized compounds showed significant antioxidant activity. The microwave assisted synthesis of 4,5,6,7-tetrahydroindazoles from ethyl cyclohexanone-4-carboxylate has been reported under mild conditions in excellent yield. Easy work up, high chemical yield, shortened reaction times, clean and no by-products formation are the major advantages of this protocol. These advantages may make this method useful for chemists who are interested in developing novel 4,5,6,7-tetrahydroindazole based drugs.

scholarly journals Optimal pH in chlorinated swimming pools – balancing formation of by-products

2013 ◽  
Vol 11 (3) ◽  
pp. 465-472 ◽  
Author(s):  
Kamilla M. S. Hansen ◽  
Hans-Jørgen Albrechtsen ◽  
Henrik R. Andersen
Keyword(s):  
Body Fluid ◽  
Product Formation ◽  
Swimming Pools ◽  
Batch Experiments ◽  
Ph Values ◽  
Precursor Ratio ◽  
Decreasing Ph ◽  
Ph Range ◽  
By Products ◽  
Optimal Ph

In order to identify the optimal pH range for chlorinated swimming pools, the formation of trihalomethanes, haloacetonitriles and trichloramine was investigated in the pH-range 6.5–7.5 in batch experiments. An artificial body fluid analogue was used to simulate bather load as the precursor for by-products. The chlorine-to-precursor ratio used in the batch experiments influenced the amounts of by-products formed, but regardless of the ratio the same trends in the effect of pH were observed. Trihalomethane formation was reduced by decreasing pH, but haloacetonitrile and trichloramine formation increased. To evaluate the significance of the increase and decrease of the investigated organic by-products at the different pH values, the genotoxicity was calculated based on literature values. The calculated genotoxicity was approximately at the same level in the pH range 6.8–7.5 and increased when pH was 6.7 or lower. An optimal pH range for by-products formation in swimming pools was identified at pH 7.0–7.2. In the wider pH range (pH 6.8–7.5), the effect on by-product formation was negligible. Swimming pools should never be maintained at lower pH than 6.8 since formation of both haloacetonitriles and trichloramine increase significantly below this value.

scholarly journals Rhodium(ii)-catalyzed C–H aminations using N-mesyloxycarbamates: reaction pathway and by-product formation

2019 ◽  
Vol 10 (3) ◽  
pp. 718-729 ◽  
Author(s):  
Emna Azek ◽  
Maroua Khalifa ◽  
Johan Bartholoméüs ◽  
Matthias Ernzerhof ◽  
Hélène Lebel
Keyword(s):  
Reaction Pathway ◽  
Product Formation ◽  
Dft Study ◽  
By Products

DFT study to elucidate the mechanism of Rh-catalyzed C–H aminations with N-mesyloxycarbamates and the pathway by which by-products formed.

scholarly journals A Review on Chitosan’s Uses as Biomaterial: Tissue Engineering, Drug Delivery Systems and Cancer Treatment

Materials ◽  
2020 ◽  
Vol 13 (21) ◽  
pp. 4995 ◽  
Author(s):  
Rayssa de Sousa Victor ◽  
Adillys Marcelo da Cunha Santos ◽  
Bianca Viana de Sousa ◽  
Gelmires de Araújo Neves ◽  
Lisiane Navarro de Lima Santana ◽  
...  
Keyword(s):  
Drug Delivery ◽  
Tissue Engineering ◽  
Metal Ions ◽  
Cancer Treatment ◽  
Drug Delivery Systems ◽  
Therapeutic Potential ◽  
Delivery Systems ◽  
Amino Groups ◽  
New Information ◽  
Acidic Conditions

Chitosan, derived from chitin, is a biopolymer consisting of arbitrarily distributed β-(1-4)-linked D-glucosamine and N-acetyl-D-glucosamine that exhibits outstanding properties— biocompatibility, biodegradability, non-toxicity, antibacterial activity, the capacity to form films, and chelating of metal ions. Most of these peculiar properties are attributed to the presence of free protonable amino groups along the chitosan backbone, which also gives it solubility in acidic conditions. Moreover, this biopolymer can also be physically modified, thereby presenting a variety of forms to be developed. Consequently, this polysaccharide is used in various fields, such as tissue engineering, drug delivery systems, and cancer treatment. In this sense, this review aims to gather the state-of-the-art concerning this polysaccharide when used as a biomaterial, providing information about its characteristics, chemical modifications, and applications. We present the most relevant and new information about this polysaccharide-based biomaterial’s applications in distinct fields and also the ability of chitosan and its various derivatives to selectively permeate through the cancer cell membranes and exhibit anticancer activity, and the possibility of adding several therapeutic metal ions as a strategy to improve the therapeutic potential of this polymer.

An improved synthesis of m-diazirinophenol

1984 ◽  
Vol 62 (9) ◽  
pp. 1767-1771 ◽  
Author(s):  
Pierre Leblanc ◽  
Gerhard E. Gerber
Keyword(s):  
High Pressure ◽  
Liquid Chromatography ◽  
Silica Gel ◽  
High Pressure Liquid Chromatography ◽  
Good Yield ◽  
Reverse Phase ◽  
Oxidation Step ◽  
Work Up

The published synthesis of phenolic diazirine was shown to result in products which were chlorinated during the hypochlorite oxidation while the desired unchlorinated product was lost during the usual work-up. A superior synthesis is described: inclusion of pyridine during the oxidation step prevents the chlorination; the desired volatile diazirine was isolated in good yield using silica gel and reverse phase high pressure liquid chromatography.

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