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Chemistry, An Asian Journal May 2020The development of advanced bioorthogonal reactions for detection and labeling of biomolecules is significant in chemical biology. Recently, researchers have found that... (Review)
Review
The development of advanced bioorthogonal reactions for detection and labeling of biomolecules is significant in chemical biology. Recently, researchers have found that multifluorinated aryl azides hold great potential for the development of improved bioorthogonal reactions. The fluorine atom can be a perfect substituent group because of its properties of excellent electronegativity and small steric hindrance. In this Minireview, we discuss recent developments of improved hydrogen sulfide (H S) fluorescence probes, fast strain-promoted azide-alkyne cycloaddition (SPAAC) and nonhydrolysis Staudinger reactions based on the use of multifluorinated aryl azides. Additionally, kinetic studies and biological applications of these reactions are also presented.
Topics: Alkynes; Azides; Cycloaddition Reaction; Fluorescent Dyes; Halogenation; Hydrogen Sulfide; Molecular Structure; Optical Imaging
PubMed: 32144862
DOI: 10.1002/asia.202000005 -
Chemistry (Weinheim An Der Bergstrasse,... May 2022A new class of attractive intermolecular interaction between azide and ethynyl structural entities in a wide range of molecular crystals is reported. This interaction...
A new class of attractive intermolecular interaction between azide and ethynyl structural entities in a wide range of molecular crystals is reported. This interaction was systematically evaluated by using 11 geometrically different structural motifs that are preorganized to direct a solid-state topochemical azide-alkyne cycloaddition (TAAC) reaction. The supramolecular features of the azide-alkyne interaction were mapped by various crystallographic and quantum chemical approaches. Topological analysis shows the noticeable participation of electron density in the azide⋅⋅⋅alkyne interactions. Interestingly, reorientation of the atomic polarizabilities in vicinal azide and alkyne groups upon interaction in crystals favors soft orbital-guided TAAC reactions. Moreover, various solid-state and gas-phase energy decomposition methods of individual azide⋅⋅⋅alkyne interactions summarize that the strength (varies from -5.7 to -30.1 kJ mol ) is primarily guided by the dispersion forces with a influencing contribution from the electrostatics.
Topics: Alkynes; Azides; Cycloaddition Reaction
PubMed: 35302679
DOI: 10.1002/chem.202200820 -
Chembiochem : a European Journal of... Nov 2003
Review
Topics: Alkynes; Animals; Azides; Catalysis; Cholinesterase Inhibitors; Molecular Structure
PubMed: 14613105
DOI: 10.1002/cbic.200300705 -
Molecules (Basel, Switzerland) Jun 2013Click chemistry is a powerful chemical reaction with excellent bioorthogonality features: biocompatible, rapid and highly specific in biological environments. For... (Review)
Review
Click chemistry is a powerful chemical reaction with excellent bioorthogonality features: biocompatible, rapid and highly specific in biological environments. For glycobiology, bioorthogonal click chemistry has created a new method for glycan non-invasive imaging in living systems, selective metabolic engineering, and offered an elite chemical handle for biological manipulation and glycomics studies. Especially the [3 + 2] dipolar cycloadditions of azides with strained alkynes and the Staudinger ligation of azides and triarylphosphines have been widely used among the extant click reactions. This review focuses on the azide-based bioorthogonal click chemistry, describing the characteristics and development of these reactions, introducing some recent applications in glycobiology research, especially in glycan metabolic engineering, including glycan non-invasive imaging, glycomics studies and viral surface manipulation for drug discovery as well as other applications like activity-based protein profiling and carbohydrate microarrays.
Topics: Azides; Click Chemistry; Glycomics; Research
PubMed: 23783454
DOI: 10.3390/molecules18067145 -
Mutation Research. Genetic Toxicology... 2022Sodium azide is a strong mutagen that has been successfully employed in mutation breeding of crop plants. In biological systems, it is metabolically converted to the...
Sodium azide is a strong mutagen that has been successfully employed in mutation breeding of crop plants. In biological systems, it is metabolically converted to the proximate mutagen azidoalanine, which requires further bioactivation to a putative ultimate mutagen that remains elusive. The nature of the DNA modifications induced by azides leading to mutations is also unknown. Other mutagenic organic azido compounds seem to share the same bioactivation pathway to the ultimate mutagenic species as they induce point mutations dependent on the same DNA repair pathways. We investigated mutations induced by the representative mutagen 3-azido-1,2-propanediol (azidoglycerol, AZG) in the human TK6 cell line. Until now, azides have been considered to be non-mutagens and non-carcinogens in mammals, including humans, as judged only by the conventional clastogenicity chromosomal aberration types of bioassays. Here, we show the potent mutagenicity of AZG in cultured human cells, comparable to alkylating agents such as methyl methanesulfonate at concentrations with similar lethality. The potent ability of an organic azide to induce base substitutions in a mammalian system raises an alert with respect to human exposure to organic and inorganic azido compounds.
Topics: Animals; Azides; Humans; Mammals; Mutagenesis; Mutagenicity Tests; Mutagens; Propylene Glycols
PubMed: 35483777
DOI: 10.1016/j.mrgentox.2022.503475 -
Acta Crystallographica. Section C,... Aug 2008The Cu(I)-catalysed 1,3-dipolar cycloaddition of an azide and a terminal alkyne is becoming an increasingly popular tool for synthetic chemists. This is the most...
The Cu(I)-catalysed 1,3-dipolar cycloaddition of an azide and a terminal alkyne is becoming an increasingly popular tool for synthetic chemists. This is the most representative of the so-called ;click reactions' and it is used to generate 1,4-disubstituted triazoles in high yield. During studies on such cycloaddition reactions, a reduced reactivity of an alpha-glucosyl azide with respect to the corresponding beta-anomer was observed. With the aim of understanding this phenomenon, the structure of the title compound, C(14)H(19)N(3)O(9), has been determined at 140 K. The glucopyranosyl ring appears in a regular (4)C(1) chair conformation with all the substituents in equatorial positions, except for the anomeric azide group, which adopts an axial orientation. The observed bond lengths are consistent with a strong anomeric effect, which is reflected in a change in dipolar character and hence reduced reactivity of the alpha-glucosyl azide.
Topics: Azides; Crystallography, X-Ray; Models, Molecular; Molecular Structure; Monosaccharides
PubMed: 18682654
DOI: 10.1107/S0108270108020702 -
Mutation Research Feb 1988Inorganic azide (N3-) mutagenicity is mediated through a metabolically synthesized organic azide, L-azidoalanine (N3-CH2-CH(-NH2)-COOH). L-Azidoalanine appears to be... (Comparative Study)
Comparative Study Review
Inorganic azide (N3-) mutagenicity is mediated through a metabolically synthesized organic azide, L-azidoalanine (N3-CH2-CH(-NH2)-COOH). L-Azidoalanine appears to be formed by the action of O-acetylserine (thiol)-Lyase (EC 4.2.99.8) using O-acetylserine and azide as substrates. In both plants and bacteria tested, azide substitutes for the natural substrate sulfide (S2-) in this reaction. Azide (L-azidoalanine) mutagenesis is highly attenuated by a deficiency in the excision of UV-like DNA damage (uvr-). Thus a premutation lesion recognizable by the bacterial excision-repair enzymes must be formed. Mutagenesis appears to proceed from this by 'direct mispairing' pathway. Azide (L-azidoalanine) mutagenicity is highly specific and involves a stereoselective process, but the molecular nature of the specificity has not been determined.
Topics: Alanine; Azides; Biotransformation; DNA Damage; DNA Repair; Mutagenicity Tests; Mutagens; Plants; Salmonella typhimurium; Serine; Sodium Azide; Structure-Activity Relationship
PubMed: 3123923
DOI: 10.1016/0027-5107(88)90101-7 -
Angewandte Chemie (International Ed. in... Sep 2022Here we report the synthesis of a trisubstituted-1,2,3-triazole-linked polymer using a topochemical azide-alkyne cycloaddition (TAAC) reaction. A cyclitol-derived...
Here we report the synthesis of a trisubstituted-1,2,3-triazole-linked polymer using a topochemical azide-alkyne cycloaddition (TAAC) reaction. A cyclitol-derived monomer having an azide and an internal alkyne group was designed. The four hydroxy groups present in this monomer dictate its crystal packing such that the monomer molecules are arranged head-to-tail, thereby placing the internal alkyne and the azide units of adjacent molecules proximally. Although the alignment of the reactive groups in the monomer crystal is not favourable for a topochemical reaction, a reactive orientation can be achieved by the rotation of the reactive groups. Upon heating the crystals, the monomer underwent topochemical polymerization to yield the trisubstituted-1,2,3-triazole-linked-polycyclitol. This study demonstrates a new synthetic strategy for cycloaddition reaction between non-polarized internal alkynes and azides to yield trisubstituted triazoles.
Topics: Alkynes; Azides; Catalysis; Copper; Cycloaddition Reaction; Polymerization; Triazoles
PubMed: 35857815
DOI: 10.1002/anie.202210453 -
Chemical Communications (Cambridge,... Dec 2022Benzylic azides, an important class of active organic synthons, were synthesized in high yields from the easily accessible -triftosylhydrazones with stable TMSN under...
Benzylic azides, an important class of active organic synthons, were synthesized in high yields from the easily accessible -triftosylhydrazones with stable TMSN under mild conditions. The reaction features high efficiency and excellent functional group tolerance, as illustrated by gram-scale synthesis and the synthesis of drug-like molecules. Mechanistic studies reveal that azidation occurs at the electron-deficient diazo-carbon the elimination of N by an azide ion.
Topics: Azides; Transition Elements; Carbon
PubMed: 36441144
DOI: 10.1039/d2cc05442f -
Basic & Clinical Pharmacology &... Mar 2021Azide is a highly toxic chemical agent to human being. Accidental, but also intentional exposure to azide occurs. To be able to confirm azide ingestion, we developed a...
Azide is a highly toxic chemical agent to human being. Accidental, but also intentional exposure to azide occurs. To be able to confirm azide ingestion, we developed a method to identify and quantify azide in biological matrices. Cyanide was included in the method to evaluate suggested in vivo production of cyanide after azide ingestion. Azide in biological matrices was first derivatized by propionic anhydride to form propionyl azide. Simultaneously, cyanide was converted into hydrogen cyanide. After thermal rearrangement of propionyl azide, ethyl isocyanate was formed, separated together with hydrogen cyanide by gas chromatography (GC) and detected using a nitrogen phosphorous detector (NPD). The method was linear from 1.0-100 µg/mL for both analytes, and azide was stable in human plasma at -20°C for at least 49 days. Azide was measured in the gastric content of two cases of suspected azide ingestion (case 1:1.2 mg/mL, case 2:1.5 mg/mL). Cyanide was only identified in the gastric content of case 1 (approximately 1.4 µg/mL). Furthermore, azide was quantified in plasma (19 µg/mL), serum (24 µg/mL), cell pellet (21 µg/mL) and urine (3.0 µg/mL) of case 2. This method can be used to confirm azide and cyanide exposure, and azide concentrations can be quantified in several biological matrices.
Topics: Adult; Azides; Chromatography, Gas; Cyanides; Female; Humans
PubMed: 33090684
DOI: 10.1111/bcpt.13523