scholarly journals Chemocatalytic Amplification Probes Enable Transcriptionally-Regulated Au(I)-Catalysis in E. coli and Sensitive Detection of SARS-CoV-2 RNA Fragments

2020 ◽  
Author(s):  
Sydnee Green ◽  
Benjamin Wigman ◽  
Sepand Nistanaki ◽  
Hayden Montgomery ◽  
Christopher G. Jones ◽  
...  
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalysis ◽  
Sensitive Detection ◽  
Metal Species ◽  
Chemical Compatibility ◽  
Biological Matrices ◽  
Reactive Metal ◽  
Hybridization Probe ◽  
Metal Catalysis ◽  
E Coli

<div>The union of transition metal catalysis with native biochemistry presents a powerful opportunity</div><div>to perform abiotic reactions within complex biological systems.(1,2) However, several chemical</div><div>compatibility challenges associated with incorporating reactive metal centers into complex</div><div>biological environments have hindered efforts in this area, despite the many opportunities it may</div><div>present. More challenging than chemical compatibility is biocommunicative transition metal</div><div>catalysis, where the reactivity of the metal species is regulated by native biological stimuli, akin</div><div>to natural biocatalytic processes. Here we report a novel Au(I)-DNAzyme that is activated by short</div><div>nucleic acids in a highly sequence-specific manner and that is compatible with complex biological</div><div>matrices. The active Au(I)-DNAzyme catalyzes the formation of a fluorescent molecule with >10</div><div>turnovers. This functional allostery, resulting in chemocatalytic signal amplification, is competent</div><div>in complex biological settings, including within recombinant E. coli cells, where the catalytic</div><div>activity of the Au(I)-DNAzyme is regulated by transcription of an inducible plasmid. We further</div><div>demonstrate the potential of this transition metal oligonucleotide complex as a highly sensitive and</div><div>selective hybridization probe, permitting the detection of attomolar concentrations (ca. 60</div><div>molecules/µL) of SARS-CoV-2 RNA gene fragments in simulated biological matrices with ≥85%</div><div>accuracy. Notably, this sensitive detection platform avoids expensive and poorly-scalable</div><div>biochemical components (e.g. post-synthetically modified oligonucleotides or enzymes) and</div><div>utilizes small molecule fluorophores, inexpensive Au salts and oligonucleotides composed of</div><div>canonical bases. This discovery highlights promising opportunities to perform abiotic catalysis in</div><div>complex biological settings under transcriptional regulation, as well as a chemocatalytic strategy</div><div>for PCR-free, direct-detection of RNA and DNA.</div><div><br></div><p>The union of transition metal catalysis with native biochemistry presents a powerful opportunity to perform abiotic reactions within complex biological systems. However, several chemical compatibility challenges associated with incorporating reactive metal centers into complex biological environments have hindered efforts in this area, despite the many opportunities it may present. More challenging than chemical compatibility is biocommunicative transition metal catalysis, where the reactivity of the metal species is regulated by native biological stimuli, akin to natural biocatalytic processes. Here we report a novel Au(I)-DNAzyme that is activated by short nucleic acids in a highly sequence-specific manner and that is compatible with complex biological matrices. The active Au(I)-DNAzyme catalyzes the formation of a fluorescent molecule with >10 turnovers. This functional allostery, resulting in chemocatalytic signal amplification, is competent in complex biological settings, including within recombinant <i>E. coli </i>cells, where the catalytic activity of the Au(I)-DNAzyme is regulated by transcription of an inducible plasmid. We further demonstrate the potential of this transition metal oligonucleotide complex as a highly sensitive and selective hybridization probe, permitting the detection of attomolar concentrations (<i>ca.</i> 60 molecules/ L) of SARS-CoV-2 RNA gene fragments in simulated biological matrices with ≥85% accuracy. Notably, this sensitive detection platform avoids expensive and poorly-scalable biochemical components (e.g. post-synthetically modified oligonucleotides or enzymes) and utilizes small molecule fluorophores, inexpensive Au salts and oligonucleotides composed of canonical bases. This discovery highlights promising opportunities to perform abiotic catalysis in complex biological settings under transcriptional regulation, as well as a chemocatalytic strategy for PCR-free, direct-detection of RNA and DNA.</p>

scholarly journals Chemocatalytic Amplification Probes Enable Transcriptionally-Regulated Au(I)-Catalysis in E. coli and Sensitive Detection of SARS-CoV-2 RNA Fragments

2020 ◽  
Author(s):  
Sydnee Green ◽  
Benjamin Wigman ◽  
Sepand Nistanaki ◽  
Hayden Montgomery ◽  
Christopher G. Jones ◽  
...  
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalysis ◽  
Sensitive Detection ◽  
Metal Species ◽  
Chemical Compatibility ◽  
Biological Matrices ◽  
Reactive Metal ◽  
Hybridization Probe ◽  
Metal Catalysis ◽  
E Coli

<div>The union of transition metal catalysis with native biochemistry presents a powerful opportunity</div><div>to perform abiotic reactions within complex biological systems.(1,2) However, several chemical</div><div>compatibility challenges associated with incorporating reactive metal centers into complex</div><div>biological environments have hindered efforts in this area, despite the many opportunities it may</div><div>present. More challenging than chemical compatibility is biocommunicative transition metal</div><div>catalysis, where the reactivity of the metal species is regulated by native biological stimuli, akin</div><div>to natural biocatalytic processes. Here we report a novel Au(I)-DNAzyme that is activated by short</div><div>nucleic acids in a highly sequence-specific manner and that is compatible with complex biological</div><div>matrices. The active Au(I)-DNAzyme catalyzes the formation of a fluorescent molecule with >10</div><div>turnovers. This functional allostery, resulting in chemocatalytic signal amplification, is competent</div><div>in complex biological settings, including within recombinant E. coli cells, where the catalytic</div><div>activity of the Au(I)-DNAzyme is regulated by transcription of an inducible plasmid. We further</div><div>demonstrate the potential of this transition metal oligonucleotide complex as a highly sensitive and</div><div>selective hybridization probe, permitting the detection of attomolar concentrations (ca. 60</div><div>molecules/µL) of SARS-CoV-2 RNA gene fragments in simulated biological matrices with ≥85%</div><div>accuracy. Notably, this sensitive detection platform avoids expensive and poorly-scalable</div><div>biochemical components (e.g. post-synthetically modified oligonucleotides or enzymes) and</div><div>utilizes small molecule fluorophores, inexpensive Au salts and oligonucleotides composed of</div><div>canonical bases. This discovery highlights promising opportunities to perform abiotic catalysis in</div><div>complex biological settings under transcriptional regulation, as well as a chemocatalytic strategy</div><div>for PCR-free, direct-detection of RNA and DNA.</div><div><br></div><p>The union of transition metal catalysis with native biochemistry presents a powerful opportunity to perform abiotic reactions within complex biological systems. However, several chemical compatibility challenges associated with incorporating reactive metal centers into complex biological environments have hindered efforts in this area, despite the many opportunities it may present. More challenging than chemical compatibility is biocommunicative transition metal catalysis, where the reactivity of the metal species is regulated by native biological stimuli, akin to natural biocatalytic processes. Here we report a novel Au(I)-DNAzyme that is activated by short nucleic acids in a highly sequence-specific manner and that is compatible with complex biological matrices. The active Au(I)-DNAzyme catalyzes the formation of a fluorescent molecule with >10 turnovers. This functional allostery, resulting in chemocatalytic signal amplification, is competent in complex biological settings, including within recombinant <i>E. coli </i>cells, where the catalytic activity of the Au(I)-DNAzyme is regulated by transcription of an inducible plasmid. We further demonstrate the potential of this transition metal oligonucleotide complex as a highly sensitive and selective hybridization probe, permitting the detection of attomolar concentrations (<i>ca.</i> 60 molecules/ L) of SARS-CoV-2 RNA gene fragments in simulated biological matrices with ≥85% accuracy. Notably, this sensitive detection platform avoids expensive and poorly-scalable biochemical components (e.g. post-synthetically modified oligonucleotides or enzymes) and utilizes small molecule fluorophores, inexpensive Au salts and oligonucleotides composed of canonical bases. This discovery highlights promising opportunities to perform abiotic catalysis in complex biological settings under transcriptional regulation, as well as a chemocatalytic strategy for PCR-free, direct-detection of RNA and DNA.</p>

scholarly journals Chemocatalytic Amplification Probes Enable Transcriptionally-Regulated Au(I)-Catalysis in E. coli and Sensitive Detection of SARS-CoV-2 RNA Fragments

2020 ◽  
Author(s):  
Sydnee Green ◽  
Benjamin Wigman ◽  
Sepand Nistanaki ◽  
Hayden Montgomery ◽  
Christopher G. Jones ◽  
...  
Keyword(s):  
Transition Metal ◽  
Direct Detection ◽  
Sensitive Detection ◽  
Metal Species ◽  
Reactive Metal ◽  
Hybridization Probe ◽  
Metal Centers ◽  
E Coli ◽  
Rna Fragments ◽  
The Many

<div>The union of transition metal catalysis with native biochemistry presents a powerful opportunity</div><div>to perform abiotic reactions within complex biological systems.(1,2) However, several chemical</div><div>compatibility challenges associated with incorporating reactive metal centers into complex</div><div>biological environments have hindered efforts in this area, despite the many opportunities it may</div><div>present. More challenging than chemical compatibility is biocommunicative transition metal</div><div>catalysis, where the reactivity of the metal species is regulated by native biological stimuli, akin</div><div>to natural biocatalytic processes. Here we report a novel Au(I)-DNAzyme that is activated by short</div><div>nucleic acids in a highly sequence-specific manner and that is compatible with complex biological</div><div>matrices. The active Au(I)-DNAzyme catalyzes the formation of a fluorescent molecule with >10</div><div>turnovers. This functional allostery, resulting in chemocatalytic signal amplification, is competent</div><div>in complex biological settings, including within recombinant E. coli cells, where the catalytic</div><div>activity of the Au(I)-DNAzyme is regulated by transcription of an inducible plasmid. We further</div><div>demonstrate the potential of this transition metal oligonucleotide complex as a highly sensitive and</div><div>selective hybridization probe, permitting the detection of attomolar concentrations (ca. 60</div><div>molecules/µL) of SARS-CoV-2 RNA gene fragments in simulated biological matrices with ≥85%</div><div>accuracy. Notably, this sensitive detection platform avoids expensive and poorly-scalable</div><div>biochemical components (e.g. post-synthetically modified oligonucleotides or enzymes) and</div><div>utilizes small molecule fluorophores, inexpensive Au salts and oligonucleotides composed of</div><div>canonical bases. This discovery highlights promising opportunities to perform abiotic catalysis in</div><div>complex biological settings under transcriptional regulation, as well as a chemocatalytic strategy</div><div>for PCR-free, direct-detection of RNA and DNA.</div><div><br></div>

Carbon‐Sulfur Bond Constructions: From Transition‐Metal Catalysis to Sustainable Catalysis

2021 ◽  
Author(s):  
Pratheepkumar Annamalai ◽  
Ke‐Chien Liu ◽  
Satpal Singh Badsara ◽  
Chin‐Fa Lee
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalysis ◽  
Metal Catalysis ◽  
Sulfur Bond

An electrochemical perspective on the roles of ligands in the merger of transition-metal catalysis and electrochemistry

2020 ◽  
Author(s):  
Ke-Yin Ye ◽  
Jun-Song Zhong ◽  
Yi Yu ◽  
Zhaojiang Shi
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Transition Metal Catalysis ◽  
Metal Catalysis

The merger of transition-metal catalysis and electrochemistry has been emerging as a very versatile and robust synthetic tool in organic synthesis. Like in their non-electrochemical variants, ligands also play crucial...

Insertion Reaction of 2-Halo-N-allylanilines with K2S Involving Trisulfur Radical Anion: Synthesis of Benzothiazole Derivatives under Transition-Metal-Free Conditions

Synthesis ◽  
2020 ◽  
Author(s):  
Yan-Wei Zhao ◽  
Shun-Yi Wang ◽  
Xin-Yu Liu ◽  
Tian Jiang ◽  
Weidong Rao
Keyword(s):  
Transition Metal ◽  
Radical Anion ◽  
Radical Cyclization ◽  
Transition Metal Catalysis ◽  
Insertion Reaction ◽  
Metal Catalysis ◽  
Metal Free ◽  
Benzothiazole Derivatives

AbstractA synthesis of benzothiazole derivatives through the reaction of 2-halo-N-allylanilines with K2S in DMF is developed. The trisulfur radical anion S3·–, which is generated in situ from K2S in DMF, initiates the reaction without transition-metal catalysis or other additives. In addition, two C–S bonds are formed and heteroaromatization of benzothiazole is triggered by radical cyclization and H-shift.

scholarly journals Enamine/Transition Metal Combined Catalysis: Catalytic Transformations Involving Organometallic Electrophilic Intermediates

2019 ◽  
Vol 377 (6) ◽  
Author(s):  
Samson Afewerki ◽  
Armando Córdova
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Carbonyl Compounds ◽  
Transition Metal Catalysis ◽  
Chemical Transformations ◽  
Considerable Effort ◽  
Metal Catalysis ◽  
First Report ◽  
Wide Range ◽  
Selective Chemical

AbstractThe concept of merging enamine activation catalysis with transition metal catalysis is an important strategy, which allows for selective chemical transformations not accessible without this combination. The amine catalyst activates the carbonyl compounds through the formation of a reactive nucleophilic enamine intermediate and, in parallel, the transition metal activates a wide range of functionalities such as allylic substrates through the formation of reactive electrophilic π-allyl-metal complex. Since the first report of this strategy in 2006, considerable effort has been devoted to the successful advancement of this technology. In this chapter, these findings are highlighted and discussed.

scholarly journals Tandem rhodium catalysis: exploiting sulfoxides for asymmetric transition-metal catalysis

2015 ◽  
Vol 13 (21) ◽  
pp. 5844-5847 ◽  
Author(s):  
K. G. M. Kou ◽  
V. M. Dong
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalysis ◽  
Metal Catalysis ◽  
Rhodium Catalysis ◽  
Alkene Hydrogenation

Sulfoxides are uncommon substrates for transition-metal catalysis due to their propensity to inhibit catalyst turnover. We have developed the first DKR of racemic allylic sulfoxides where rhodium catalyzed both sulfoxide epimerization and alkene hydrogenation.

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