Chemical Control over T-Cell Activation <i>in Vivo</i> Using Deprotection of <i>trans</i>-Cyclooctene-Modified Epitopes

Gracht, Anouk M F van der; Geus, Mark A. R. de; Camps, Marcel; Ruckwardt, Tracy J.; Sarris, Alexi J C; Bremmers, Jessica S.; Maurits, Elmer; Pawlak, Joanna B.; Posthoorn, Michelle M; Bonger, Kimberly M.; Filippov, Dmitri V.; Overkleeft, Herman S.; Robillard, Marc S.; Ossendorp, Ferry; Kasteren, Sander I. van

doi:10.1021/acschembio.8b00155

Cited by 44 publications

(39 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[6] The IEDDA/pyridazine elimination reaction, [7] a" click-to-release" reaction in which an allylic substituent on trans-cyclooctene( 2-TCO,a xial (E)-cyclooct-2-en-1-ol) is eliminated upon rearrangement of the pyridazinei ntermediate, has proven particularly favorable in this regard and it showse xcellent biocompatibility [8] and low toxicity. [9] In vivo applicationsi nclude the chemical control of drug release, [10] control over T-cell activation, [11] releaseo f drugs from hydrogels, [12] as well as control over kinase activity in mice. [9] Mechanistic insights into this reactionh ave provided ap athway to improvingt his ligation/elimination reaction.…”

Section: Introductionmentioning

confidence: 99%

Fast and pH‐Independent Elimination of trans‐Cyclooctene by Using Aminoethyl‐Functionalized Tetrazines

Sarris

Hansen

Geus

et al. 2018

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The inverse-electron-demand Diels-Alder/pyridazine elimination tandem reaction, in which the allylic substituent on trans-cyclooctene is eliminated following reaction with tetrazines, is gaining interest as a versatile bioorthogonal process. One potential shortcoming of such currently used reactions is their propensity to proceed faster and more efficiently at lower pH, a feature caused by the nature of the tetrazines used. Here, we present aminoethyl-substituted tetrazines as the first pH-independent reagents showing invariably fast elimination kinetics at all biologically relevant pH values.

show abstract

Section: Introductionmentioning

confidence: 99%

Fast and pH‐Independent Elimination of trans‐Cyclooctene by Using Aminoethyl‐Functionalized Tetrazines

Sarris

Hansen

Geus

et al. 2018

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…[86] The faster kinetics of the trans-cyclooctene/tetrazine chemistry relative to the Staudinger reaction enabled the control of T-cell activationi n vivo by using epitopes with trans-cyclooctene-caged lysines. [87] Wang et al further used dissociative bioorthogonal chemistry to manipulate the chargeonc ell-surface glycans to controlc ell clustering. [24] These studies showedt he broad applicability of the chemical unmasking of protein residues.…”

Section: Using Dissociative Chemistry To Control the Activityo F Protmentioning

confidence: 99%

“…The azide group prevented recognition of the peptide by cognate T cells; after Staudinger reduction to the lysine, the antigen peptide could be detected by T cells, and this activated them in vitro . The faster kinetics of the trans ‐cyclooctene/tetrazine chemistry relative to the Staudinger reaction enabled the control of T‐cell activation in vivo by using epitopes with trans ‐cyclooctene‐caged lysines . Wang et al.…”

Section: Applications Of Dissociative Bioorthogonal Reactions In the mentioning

confidence: 99%

Dissociative Bioorthogonal Reactions

Franzini

2019

ChemBioChem

View full text Add to dashboard Cite

Bioorthogonal reactions that proceed readily under physiological conditions without interference from biomolecules have found widespread application in the life sciences. Complementary to the bioorthogonal reactions that ligate two molecules, reactions that release a molecule or cleave a linker are increasingly attracting interest. Such dissociative bioorthogonal reactions have a broad spectrum of uses, for example, in controlling bio‐macromolecule activity, in drug delivery, and in diagnostic assays. This review article summarizes the developed bioorthogonal reactions linked to a release step, outlines representative areas of the applications of such reactions, and discusses aspects that require further improvement.

show abstract

“…Since our original description of the flow photoisomerization protocol, it has been employed by a number of groups for trans ‐cyclooctene synthesis with applications that include radiochemistry, cellular imaging, drug delivery and materials science . There have also been a number of modifications to the flow procedure that have been introduced.…”

Section: Figurementioning

confidence: 99%

Flow Photochemical Syntheses of trans‐Cyclooctenes and trans‐Cycloheptenes Driven by Metal Complexation

Pigga

Fox

2019

Israel Journal of Chemistry

View full text Add to dashboard Cite

trans-Cyclooctenes and trans-cycloheptenes have long been the subject of physical organic study, but the broader application had been limited by synthetic accessibility. This account describes the development of a general, flow photochemical method for the preparative synthesis of trans-cycloalkene derivatives. Here, photoisomerization takes place in a closed-loop flow reactor where the reaction mixture is continuously cycled through Ag(I) on silicagel. Selective complexation of the trans-isomer by Ag(I) during flow drives an otherwise unfavorable isomeric ratio toward the transisomer. Analogous photoreactions under batch-conditions are low yielding, and flow chemistry is necessary in order to obtain trans-cycloalkenes in preparatively useful yields. The applications of the method to bioorthogonal chemistry and stereospecific transannulation chemistry are described.The unusual reactivity and well-defined chiral structure of trans-cycloalkenes has made them attractive targets for synthesis for nearly 70 years. [1][2][3] For example, trans-cyclooctene possesses planar chirality and displays a high barrier to racemization (E a = 35.6 kcal/mol), [4] and the most stable "crown" conformer has an alternating sequence of equatorial and axial hydrogens that is akin to chair cyclohexane. [5][6] The double bond of trans-cyclooctene is twisted severely in the crown conformation, [7] and as a consequence the HOMO of trans-cyclooctene is relatively high in energy. [8] trans-Cycloheptene also has a rigid structure with a distorted alkene. [7] The double bonds of medium-ring trans-alkenes are twisted. [7] trans-Cycloalkenes display unusual reactivity in HOMOalkene controlled cycloaddition reactions with dienes, [9] 1,3dipoles [8] and ketenes. [10] Strained trans-cycloalkenes also serve as ligands for transition metals. [11][12][13][14][15][16] This reactivity profile has made trans-cycloalkanes interesting targets for applications in synthesis and biology.The broadest applications of trans-cycloalkenes are in the field of bioorthogonal chemistry. The inverse-electron demand Diels-Alder reaction between tetrazines and strained alkenes has a rich history in physical organic and synthetic chemistry (Figure 1). [17][18][19] In 2008, three groups described the bioorthogonal reactions of tetrazines with strained alkenes. [20][21][22] The variant introduced by our group that used trans-cyclooctene is marked by exceptionally rapid kinetics, with rate constants that can exceed 10 6 M À 1 s À 1 in the fastest cases. [23][24] With the advances including the development of fluorogenic tetrazines [25] and reactions in live cells [26] and animals, [27] the tetrazine ligation has become a widely used tool for applications that span chemical biology, biomedical imaging, and materials science. [28][29][30][31][32][33][34][35][36][37] This account describes the development of general, flow photochemical methods for the preparative synthesis of transcycloalkene derivatives and enabled applications in synthesis and bioorthogonal chemistry. Selectiv...

show abstract

Chemical Control over T-Cell Activation in Vivo Using Deprotection of trans-Cyclooctene-Modified Epitopes

Cited by 44 publications

References 55 publications

Fast and pH‐Independent Elimination of trans‐Cyclooctene by Using Aminoethyl‐Functionalized Tetrazines

Fast and pH‐Independent Elimination of trans‐Cyclooctene by Using Aminoethyl‐Functionalized Tetrazines

Dissociative Bioorthogonal Reactions

Flow Photochemical Syntheses of trans‐Cyclooctenes and trans‐Cycloheptenes Driven by Metal Complexation

Contact Info

Product

Resources

About