Academic literature on the topic 'Chemoselective Synthesis'

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Journal articles on the topic "Chemoselective Synthesis"

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Verlee, Arno, Thomas Heugebaert, Tom van der Meer, Pavel I. Kerchev, Frank Van Breusegem, and Christian V. Stevens. "A chemoselective and continuous synthesis of m-sulfamoylbenzamide analogues." Beilstein Journal of Organic Chemistry 13 (February 16, 2017): 303–12. http://dx.doi.org/10.3762/bjoc.13.33.

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For the synthesis of m-sulfamoylbenzamide analogues, small molecules which are known for their bioactivity, a chemoselective procedure has been developed starting from m-(chlorosulfonyl)benzoyl chloride. Although a chemoselective process in batch was already reported, a continuous-flow process reveals an increased selectivity at higher temperatures and without catalysts. In total, 15 analogues were synthesized, using similar conditions, with yields ranging between 65 and 99%. This is the first automated and chemoselective synthesis of m-sulfamoylbenzamide analogues.
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Cheng, Shuihong, Paeton L. Wantuch, Megan E. Kizer, Dustin R. Middleton, Ruitong Wang, Mikaela DiBello, Mingli Li, et al. "Glycoconjugate synthesis using chemoselective ligation." Organic & Biomolecular Chemistry 17, no. 10 (2019): 2646–50. http://dx.doi.org/10.1039/c9ob00270g.

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Wu, Xiao-Na, Zhi-Hao You, and Yan-Kai Liu. "Different hybridized oxygen atoms controlled chemoselective formation of oxocarbenium ions: synthesis of chiral heterocyclic compounds." Organic & Biomolecular Chemistry 16, no. 35 (2018): 6507–20. http://dx.doi.org/10.1039/c8ob01743c.

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Chande, Madhukar S., Kiran A. Puthamane, Pravin A. Barve, Rahul R. Khanwelkar, and Deepak S. Venkataraman. "Chemoselective synthesis of novel thiatriazolophanes." Journal of the Brazilian Chemical Society 19, no. 1 (2008): 42–52. http://dx.doi.org/10.1590/s0103-50532008000100008.

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Salama, P. "Chemoselective Synthesis of Functionalized Diselenides." Tetrahedron Letters 36, no. 32 (August 7, 1995): 5711–14. http://dx.doi.org/10.1016/00404-0399(50)1112u-.

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He, Lisheng, Yuzhu Yang, Xiaolan Liu, Guangyan Liang, Chunyan Li, Daoping Wang, and Weidong Pan. "Iodine-Mediated Oxidative Cyclization of 2-(Pyridin-2-yl)acetate Derivatives with Alkynes: Condition-Controlled Selective Synthesis of Multisubstituted Indolizines." Synthesis 52, no. 03 (October 29, 2019): 459–70. http://dx.doi.org/10.1055/s-0039-1690229.

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An iodine-mediated oxidative cyclization reaction between 2-(pyridin-2-yl)acetate derivatives and different alkynes has been developed, which provides regioselective and chemoselective syntheses of multiply substituted indolizines under modified reaction conditions. Plausible mechanisms have been proposed to explain the selective syntheses of indolizines. This protocol can be also applied to the stepwise synthesis of 2,2′-biindolizines.
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Kaiser, Daniel, Adriano Bauer, Miran Lemmerer, and Nuno Maulide. "Amide activation: an emerging tool for chemoselective synthesis." Chemical Society Reviews 47, no. 21 (2018): 7899–925. http://dx.doi.org/10.1039/c8cs00335a.

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Bressy, Cyril, Mokhtaria Belkheira, Douniazad El Abed, and Jean-Marc Pons. "Chemoselective Organoclick–Click Sequence." Synthesis 50, no. 21 (July 19, 2018): 4254–62. http://dx.doi.org/10.1055/s-0037-1610192.

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A highly chemoselective bis-triazole synthesis based on a sequence organocatalyzed click reaction/copper-catalyzed click reaction is described in this paper. A range of bis-azides react with various ketones using proline catalysis through the aryl azide moiety while the alkyl azide one remains available for a metal-catalyzed triazole synthesis.
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Lu, Jiaqing, Yuning Man, Yabin Zhang, Bo Lin, Qi Lin, and Zhiqiang Weng. "Copper-catalyzed chemoselective synthesis of 4-trifluoromethyl pyrazoles." RSC Advances 9, no. 53 (2019): 30952–56. http://dx.doi.org/10.1039/c9ra07694h.

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Chinta, Bhavani Shankar, and Beeraiah Baire. "Formal total synthesis of selaginpulvilin D." Organic & Biomolecular Chemistry 15, no. 28 (2017): 5908–11. http://dx.doi.org/10.1039/c7ob00950j.

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Dissertations / Theses on the topic "Chemoselective Synthesis"

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Kasper, Marc-André. "Chemoselective synthesis of functional drug conjugates." Doctoral thesis, Humboldt-Universität zu Berlin, 2020. http://dx.doi.org/10.18452/20870.

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In der vorliegenden Arbeit wird eine modulare Reaktionssequenz von zwei aufeinanderfolgenden chemoselektiven Umwandlungen vorgestellt: Es wird gezeigt, dass Vinyl- und Ethynylphosphonamidate chemoselektiv mit Cysteinen von Proteinen und Antikörpern reagieren. Weiterhin wird gezeigt, dass elektrophile Phosphonamidate durch eine vorhergehende chemoselektive Staudinger-Phosphonit Reaktion zwischen Aziden und ungesättigten Phosphoniten in das gewünschte Molekül eingebaut werden können. Hierbei wird ein elektronenreiches Phosphonit in ein elektronenarmes Phosphonamidat umgewandelt, welches somit für die nachfolgende Thiol-Addition aktiviert wird. Die beschriebene Methode erweitert das bestehende Repertoire von Biokonjugationen durch die Einführung eines neuen Konzepts: Eine chemoleselektive Reaktion, die Reaktivität für eine nachfolgende Biokonjugation induziert. Da Phosphonamidat-Konjugationen an Cysteine herausragende Eigenschaften, wie hohe Selektivität für Cysteine, saubere Reaktionsprodukte und eine hervorragende Stabilität mitbringen, wird im zweiten Teil beschrieben wie Phosphonamidate für die Anbindung von zytotoxischen Wirkstoffen an tumor-bindende Antikörper genutzt werden können um Antikörper-Wirkstoff-Konjugate (ADCs) herzustellen. Ein einfaches Syntheseprotokoll für die Herstellung, ausgehend von einem nicht gentechnisch veränderten Antikörper mit nur geringen Überschüssen des Wirkstoffs wird vorgestellt. Phosphonamidat-verbundene ADCs zeigen im direkten Vergleichen zum zugelassenen, Maleimid-verbundenen Adcetris überlegende Eigenschaften, wie eine erhöhte Stabilität in Serum und eine erhöhte in vivo Wirksamkeit in einem Tumor Mausmodel. Zusammenfassend verbindet die hier vorgestellte Methode einen einfachen synthetischen Zugang mit hoher Selektivität, überragender Konjugat-Stabilität und der Möglichkeit hochwirksame Wirkstoffkonjugate herzustellen und wird daher aller Voraussicht nach einen großen Beitrag zum Gebiet der zielgerichteten Therapie leisten.
The present work introduces a modular reaction sequence of two chemoselective manipulations in a row. It is shown that vinyl- and ethynylphosphonamidates react selectively with cysteine residues on proteins and antibodies. Most importantly, those electrophilic phosphonamidates can be incorporated into a given molecule in another preceding chemoselective Staudinger-phosphonite reaction (SPhR) from unsaturated phosphonites and azides. During this reaction, an electron-rich phosphonite is transformed into an electron-deficient phosphonamidate that is thereby activated for the subsequent thiol addition. The described technique thereby extends the existing repertoire of bioconjugations by introducing a new concept in protein synthesis: A chemoselective reaction that induces reactivity for a subsequent bioconjugation. Since phosphonamidate conjugations to cysteine hold outstanding features such as high selectivity for cysteine, clean reaction products and excellent stability of the protein adducts in biological environments, it is described in the second part of the present work how ethynylphosphonamidates can be employed for the conjunction of tumor-sensing antibodies and cytotoxic drugs to generate Antibody-Drug-Conjugates (ADCs). A simple synthetic protocol starting from unengineered antibodies, using only a slight excess of the desired drug in a one-pot synthesis protocol is introduced. In a direct comparison to the maleimide containing FDA-approved Adcetris, phosphonamidate linked ADCs show a superior behaviour in terms of linkage stability in serum, combined with an increased in vivo efficacy in a tumor xenograft mouse model. Taken together, the method described herein combines simple synthetic access with high selectivity, superior conjugate stability and the possibility to synthesize highly efficacious drug conjugates and is therefore likely to have a great contribution to the field of targeted therapeutics.
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Li, Ronald Chuan-Teh. "Synthesis of polymer scaffolds for bioconjugation via chemoselective reactions." Diss., Restricted to subscribing institutions, 2008. http://proquest.umi.com/pqdweb?did=1781842041&sid=3&Fmt=2&clientId=1564&RQT=309&VName=PQD.

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李安怡 and On-yi Lee. "Synthesis of heterocycles via phenylseleno group transfer radical cyclization and chemoselective reductive amination promoted by InCl3." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2007. http://hub.hku.hk/bib/B3955756X.

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Steffensen, Mackay Bagley. "Methods for the syntheses of compositionally diverse dendrimers." Texas A&M University, 2004. http://hdl.handle.net/1969.1/2724.

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Dendrimers are a unique class of macromolecules that present perfect branching on a molecular scale. The pattern of branching at the atomic scale is compared to the branching of trees, from whence dendrimers get their name. Dendrimers have been attractive synthetic targets for the past twenty years. The methods and building blocks used in the synthesis of dendrimers vary, but molecules of this class of polymeric materials all possess symmetrical branching emanating from the core. At each branch point the number of groups increases exponentially. Efforts directed toward the synthesis of dendrimers presenting multiple functional groups at the surface and within the dendrimer structure are described. Methods are described which provide access to dendrimers in a one-pot per generation fashion, with triazines as the common moiety. Chemoselective routes utilize the temperature dependant substitution of cyanuric chloride to construct dendrimers, obviating the use of protected monomers or the need to manipulate functional groups during the synthesis. These methods are atom economical, as the only by-products are HCl and a base to scavenge it. The methods are efficient, with typical isolated yields of product in the middle to high ninety percent range, often on a multi-gram scale. Methods are described for conducting three separate reactions in a single pot. Specific emphasis is placed on structural control of the interior and surface groups of the dendrimers. The synthesis of a G3 dendrimer of layered composition is described. The use of a different difunctional linkage group for each generation of dendrimer growth produced a G3 dendrimer with layered composition without the use of protecting groups or functional group interconversions. A G3 dendrimer was synthesized presenting five different functionalities at the periphery on a 10 gram scale, resulting in approximately 70% overall yield. The peripheral groups are composed of orthogonal functionality, which can be independently and selectively unmasked or manipulated in the presence of the other functionality. The syntheses of dendrimers incorporating the short linker hydrazine produce materials with interesting physical properties as well as a low ratio of carbon to nitrogen. The use of dendrimers in the construction of novel macromolecular constructs is also described.
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Nischan, Nicole [Verfasser]. "Chemoselective Synthesis of Functional Peptide- and Protein-Conjugates for Intracellular Applications / Nicole Nischan." Berlin : Freie Universität Berlin, 2015. http://d-nb.info/1070820040/34.

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Imayoshi, Ayumi. "Discrimination of Mobile Supramolecular Chirality: Acylative Molecular Transformation by Organocatalysis." 京都大学 (Kyoto University), 2016. http://hdl.handle.net/2433/215486.

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He, Lu-Ying [Verfasser]. "Chemoselective Cross-Coupling Reactions as Tools in Synthesis and Applications for Polymer Chemistry / Lu-Ying He." Kiel : Universitätsbibliothek Kiel, 2015. http://d-nb.info/1070819247/34.

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Lee, On-yi. "Synthesis of heterocycles via phenylseleno group transfer radical cyclization and chemoselective reductive amination promoted by InCl3." Click to view the E-thesis via HKUTO, 2007. http://sunzi.lib.hku.hk/HKUTO/record/B3955756X.

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Hahn, Gabriela [Verfasser], and Rhett [Akademischer Betreuer] Kempe. "Reusable Ni-Catalysts for the Highly Chemoselective Synthesis of Primary Amines / Gabriela Hahn ; Betreuer: Rhett Kempe." Bayreuth : Universität Bayreuth, 2019. http://d-nb.info/1189207222/34.

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Kasper, Marc-André [Verfasser], Christian [Gutachter] Hackenberger, Dorothea [Gutachter] Fiedler, and Jeffrey W. [Gutachter] Bode. "Chemoselective synthesis of functional drug conjugates / Marc-André Kasper ; Gutachter: Christian Hackenberger, Dorothea Fiedler, Jeffrey W. Bode." Berlin : Humboldt-Universität zu Berlin, 2020. http://d-nb.info/1203126840/34.

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Books on the topic "Chemoselective Synthesis"

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Chan, W., and Peter White, eds. Fmoc Solid Phase Peptide Synthesis. Oxford University Press, 1999. http://dx.doi.org/10.1093/oso/9780199637256.001.0001.

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In the years since the publication of Atherton and Sheppard's volume, the technique of Fmoc solid-phase peptide synthesis has matured considerably and is now the standard approach for the routine production of peptides. The basic problems outstanding at the time of publication of this earlier work have now been, for the most part, solved. As a result, innovators in the field have focussed their efforts to develop methodologies and chemistry for the synthesis of more complex structures. The focus of this new volume is much broader, and covers not only the essential procedures for the production of linear peptides but also more advanced techniques for preparing cyclic, side-chain modified, phospho- and glycopeptides. Many other methods also deserving attention have been included: convergent peptide synthesis; peptide-protein conjugation; chemoselective ligation; and chemoselective purification. The difficult preparation of cysteine and methionine-containing peptides is also covered, as well as methods for overcoming aggregation during peptide chain assembly and a survey of available automated instrumentation.
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Book chapters on the topic "Chemoselective Synthesis"

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Das, Shoubhik. "Chemoselective Reduction of Amides and Imides." In New Strategies in Chemical Synthesis and Catalysis, 59–78. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA, 2012. http://dx.doi.org/10.1002/9783527645824.ch3.

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Xu, Liang, Shuai Zhang, and Pengfei Li. "Di- and Polyboron Compounds: Preparation and Chemoselective Transformations." In Boron Reagents in Synthesis, 415–44. Washington, DC: American Chemical Society, 2016. http://dx.doi.org/10.1021/bk-2016-1236.ch013.

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Hackenberger, Christian P. R., Jeffrey W. Bode, and Dirk Schwarzer. "Chemoselective Peptide Ligation: A Privileged Tool for Protein Synthesis." In Amino Acids, Peptides and Proteins in Organic Chemistry, 445–93. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA, 2011. http://dx.doi.org/10.1002/9783527631803.ch13.

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Farnung, Jakob, Haewon Song, and Jeffrey W. Bode. "Chemical Protein Synthesis by Chemoselective #x03B1;-Ketoacid–Hydroxylamine (KAHA) Ligations with 5-Oxaproline." In Methods in Molecular Biology, 151–62. New York, NY: Springer US, 2021. http://dx.doi.org/10.1007/978-1-0716-1617-8_14.

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Ni, Qiang, and Luping Yu. "Synthesis of Thioester End-Functionalized Poly(ε-caprolactone) and Its Application in Chemoselective Ligation." In ACS Symposium Series, 92–104. Washington, DC: American Chemical Society, 1998. http://dx.doi.org/10.1021/bk-1998-0709.ch006.

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Armishaw, Christopher J., Julie Dutton, Ron C. Hogg, David J. Adams, David J. Craik, and Paul F. Alewood. "Synthesis of N to C Terminal Cyclic Analogues of α-Conotoxin Iml by Chemoselective Ligation of Unprotected Linear Precursors." In Peptides: The Wave of the Future, 113–14. Dordrecht: Springer Netherlands, 2001. http://dx.doi.org/10.1007/978-94-010-0464-0_50.

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Tam, James P., and Y. A. Lu. "Chemoselective and orthogonal ligation techniques." In Fmoc Solid Phase Peptide Synthesis. Oxford University Press, 1999. http://dx.doi.org/10.1093/oso/9780199637256.003.0015.

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Peptide synthesis through segment ligation of unprotected peptides (total synthesis) and peptides to proteins (semi-synthesis) in aqueous solution is appealingly simple and efficient because protection and activation steps are not required. In addition, this method offers the potential to access a diverse group of macromolecules such as circular proteins, branched peptides, and protein conjugates which are difficult to obtain through conventional approaches using protecting group strategies. Furthermore, the use of unprotected peptide segments overcomes the problem of solubility encountered in the conventional approach to the synthesis of large peptides or proteins in solution. Conceptually, ligation can be approached two ways. In the first approach, a non-amide bond is formed between two peptide segments through a pair of mutually reactive functional groups. Typical methods of non-amide ligation include oxime, hydrazone, and thiazolidine as the coupling linkages. This type of reaction is traditionally referred to as chemoselective ligation. Non-amide ligation is characteristically flexible in joining two segments that result in amino-to-amino end, carboxyl-to-amine or end-to- side chain structures. This flexibility permits synthesis of protein mimetics and branched peptide dendrimers. In the second approach, an amide bond is formed through a two-step reaction sequence involving four functional moieties, two nucleophiles and two electrophiles in the reaction centre. This reaction is usually used for end-to-end coupling between the Cα-moiety of one peptide segment and the Nα-terminus of another peptide segment resulting in a peptide-backbone product. Similar to the non-amide chemoselective ligation, the first step in orthogonal ligation is a capture reaction by a pair of mutually reactive groups. In general, two nucleophiles, a weak-base nucleophile on the side chain and an α-amino, are located at the N-terminus as an N-terminal nucleophile 5 (NTN). The two electrophiles, usually an O-glycol-aldehyde or an S-ester 4, are located at the C-terminus of the another peptide segment. The initial non-amide capture of two segments through the side chain NTN with the O- or S-ester to form a covalent intermediate 6 enables the spontaneous proximity-driven intramolecular acyl transfer to occur. This intramolecular acyl migration achieves orthogonality in amide bond formation 7 between a specific α-amine in the presence of other free α- and ɛ-amines.
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Malins, L. R., and R. J. Payne. "21.11.7 Chemoselective Ligation Methods Based on the Concept of Native Chemical Ligation." In Science of Synthesis: Knowledge Updates 2021/3. Stuttgart: Georg Thieme Verlag KG, 2021. http://dx.doi.org/10.1055/sos-sd-121-00066.

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AbstractThis chapter extends from the earlier Science of Synthesis contribution on peptide synthesis (Section 21.11) and focuses on recent developments in chemoselective ligation chemistry based on the logic of native chemical ligation. Synthetic strategies that broaden the scope and versatility of the ligation reaction and that have been widely adopted for the preparation of homogeneous peptides and proteins are highlighted. Methods enabling the efficient preparation of peptide ligation precursors are also included in this chapter.
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Kobayashi, S., K. Manabe, H. Ishitani, and J. I. Matsuo. "Chemoselective Synthesis of Silyl Enol Ethers." In Compounds of Groups 15 (As, Sb, Bi) and Silicon Compounds, 1. Georg Thieme Verlag KG, 2002. http://dx.doi.org/10.1055/sos-sd-004-00352.

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Mascagni, Paolo. "Purification of large peptides using Chemoselective tags." In Fmoc Solid Phase Peptide Synthesis. Oxford University Press, 1999. http://dx.doi.org/10.1093/oso/9780199637256.003.0016.

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In solid phase peptide synthesis (SPPS), deletion sequences are generated at each addition of amino acid due to non-quantitative coupling reactions. Their concentration increases exponentially with the length of the peptide chain, and after many cycles not only do they represent a large proportion of the crude preparation, but they can also exhibit physicochemical characteristics similar to the target sequence. Thus, these deletion-sequence contaminants present major problems for removal, or even detection. In general, purification of synthetic peptides by conventional chromatography is based on hydrophobicity differences (using RP-HPLC) and charge differences (using ion-exchange chromatography). For short sequences, the use of one or both techniques is in general sufficient to obtain a product with high purity. However, on increasing the number of amino acid residues, the peptide secondary and progressively tertiary and quaternary structures begin to play an important role and the conformation of the largest peptides can decisively affect their retention behaviour. Furthermore, very closely related impurities such as deletion sequences lacking one or few residues can be chromatographically indistinguishable from the target sequence. Therefore, purification of large synthetic peptides is a complex and time-consuming task that requires the use of several separation techniques with the inevitable dramatic reduction in yields of the final material. Permanent termination (capping) of unreacted chains using a large excess of an acylating agent after each coupling step prevents the formation of deletion sequences and generates N-truncated peptides. However, even under these more favourable conditions, separation of the target sequence from chromatographically similar N-capped polypeptides requires extensive purification. If the target sequence could be specifically and transiently labelled so that the resulting product were selectively recognized by a specific stationary phase, then separation from impurities should be facilitated. This chapter deals with such an approach and in particular with the purification of large polypeptides, assembled by solid phase strategy, using lipophilic and biotin-based 9-fluorenylmethoxycarbonyl (Fmoc) chromatographic probes. Assuming that the formation of deletion sequences is prevented by capping unreacted chains, a reciprocal strategy can be applied that involves functional protection of all polymer-supported peptide chains that are still growing, with a specially chosen affinity reagent or chromatographic probe.
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Conference papers on the topic "Chemoselective Synthesis"

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Bernardes, Gonçalo J. L. "Chemoselective Transformations for Bioimaging and Targeted Therapeutics." In 15th Brazilian Meeting on Organic Synthesis. São Paulo: Editora Edgard Blücher, 2013. http://dx.doi.org/10.5151/chempro-15bmos-young2.

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Paim, Gisele R., Helio G. Bonacorso, Liliane M. F. Porte, Everton P. Pittaluga, Nilo Zanatta, and Marcos A. P. Martins. "Chemoselective Reactivity Study of 6-Hydrazinonicotinic Acid Hydrazide." In 14th Brazilian Meeting on Organic Synthesis. São Paulo: Editora Edgard Blücher, 2013. http://dx.doi.org/10.5151/chempro-14bmos-r0145-2.

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Macmillan, Derek, and Alison M. Daines. "SEMI-SYNTHESIS OF GLYCOSYLATED PROTEINS AND MIMICS USING CHEMOSELECTIVE LIGATIONS." In XXIst International Carbohydrate Symposium 2002. TheScientificWorld Ltd, 2002. http://dx.doi.org/10.1100/tsw.2002.438.

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da Silva, A. J. M., C. Schneider, and V. Snieckus. "Construction of Polyarylated Fluorenones via chemoselective Ru- and Pd-Catalyzed Suzuki Cross-Coupling Reactions." In 14th Brazilian Meeting on Organic Synthesis. São Paulo: Editora Edgard Blücher, 2013. http://dx.doi.org/10.5151/chempro-14bmos-r0007-1.

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Porte, Liliane M. F., Helio G. Bonacorso, Gisele R. Paim, Jussara Navarini, Nilo Zanatta, and Marcos A. P. Martins. "Chemoselective fluorination of 2-hydroxy-3,4,7,8-tetrahydro- 2H-chromen-5(6H)-ones using DAST." In 14th Brazilian Meeting on Organic Synthesis. São Paulo: Editora Edgard Blücher, 2013. http://dx.doi.org/10.5151/chempro-14bmos-r0147-1.

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Chen, Kok Hao, and Jong Hyun Choi. "DNA Oligonucleotide-Templated Nanocrystals: Synthesis and Novel Label-Free Protein Detection." In ASME 2009 International Mechanical Engineering Congress and Exposition. ASMEDC, 2009. http://dx.doi.org/10.1115/imece2009-11958.

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Semiconductor and magnetic nanoparticles hold unique optical and magnetic properties, and great promise for bio-imaging and therapeutic applications. As part of their stable synthesis, the nanocrystal surfaces are usually capped by long chain organic moieties such as trioctylphosphine oxide. This capping serves two purposes: it saturates dangling bonds at the exposed crystalline lattice, and it prevents irreversible aggregation by stabilizing the colloid through entropic repulsion. These nanocrystals can be rendered water-soluble by either ligand exchange or overcoating, which hampers their widespread use in biological imaging and biomedical therapeutics. Here, we report a novel scheme of synthesizing fluorescent PbS and magnetic Fe3O4 nanoparticles using DNA oligonucleotides. Our method of PbS synthesis includes addition of Na2S to the mixture solution of DNA sequence and Pb acetate (at a fixed molar ratio of DNA/S2−/Pb2+ of 1:2:4) in a standard TAE buffer at room temperature in the open air. In the case of Fe3O4 particle synthesis, ferric and ferrous chloride were mixed with DNA in DI water at a molar ratio of DNA/Fe2+/Fe3+ = 1:4:8 and the particles were formed via reductive precipitation, induced by increasing pH to ∼11 with addition of ammonium hydroxide. These nanocrystals are highly stable and water-soluble immediately after the synthesis, due to DNA termination. We examined the surface chemistry between oligonucleotides and nanocrystals using FTIR spectroscopy, and found that the different chemical moieties of nucleobases passivate the particle surface. Strong coordination of primary amine and carbonyl groups provides the chemical and colloidal stabilities, leading to high particle yields (Figure 1). The resulting PbS nanocrystals have a distribution of 3–6 nm in diameter, while a broader size distribution is observed with Fe3O4 nanoparticles as shown in Figure 1b and c, respectively. A similar observation was reported with the pH change-induced Fe3O4 particles of a bimodal size distribution where superparamagnetic and ferrimagnetic magnetites co-exist. In spite of the differences, FTIR measurements suggest that the chemical nature of the oligonucleotide stabilization in this case is identical to the PbS system. As a particular application, we demonstrate that aptamer-capped PbS QD can detect a target protein based on selective charge transfer, since the oligonucleotide-templated synthesis can also serve the additional purpose of providing selective binding to a molecular target. Here, we use thrombin and a thrombin-binding aptamer as a model system. These QD have diameters of 3∼6 nm and fluoresce around 1050 nm. We find that a DNA aptamer can passivate near IR fluorescent PbS nanocrystals, rendering them water-soluble and stable against aggregation, and retain the secondary conformation needed to selectively bind to its target, thrombin, as shown in Figure 2. Importantly, we find that when the aptamer-functionalized nanoparticles binds to its target (only the target), there is a highly systematic and selective quenching of the PL, even in high concentrations of interfering proteins as shown in Figure 3a and b. Thrombin is detected within one minute with a detection limit of ∼1 nM. This PL quenching is attributed to charge transfer from functional groups on the protein to the nanocrystals. A charge transfer can suppress optical transition mechanisms as we observe a significant decrease in QD absorption with target addition (Figure 3c). Here, we rule out other possibilities including Forster resonance energy transfer (FRET) and particle aggregation, because thrombin absorb only in the UV, and we did not observe any significant change in the diffusion coefficient of the particles with the target analyte, respectively. The charge transfer-induced photobleaching of QD and carbon nanotubes was observed with amine groups, Ru-based complexes, and azobenzene compounds. This selective detection of an unlabeled protein is distinct from previously reported schemes utilizing electrochemistry, absorption, and FRET. In this scheme, the target detection by a unique, direct PL transduction is observed even in the presence of high background concentrations of interfering negatively or positively charged proteins. This mechanism is the first to selectively modulate the QD PL directly, enabling new types of label free assays and detection schemes. This direct optical transduction is possible due to oligonucleotidetemplated surface passivation and molecular recognition. This chemistry may lead to more nanoparticle-based optical and magnetic probes that can be activated in a highly chemoselective manner.
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Yus, Miguel, Abdeslam Abou, and Francisco Foubelo. "Chemoselective lithiation of 6-chloro-1-halohex-1-ynes with lithium/naphthalene." In The 10th International Electronic Conference on Synthetic Organic Chemistry. Basel, Switzerland: MDPI, 2006. http://dx.doi.org/10.3390/ecsoc-10-01400.

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Ocampo, Romina, Liliana Koll, Norma D'Accorso, and Mirta Fascio. "Highly Efficient and Chemoselective Synthetic Route to de Thiazolidinones via a Microwave Assisted, Three Component Reaction." In The 18th International Electronic Conference on Synthetic Organic Chemistry. Basel, Switzerland: MDPI, 2014. http://dx.doi.org/10.3390/ecsoc-18-c002.

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Naimi-Jamal, Mohammad Reza, Sakineh Mahdian, and Leila Panahi. "Chemoselective Protection of hydroxyl and amine functional groups catalysed by MOFs." In The 20th International Electronic Conference on Synthetic Organic Chemistry. Basel, Switzerland: MDPI, 2016. http://dx.doi.org/10.3390/ecsoc-20-a032.

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Ocampo, Romina, Aldana Quiroga, Ignacio Costilla, Fernando Lorenzo, Juan Calmels, Daniela Villafain, Sandra Mandolesi, and Norma D'Accorso. "Study of the effect of solvent and different Lewis acids in one pot multicomponent microwave assisted reaction for the chemoselective generation of 1.4-thiazepan-3-ones and 4-tiazolidinones." In The 21st International Electronic Conference on Synthetic Organic Chemistry. Basel, Switzerland: MDPI, 2017. http://dx.doi.org/10.3390/ecsoc-21-04792.

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