Simon H. Zientek, Stephen Thompson, Franklin I. Aigbirhio, Selena Milicevic Sephton
{"title":"Potential of miRNA as Imaging Targets for PET","authors":"Simon H. Zientek, Stephen Thompson, Franklin I. Aigbirhio, Selena Milicevic Sephton","doi":"10.1002/hlca.202400014","DOIUrl":"10.1002/hlca.202400014","url":null,"abstract":"<p>Positron Emission Tomography (PET) is an important part of the medical imaging field which is continually exploring novel biological targets as exemplified by PET imaging of neuroinflammation. Due to limitations stemming from either sub-optimal biological targets or a lack of available selective radiotracers, alternative biomarkers and PET imaging agent candidates are considered. One such possible target is microRNA (miRNA) and herein, we discuss the potential of miRNA for PET imaging. With the aim of addressing key strategies for imaging miRNA with PET, we identify three distinct approaches as follows: small molecules directly targeting miRNA, small molecules indirectly targeting Argonaute 2 (AGO2)-protein complexes, and direct chemical modification of antisense oligonucleotides. The radiosynthetic approaches are based on the methods of direct radiolabelling of respective antisense oligonucleotides and several examples are described herein, showcasing the potential of miRNA in PET imaging. Whilst these approaches offer different radiolabelling strategies, application of these radiolabelled molecules towards PET imaging of miRNA are scarce with only one, limited example applied to bone remodeling reported in the literature.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 8","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400014","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141577339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Platinum-Catalyzed Isomerization of Cyclopropenes to 1,3-Dienes","authors":"Vladyslav Smyrnov, Antonin Homassel, Leander Choudhury, Jerome Waser","doi":"10.1002/hlca.202400105","DOIUrl":"10.1002/hlca.202400105","url":null,"abstract":"<p>Herein we report a platinum-catalyzed isomerization of cyclopropenes to 1,3-dienes. Diverse dienylated alcohols were obtained in 42–98 % yield. The synthetic potential of the products was demonstrated by their use in Diels–Alder cycloadditions with various dienophiles. Isotope labelling studies provide strong support for a mechanism involving pericyclic [1,5]-σ-bond rearrangement of a vinyl platinum carbene intermediate.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 9","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400105","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141577340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Fluorinated-Thiolate Osmium(III) and Osmium(IV) Complexes Bearing N,N-diethyldithiocarbamate and Substituted Phosphines. Synthesis, Crystal Structures and DFT-Studies","authors":"Bertín Anzaldo, Andrés Álvarez-García, Sylvain Bernès, Armando Ramírez-Monroy, Maribel Arroyo-Carranza","doi":"10.1002/hlca.202400066","DOIUrl":"10.1002/hlca.202400066","url":null,"abstract":"<p>The paramagnetic osmium(III) [Os(SR<sub>F</sub>)(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub>(P(C<sub>6</sub>H<sub>4</sub>X-4)<sub>3</sub>)] (R<sub>F</sub>=C<sub>6</sub>F<sub>4</sub>H−4, C<sub>6</sub>F<sub>5</sub>; X=OCH<sub>3</sub>, CH<sub>3</sub>, F) (<b>1–6</b>) along with diamagnetic osmium(IV) [Os(SR<sub>F</sub>)<sub>2</sub>(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub>] (<b>7–8</b>) complexes were obtained from [Os(SR<sub>F</sub>)<sub>4</sub>(P(C<sub>6</sub>H<sub>4</sub>-X)<sub>3</sub>)] and NaS<sub>2</sub>CNEt<sub>2</sub>, which were characterized by FAB mass spectrometry, IR spectroscopy, single crystal X-ray diffraction, and for the diamagnetic <b>7</b> also by NMR. TD-DFT calculations were performed to simulate the absorption spectra of complexes. In the visible region, LMCT transitions contribute to the calculated intensities, which are somewhat related to the color of the synthesized compounds. In the ultraviolet region, the phosphine ligand plays a significant role in MLCT transitions, which results in Os(III) complexes exhibiting an intense band in that region. Topological analysis and electron localization function (ELF) maps calculated for <b>6</b> and <b>7</b> confirm the strong ionic character of the Os−S coordination bonds formed by the thiophenolate and dithiocarbamate ligands. This comprehensive study provides information on the structure, bonding, and electronic properties of osmium complexes, for potential applications in catalysis, materials science, and biological systems.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 9","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141577341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maygan M. McGuire, Andrew C. Bach, Maren Pink, Thomas N. Snaddon
{"title":"En Route to Enantioenriched Quaternary Stereocenters via Lewis Base/Palladium Cooperative Catalysis","authors":"Maygan M. McGuire, Andrew C. Bach, Maren Pink, Thomas N. Snaddon","doi":"10.1002/hlca.202400089","DOIUrl":"10.1002/hlca.202400089","url":null,"abstract":"<p>The prevalence of quaternary stereogenic centers in bioactive molecules coupled with innate challenges associated with their enantioselective preparation continues to provide powerful impetus for the development of catalytic asymmetric methods capable of their construction. Herein, we describe a cooperative isothiourea Lewis base-palladium catalyst system that enables the enantioselective alkylation of α-substituted-α-cyano esters with allyl methanesulfonate. While the levels of enantioselection are modest, this study represents the first time we have successfully constructed quaternary-substituted stereogenic centers using this Lewis base-palladium cooperative catalysis scheme. Further, this strategy constitutes a departure from ligand-based enantiocontrol and suggests that, when using acidic pro-nucleophiles, the development of protocols where Lewis base catalysis can outcompete direct deprotonation might be within reach.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 9","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400089","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141509276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Cost-Effective and Scalable Enzyme-Mediated Preparation of Short-Chain Primary Amines","authors":"Stefania Gianolio, Beatrice Rassati, Francesca Paradisi","doi":"10.1002/hlca.202400078","DOIUrl":"10.1002/hlca.202400078","url":null,"abstract":"<p>Amines, crucial components in various industries, play a pivotal role in the synthesis of pharmaceuticals, agrochemicals, and specialty chemicals. Recognizing the environmental impact of conventional methods for their preparation, our study centers on the utilization of abundantly available natural molecules, specifically amino acids, as precursors for short chain amine synthesis. This paper focuses on the biocatalyst, L-valine decarboxylase from <i>Streptomyces viridifaciens</i> (VlmD), delving into the substrate scope, catalytic activity, and cost-effective scalability of an enzymatic process for amine synthesis. Additionally, we investigate the feasibility of immobilizing VlmD, aiming to pave the way for its effective use in industrial applications. Our study exploits the SpinChem system and provides a comprehensive understanding of the potential and limitations of this biocatalyst. Notably, our yields for key amines (8.42 g ⋅ d<sup>−1</sup> for isobutylamine, 5.23 g ⋅ d<sup>−1</sup> for isoamylamine, 5.16 g ⋅ d<sup>−1</sup> for (<i>S</i>)-2-methylbutylamine, 3.78 g ⋅ d<sup>−1</sup> for 3-(methylthio)propylamine, and 10.52 g ⋅ d<sup>−1</sup> for (<i>R</i>)-1-amino-2-propanol) demonstrate the process efficiency and potential for industrial scalability.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 8","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400078","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141509277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qiongmei Zhang, Kun Peng, Werner Bonrath, Zili Zhang, Zhibin Zhu, Yuehan Xing, Xiaoyan Wang, Bo Gao, Jonathan A. Medlock
{"title":"A Novel, Industrially-feasible Synthetic Route to (+)-Biotin from L-Cysteine","authors":"Qiongmei Zhang, Kun Peng, Werner Bonrath, Zili Zhang, Zhibin Zhu, Yuehan Xing, Xiaoyan Wang, Bo Gao, Jonathan A. Medlock","doi":"10.1002/hlca.202400090","DOIUrl":"10.1002/hlca.202400090","url":null,"abstract":"<p>A novel, industrially viable synthetic route to (+)-biotin has been developed starting from <i>L</i>-cysteine <i>via</i> the known key thiolactone intermediate. The route takes advantage of the in-built stereochemistry of the cysteine starting material and the best features of the two current industrialized processes. The key transformations are the conversion of <i>L</i>-cysteine into a hydantoin avoiding racemization followed by catalytic cyanation and thiolactonization to form the required thiolactone intermediate. This known intermediate can be readily further transformed into (+)-biotin.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 9","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141509278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pedro Castro-Fernández, Alexander I. Serykh, Melis Yarar, Deni Mance, Paula M. Abdala, Christophe Copéret, Alexey Fedorov, Christoph R. Müller
{"title":"The Relation between Nature and Stability of H2-Dissociating Sites and Propene Selectivity in Silica-Supported (Ga,Al)2O3 Mixed Oxide Propane Dehydrogenation Catalysts","authors":"Pedro Castro-Fernández, Alexander I. Serykh, Melis Yarar, Deni Mance, Paula M. Abdala, Christophe Copéret, Alexey Fedorov, Christoph R. Müller","doi":"10.1002/hlca.202400076","DOIUrl":"https://doi.org/10.1002/hlca.202400076","url":null,"abstract":"<p>Colloidal solutions of gallia-alumina (Ga,Al)<sub>2</sub>O<sub>3(<i>x</i>:<i>y</i>)</sub> solid-solution nanoparticles with nominal atomic Ga : Al (<i>x:y</i>) ratios of 1 : 6, 1 : 3, 3 : 1, and 1:0 were used to prepare silica-supported catalysts for propane dehydrogenation (PDH). A comparison of the unsupported and silica-supported catalysts reveals that the dispersion on silica increases the Ga-normalized PDH rates for all catalysts, albeit with a notably lower propene selectivity for (Ga,Al)<sub>2</sub>O<sub>3(1:6)</sub>/SiO<sub>2</sub>. Fourier transform infrared (FTIR) spectroscopy allows contrasting the H<sub>2</sub> dissociation sites in the calcined and H<sub>2</sub>-treated (Ga,Al)<sub>2</sub>O<sub>3(<i>x</i>:<i>y</i>)</sub>/SiO<sub>2</sub>, indicating a transformation of Ga<sup>3+</sup> surface sites with Al (mainly) and Ga atoms in the second coordination sphere (Ga<sub>(Al/Ga)</sub> sites) in the calcined (Ga,Al)<sub>2</sub>O<sub>3(1:6)</sub>/SiO<sub>2</sub> to predominantly Ga<sub>(Ga/Si)</sub> surface sites in the H<sub>2</sub>-treated material. The resulting sites are similarly unselective as in amorphous gallia on silica. H<sub>2</sub> produced during the PDH reaction can cause a similar transformation as H<sub>2</sub> pretreatment in (Ga,Al)<sub>2</sub>O<sub>3(1:6)</sub>/SiO<sub>2</sub>, rapidly resulting in a notably lowered selectivity. The stable and selective Ga<sub>(Al/Ga)</sub> surface sites in (Ga,Al)<sub>2</sub>O<sub>3(1:3)</sub>/SiO<sub>2</sub> yield a Ga−H band at ca. 1990 cm<sup>−1</sup> under H<sub>2</sub> dissociation conditions while the less selective surface sites, observed for the other Ga : Al ratios, give Ga−H bands at ca. 2040 and 2060 cm<sup>−1</sup>.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 8","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400076","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142002523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yeerlan Adeli, Thulasinath Raman Venkatesan, Frank A. Nüesch, Dorina M. Opris
{"title":"Elastomers Based on Polynorbornene with Polar Polysiloxane Brushes for Soft Transducer Applications","authors":"Yeerlan Adeli, Thulasinath Raman Venkatesan, Frank A. Nüesch, Dorina M. Opris","doi":"10.1002/hlca.202400032","DOIUrl":"10.1002/hlca.202400032","url":null,"abstract":"<p>Elastomers based on cross-linked bottlebrush polymers combine an extreme softness at low strains with a strain-stiffening effect, which makes them attractive as active components in dielectric elastomer actuators (DEA). Their main disadvantage concerns the small relative permittivity, which is about 3.5, requiring relatively high driving voltage in actuators. We synthesized a bottlebrush polymer elastomer with polar brushes, which exhibit an enhanced dielectric permittivity of 4.4. Anionic ring-opening polymerization of a polar cyclosiloxane gave telechelic polar brushes, while ring-opening polymerization of a norbornene macromonomer gave a bottlebrush polymer which was cross-linked to elastomers by a thiol-ene reaction. Elastomers with a small elastic modulus below 100 kPa, strain at break exceeding 100 %, attractive elasticity, and small mechanical loss factors (<i>tanδ</i>) were achieved. Temperature-dependent impedance measurements revealed a transition temperature of −95 °C and an interfacial polarization. The multigram scale synthesis demonstrates the potential for scaling up, which opens the door to broader applications of these materials beyond actuators, such as capacitive sensors, batteries, and electroluminescent devices. Notably, these devices operate at extremely low voltages where the dielectric breakdown does not limit their functionality, but still, the softness and the increased dielectric permittivity are a plus.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 8","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400032","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141363525","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Nickel(II)-Catalyzed Hydrocarbamoylation of Alkynes with Formamides towards Unsaturated Amides","authors":"Tiangui Li, Shiyang Wang, Zongxiang Xia, Jinbo Zhao, Dongyue Zhang, Yuanqi Wu, Yu Liu","doi":"10.1002/hlca.202400020","DOIUrl":"10.1002/hlca.202400020","url":null,"abstract":"<p>Ni-catalyzed activation of C(sp<sup>2</sup>)−H bond remains an elusive challenge. Herein, we realized a Ni-catalyzed selective activation of C(sp<sup>2</sup>)−H bond of formamides, which underwent addition reaction with internal alkynes to provide α,β-unsaturated amide compounds in high yields. The protocol was featured by the cheap and nontoxic catalyst system. Preliminary mechanistic studies shed light on the reaction pathways.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 8","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141269387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}