ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.254
Robin Nussbaum, Eric Bakker
{"title":"Overcoming Limitations for Ultrasensitive <i>In Situ </i>pH Measurements in Marine Waters while Maintaining Traceability to Primary Standards.","authors":"Robin Nussbaum, Eric Bakker","doi":"10.2533/chimia.2026.254","DOIUrl":"https://doi.org/10.2533/chimia.2026.254","url":null,"abstract":"<p><p>Historically, pH was defined by Sørensen as the negative logarithm of the hydrogen ion activity. Today, primary pH standards are prepared and characterized by electrochemical measurements performed in metrological institutes. As such standards must have an ionic strength below 0.1 mol·kg-1, uncertainties arise when studying seawater pH. For this and other practical reasons, oceanographers prefer to use the total hydrogen ion concentration scale and measure pH optically with pH indicator dyes rather than using electrochemical methods. Yet only the latter directly measure ion activity and are directly traceable to primary standards. To address this challenge our group focuses on improving the precision of electrochemical measurements using pH glass electrodes to about 0.001 pH units. This work highlights recent advances in enhancing electrode sensitivity using a novel coulometric method, reducing pH measurement uncertainty while maintaining traceability, and developing a submersible pH probe for in situ measurements in marine waters.</p>","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"254-257"},"PeriodicalIF":1.6,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863787","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}
ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.238
Vladislav Slama, Ursula Rothlisberger
{"title":"Electronic and Optical Properties of Paracyclophanes.","authors":"Vladislav Slama, Ursula Rothlisberger","doi":"10.2533/chimia.2026.238","DOIUrl":"https://doi.org/10.2533/chimia.2026.238","url":null,"abstract":"<p><p>Paracyclophanes (PCPs) offer tunable electronic and optical properties through through-space interactions, yet their excited states, especially charge-transfer (CT) states, are difficult to model accurately. We present a computational framework combining CC2 and range-separated TD-DFT with solvation to achieve balanced accuracy for locally excited and CT states. A proposed fragment-based excitonic description reduces computational cost while preserving quantitative reliability. Applied to pyrene-naphthalene diimide PCPs, the approach reveals how linker-controlled geometry governs CT formation, exciton coupling, and optical response, enabling quantitative simulation of spectra and excited-state properties.</p>","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"238-241"},"PeriodicalIF":1.6,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863796","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}
ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.201
Eva Freisinger, Michal Juríček, Hans Peter Lüthi
{"title":"Editorial.","authors":"Eva Freisinger, Michal Juríček, Hans Peter Lüthi","doi":"10.2533/chimia.2026.201","DOIUrl":"https://doi.org/10.2533/chimia.2026.201","url":null,"abstract":"","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"201"},"PeriodicalIF":1.6,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863725","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}
ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.245
Iris Nogueroles-Langa, Yuzhen Ge, Cecilia Salah, Gonzalo Guillén-Gosálbez, Antonio J Martín, Javier Pérez-Ramírez
{"title":"Bridging Catalyst Design and Process-Level Analysis for Sustainable Polyethylene Recycling <i>via</i> Hydrogenolysis.","authors":"Iris Nogueroles-Langa, Yuzhen Ge, Cecilia Salah, Gonzalo Guillén-Gosálbez, Antonio J Martín, Javier Pérez-Ramírez","doi":"10.2533/chimia.2026.245","DOIUrl":"https://doi.org/10.2533/chimia.2026.245","url":null,"abstract":"<p><p>Aligning catalyst development with process-level sustainability metrics is crucial for advancing the chemical recycling of plastics. We bridge both elements to study hydrogenolysis of high-density polyethylene and report Ru-Ni alloy nanoparticles supported on titania that yield up to 55% liquid alkane products (C6-C45) under optimized conditions. Operando spectroscopy reveals Ru-Ni alloy sites formed in situ, and temperature-programmed experiments suggest an enhanced preference for internal instead of terminal scission over the bimetallic catalysts. By integrating these experimental insights with life cycle and techno-economic analyses, we identify a minimum average-chain-length threshold of C11 for product distributions as a catalyst design guideline to reconcile environmental and economic objectives, illustrating the value of bridging catalyst design and process-level analyses.</p>","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"245-249"},"PeriodicalIF":1.6,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863773","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}
ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.222
Mathilde Vincent, Jonathan Hall
{"title":"Properties of Stereopure Phosphorothioate Groups in RNA-PROTACs.","authors":"Mathilde Vincent, Jonathan Hall","doi":"10.2533/chimia.2026.222","DOIUrl":"10.2533/chimia.2026.222","url":null,"abstract":"<p><p>Proteolysis-targeting chimeras (PROTACs) are an emerging therapeutic modality that enable the degradation of target proteins via the endogenous ubiquitin-proteasome pathway. We are applying this concept to the degradation of RNA-binding proteins (RBPs), which often lack drug-like binding pockets for small molecules. When targeting RBPs with RNA-PROTACs, the targeting ligand consists of short, chemically modified oligoribonucleotides that are iso-sequential with endogenous RNA consensus sequences. Specifically, we are investigating the phosphorothioate (PS) backbone, in which a sulfur atom replaces a non-bridging oxygen in the RNA phosphodiester linkage. PS modifications enhance stability against nucleases, but introduce chirality at the phosphorus atom, when introduced using conventional synthesis reagents, generating diastereoisomers whose stereochemistry can significantly enhance RNA-protein interactions.</p>","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"222-225"},"PeriodicalIF":1.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863900","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}
ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.230
Francisca Figueiredo, Martin Albrecht
{"title":"Histidine-derived N-heterocyclic Carbenes in Metal Peptide Conjugates for Abiotic Catalysis.","authors":"Francisca Figueiredo, Martin Albrecht","doi":"10.2533/chimia.2026.230","DOIUrl":"10.2533/chimia.2026.230","url":null,"abstract":"<p><p>Histidinium (Hum), a N,N'-dimethylated variant of histidine, serves as a non-canonical amino acid that provides an N-heterocyclic carbene (NHC) binding site for metal coordination. This amino acid therefore allows for combining peptides and proteins with NHC metal complexes, one of the most prolific scaffolds of homogeneous catalysis of the recent past. Here, we review our efforts in combining these two areas by constructing chemically synthesized tetrapeptide NHC rhodium conjugates for hydrosilylation and larger peptide metal systems obtained from solid phase peptide synthesis for abiotic iridium-catalysed hydrogenation of ketones.</p>","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"230-233"},"PeriodicalIF":1.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863776","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}
ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.258
Nora M Bernet, Thomas B Hofstetter
{"title":"Perspectives for the Study of <sup>18</sup>O Isotope Effects of Enzymatic Phosphoryl Transfer Reactions by ESI-Orbitrap MS.","authors":"Nora M Bernet, Thomas B Hofstetter","doi":"10.2533/chimia.2026.258","DOIUrl":"10.2533/chimia.2026.258","url":null,"abstract":"<p><p>Isotope effects play an important role in investigating enzymatic phosphoryl transfer reactions, which are central in biochemical pathways and environmental metabolism. However, resolving different isotope effects for mechanistic insights into phosphoryl transfer reactions with stable isotope analysis at natural abundance remains challenging. Current analytical methods primarily allow 18O/16O ratio measurements of phosphate and preclude efficient quantification at different reaction extents. Moreover, various oxygen bond changes make mechanistic interpretation of observable O isotope fractionation particularly difficult. Here, we review recent advances in electrospray ionization Orbitrap mass spectrometry for O isotope analysis in phosphate and organophosphates, and the state-of-knowledge on position-specific isotope effects in phosphoryl transfer reactions. Using a kinetic toy model, we illustrate that further development of 18O/16O ratio analysis with Orbitrap MS should include quantification of O isotope fractionation in organophosphate substrates and alcohol leaving groups to evaluate nucleophilic attack and leaving group departure isotope effects.</p>","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"258-261"},"PeriodicalIF":1.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863809","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}
ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.208
Victoria Lohmann, Athina Anastasaki
{"title":"Beyond the Chemical Recycling of Polymethacrylates: Depolymerization of Polymethacrylamides.","authors":"Victoria Lohmann, Athina Anastasaki","doi":"10.2533/chimia.2026.208","DOIUrl":"https://doi.org/10.2533/chimia.2026.208","url":null,"abstract":"<p><p>Over the past years, depolymerization has become a focal point of polymer research aiming at improving chemical recycling of various polymer classes. Herein, we present the purely thermal depolymerization of polymethacrylamides made by reversible addition-fragmentation chain-transfer polymerization at temperatures as low as 90 °C. By addition of a free radical initiator, a rapid depolymerization to high conversions was achieved, overcoming end-group degradation that previously led to lower yields. The developed methodology was subsequently applied to a crosslinked hydrogel, which could be effectively reverted back to its monomer, thus highlighting the versatility of our strategy.</p>","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"208-211"},"PeriodicalIF":1.6,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863798","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}
ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.242
Stefan P Schmid, Kjell Jorner
{"title":"General Reaction Conditions <i>via</i> Data-driven Optimisation.","authors":"Stefan P Schmid, Kjell Jorner","doi":"10.2533/chimia.2026.242","DOIUrl":"https://doi.org/10.2533/chimia.2026.242","url":null,"abstract":"<p><p>General reaction conditions are a long-standing goal in chemical synthesis, as such conditions facilitate library synthesis and a broad substrate scope. However, despite their importance, the generality of reaction conditions is mostly an afterthought when reaction conditions are optimised. Considering multiple substrates during reaction condition optimisation alleviates this problem and enables the identification of conditions that work well for multiple substrates. Inspired by data-driven optimisation techniques for one model substrate, machine learning based strategies have also been proposed to optimise reactions towards general reaction conditions. In this work, we describe recent algorithmic advances in this domain, including our state-of-the-art algorithm. This algorithm is also available as an easy-to-use website to allow experimental chemists to use it without code.</p>","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"242-244"},"PeriodicalIF":1.6,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863743","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}
ChimiaPub Date : 2026-04-29DOI: 10.2533/chimia.2026.204
Henriette Lämmermann
{"title":"A HaloTag-Based Reporter System Enabling Two-Color Timestamped Gene Expression Monitoring.","authors":"Henriette Lämmermann","doi":"10.2533/chimia.2026.204","DOIUrl":"10.2533/chimia.2026.204","url":null,"abstract":"<p><p>Precise gene expression regulation is essential for cellular homeostasis, particularly in stress response pathways. In the endoplasmic reticulum, the unfolded protein response (UPRER) plays an important role in maintaining the protein folding capacity. We developed a chemigenetic gene expression reporter system for BiP/GRP78, a key regulator of the UPRER, based on co-expression of the self-labeling HaloTag protein. We designed a two-color sequential labelling strategy for improved readout sensitivity and applied our system in a high-content screening, identifying a promising novel activator of BiP/GRP78 expression.</p>","PeriodicalId":9957,"journal":{"name":"Chimia","volume":"80 4","pages":"204-207"},"PeriodicalIF":1.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147863788","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}