Philipp Willmer, Adam C. Hundahl, Rodolphe Marie, Henrik Jensen
{"title":"Continuous Titration Based Method for Rapid In-Solution Analysis of Non-Covalent Interactions","authors":"Philipp Willmer, Adam C. Hundahl, Rodolphe Marie, Henrik Jensen","doi":"10.1002/cmtd.202400059","DOIUrl":"https://doi.org/10.1002/cmtd.202400059","url":null,"abstract":"<p>Development of new drugs typically involves the identification and validation of molecular inhibitors or promotors of endogenous biological processes. The identification of ligands that can bind the target of interest is typically achieved by screening large libraries of small molecules, using analytical methods that only provide yes/no answers. These methods are only qualitative and often associated with unacceptable amounts of false positives and negatives. Quantitative methods are in general more accurate but time intensive. This is mainly due to repeating measurements of a dilution series in order to generate a titration curve and measure the dissociation constant (<i>K<sub>d</sub></i>). In this work, we introduce Continuous Titration Based Spectral Related Intensity Change (cSPRING), that combines Taylor dispersion analysis (TDA) with ratiometric fluorescence detection to measure a <i>K<sub>d</sub></i> in a single experiment. cSPRING is an in-solution method that reduces the sample preparation time 8-fold and requires only nanograms of protein. We show a good agreement of cSPRING with other quantitative methods for three well-known protein-small molecule interactions with binding affinities ranging from the low nanomolar to high micromolar. In addition, we show that cSPRING is able to measure binding affinities in under a minute, highlighting its efficiency and potential for screening applications.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 5","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400059","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Cover Picture: All-in-One Portable Electrochemical Strips for Drug Release, Delivery and Monitoring (Chem. Methods 2/2025)","authors":"Sima Singh, Mohga Khater, Ada Raucci, Ovidio Catanzano, Fabiana Quaglia, Stefano Cinti","doi":"10.1002/cmtd.202580201","DOIUrl":"https://doi.org/10.1002/cmtd.202580201","url":null,"abstract":"<p><b>The Front Cover</b> illustrates a novel approach to use printed electrochemical strips for triggering the controlled release of copper ions onto skin for wound healing application. Using the same portable device, copper ions are delivered and subsequently the amount is monitored, in order to personalize the treatment and evaluate its efficacy. The all-in-one system is easily generalizable towards the delivery of other species of interest depending on the therapeutic need. For more details, see the Research Article by Sima Singh, Stefano Cinti, and co-workers (DOI: 10.1002/cmtd.202400079.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 2","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202580201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Laura Maestro-Guijarro, Mercedes Sedano, Nadine Schibille, Trinitat Pradell, Marta Castillejo, Mohamed Oujja, Teresa Palomar
{"title":"Determination of Boron Content in Surface Paintings From Historical Stained-Glass Windows","authors":"Laura Maestro-Guijarro, Mercedes Sedano, Nadine Schibille, Trinitat Pradell, Marta Castillejo, Mohamed Oujja, Teresa Palomar","doi":"10.1002/cmtd.202400057","DOIUrl":"https://doi.org/10.1002/cmtd.202400057","url":null,"abstract":"<p>Stained-glass windows are often painted with grisailles and enamels. These glassy materials have a low melting temperature and are fixed to the base glass by firing processes. Lead and/or boron are commonly added to the painting material to lower their melting temperature so that they can melt without deforming the glass support. In the present study, model glass samples (with well-known boron content), replica and historical materials were analysed for their composition using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Laser Induced Breakdown Spectroscopy (LIBS). The imprint left on the analysed samples after laser irradiation was observed using optical profilometry. The feasibility of using LIBS in situ as a suitable quantitative analytical technique to detect the presence of boron in historical enamels even in very small quantities was assessed. Quantitative information on historical Spanish enamels and grisailles was obtained from calibration curves generated from the model glass samples with known boron content. The proposed procedure enables a satisfactory chemical quantitative study of historical glass materials <i>in situ</i>, regardless of their size, provenance, and chronology.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 5","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400057","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944875","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Francesco Zaccaria, Alceo Macchioni, Cristiano Zuccaccia
{"title":"Accurate Determination of Molecular Sizes of a Solute in Water From its Translational Self-Diffusion Coefficient","authors":"Francesco Zaccaria, Alceo Macchioni, Cristiano Zuccaccia","doi":"10.1002/cmtd.202400063","DOIUrl":"https://doi.org/10.1002/cmtd.202400063","url":null,"abstract":"<p>Determining accurate molecular dimensions in water, from measured translational self-diffusion coefficients (<i>D</i><sub>t</sub>), is extremely important in biochemistry, supramolecular chemistry, organometallic chemistry and beyond, but it still represents a big challenge especially for small and medium-sized molecules. Indeed, current semiempirical adaptations of the Stokes-Einstein equation, which allow accurate determination of molecular size of solutes in organic solvents, proved inadequate for aqueous systems. To overcome such a major limitation, herein, we introduce a novel approach that unlocks the quantitative interpretation of <i>D</i><sub>t</sub> in water. By analyzing ~70 diverse molecules with volumes ranging from 10<sup>1</sup> Å<sup>3</sup> to 10<sup>3</sup> Å<sup>3</sup>, and selecting the partial molar radius (<i>r</i><sub>M</sub>) as a reliable proxy for the hydrodynamic radius (<i>r</i><sub>H</sub>), we derived a semiempirical equation that enables accurate determination of hydrodynamic volume (<i>V</i><sub>H</sub>) of solutes in aqueous solutions, effectively accounting for the distinctive hydrogen-bonding properties of water. This approach fills a crucial gap, enhancing precise molecular characterization of polar and non-polar solutes in water.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 5","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400063","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944873","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yik-Hoi Yeung, Pak-Lun Lam, Dr. Waygen Thor, Hei-Yui Kai, Tsz-Lam Cheung, Dr. Yue Wu, Prof. Dr. Ga-Lai Law, Prof. Dr. Nicholas J. Long, Prof. Dr. Ka-Leung Wong
{"title":"An Efficient Solid-Phase Synthetic Approach to Prepare TACN-Functionalized Peptides","authors":"Yik-Hoi Yeung, Pak-Lun Lam, Dr. Waygen Thor, Hei-Yui Kai, Tsz-Lam Cheung, Dr. Yue Wu, Prof. Dr. Ga-Lai Law, Prof. Dr. Nicholas J. Long, Prof. Dr. Ka-Leung Wong","doi":"10.1002/cmtd.202400053","DOIUrl":"https://doi.org/10.1002/cmtd.202400053","url":null,"abstract":"<p>1,4,7-triazacyclononane (TACN) derivatives play important roles in various metal-based biomedical applications. However, the unmanageable functionalization of TACN remains a long-standing challenge to yield useful partially substituted building blocks. Herein, by utilizing nitrobenzoxadiazole (NBD) as a thiol-liable protecting group for secondary amines, a <i>bis</i>-NBD-substituted TACN was obtained as the first example in the preparation of partially substituted TACN without strict stoichiometric control and column chromatography. Upon facile deprotection of NBD using solid-phase synthesis, a series of TACN-peptide conjugates with different bioactive peptides and chelating units were derivatized from the TACN building block, demonstrating the potential widespread application of this work.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 5","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400053","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Physicochemical vs Electrochemical Technologies for Metal Recovery – Main Insights, Comparison, Complementarity and Challenges","authors":"Stefanos Mourdikoudis, Xochitl Dominguez-Benetton","doi":"10.1002/cmtd.202400046","DOIUrl":"https://doi.org/10.1002/cmtd.202400046","url":null,"abstract":"<p>The quest toward the development of new, more eco-friendly removal/recycling/recovery methods for a range of valuable elements is intense nowadays. In this Review we present and discuss in a critical way the best available physicochemical processes versus modern electrochemical approaches for metal recovery of elements which form part of spent catalysts or other sources such as wastewater, mining waste and spent batteries. These techniques include coagulation/flocculation, precipitation, electrocoagulation/electroflotation, membrane electrolysis, electrodeposition/electrowinning and gas-diffusion electrocrystallization (GDEx). Several key performance indicators (KPIs) are utilized to facilitate the critical analysis of the different recovery methods. Such indicators have to do, for example, with the efficiency, the cost, the complexity, and the environmental friendliness of the methods used. In some cases, the recovered metals can be further used for specific applications, including the fabrication of electrocatalysts for reactions of interest. When possible, the more novel electrified technologies are benchmarked versus the state-of-the art approaches. This manuscript helps to summarize all types of approaches in a comparative manner. When the targeted metal cannot be recovered by any of the technologies explored, its removal can also be considered as satisfactory in some extent, especially if the element under discussion poses a risk of toxicity for the environment or for human health. Recovery technologies are sometimes combined for an optimum effect, exploiting the advantages of each approach and mitigating their drawbacks. Our review provides also some examples for ‘removal-only’ possibilities of the studied methods, though its primary focus is the metal recovery aiming for metal reuse in the best possible scenarios.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 3","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143581481","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dr. Katarzyna Dziubińska-Kühn, Dr. Guzel Musabirova, Sophie Effertz, Prof. Jörg Matysik, Prof. Renaud Blaise Jolivet
{"title":"Sodium-Potassium Competition as a Tool for Chemoselective Cucurbit[n]uril-Xenon Host–Guest Complexation in Imaging Applications","authors":"Dr. Katarzyna Dziubińska-Kühn, Dr. Guzel Musabirova, Sophie Effertz, Prof. Jörg Matysik, Prof. Renaud Blaise Jolivet","doi":"10.1002/cmtd.202400033","DOIUrl":"https://doi.org/10.1002/cmtd.202400033","url":null,"abstract":"<p>Cucurbit[<i>n</i>]urils (CB[<i>n</i>]) are a family of macromolecules, capable of encapsulating neutral or charged species. Due to their low toxicity, good solubility, and transport properties resulting from the structure forming the cage, they have gained popularity in imaging-oriented studies. <i>In vitro</i> studies have shown that one of the guests compatible with the CB[<i>n</i>] hosts are Xe atoms, leading to high-resolution <sup>129</sup>Xe magnetic resonance signals in pulmonary medical imaging. This prompts the question of whether similar results could be achieved <i>in vivo</i> in other tissues and body fluids. Here, we demonstrate how the varying efficacy of Xe encapsulation by a CB[6] cage is governed by the Na<sup>+</sup> : K<sup>+</sup> molecular ratio in simulated body fluids. Moving from a high concentration of Na<sup>+</sup> to an excess of K<sup>+</sup> in the solution significantly increases Xe encapsulation by the macromolecules. This finding indicates chemoselectivity of cucurbit[6]uril host-guest interactions. Since Na<sup>+</sup> and K<sup>+</sup> are the most abundant ions in human body fluids, our results provide a theoretical foundation for future liquid-state <i>in vivo</i> Xe imaging in medical applications.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 3","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dr. Xian Suo, Dr. Juntian Fan, Dr. Liqi Qiu, Dr. Meijia Li, Dr. Bishnu P. Thapaliya, Dr. Chi-Linh Do-Thanh, Dr. Ziyang Lu, Dr. Ilja Popovs, Dr. Shannon M. Mahurin, Dr. Zhenzhen Yang, Dr. Sheng Dai
{"title":"Construction of Porous Tetrazine-Functionalized Networks: From Two- to Three-Dimensional Counterparts with Tunable Properties","authors":"Dr. Xian Suo, Dr. Juntian Fan, Dr. Liqi Qiu, Dr. Meijia Li, Dr. Bishnu P. Thapaliya, Dr. Chi-Linh Do-Thanh, Dr. Ziyang Lu, Dr. Ilja Popovs, Dr. Shannon M. Mahurin, Dr. Zhenzhen Yang, Dr. Sheng Dai","doi":"10.1002/cmtd.202400042","DOIUrl":"https://doi.org/10.1002/cmtd.202400042","url":null,"abstract":"<p>Porous organic networks (PONs) linked by aza-fused rings are extensively studied and demonstrated wide applications in diverse fields. It is a long-term attractive and challenging subject to explore novel PONs functionalized by unexplored aza-fused moieties. Herein, a series of tetrazine-linked PONs (Tz-PONs) were constructed from two-dimensional to three-dimensional counterparts with tunable properties. The reaction pathway composed of the amidrazone intermediates formation using multiply substituted aromatic nitrile monomers was catalyzed by zinc salts with Lewis super acidity in the presence of hydrazine, and the subsequent tetrazine formation was assisted by sodium nitrite solution. Textural property of the as-constructed scaffolds could be tuned by the acidity of the zinc salts, as well as the organic solvents. As an initial assessment, those Tz-PONs displayed different photo absorption behavior, which may influence the corresponding photocatalysis.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 4","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400042","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143793817","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Daniël W. Groefsema, Dr. Freddy T. Rabouw, Michiel Boele, Dr. Alexander P. van Bavel, Prof. Dr. Bert M. Weckhuysen
{"title":"Operando Luminescence Thermometry of a Solid Catalyst in a Reactor during a High-Temperature Chemical Process","authors":"Daniël W. Groefsema, Dr. Freddy T. Rabouw, Michiel Boele, Dr. Alexander P. van Bavel, Prof. Dr. Bert M. Weckhuysen","doi":"10.1002/cmtd.202400044","DOIUrl":"https://doi.org/10.1002/cmtd.202400044","url":null,"abstract":"<p>In most catalytic processes, thermal energy is released or consumed locally in a reactor due to the exothermicity or endothermicity of the chemical reactions. This causes the actual operating temperature of the catalyst material to deviate from the reactor temperature, which can lead to underperformance, reduced catalyst stability, or even thermal runaway. Conventional methods to measure the catalyst temperature, with a thermocouple in the reactor oven or in the catalyst bed, suffer from complications because of separation between the sensor and catalyst material, chemical activity of the thermocouple/coating material, added complexity of the setup, and disruption of the reactant flow and heat flow through the catalyst bed. Here, we show the possibilities and challenges of luminescence thermometry as an analytical technique for remote temperature monitoring of the local catalyst temperature in a strongly exothermic high-temperature reaction environment. We observe that the luminescence lifetime depends not only temperature, but also on oxygen concentration, which can introduce a significant systematic error of up to 40 °C in the recorded temperature. In the case of ratiometric luminescence thermometry, this error is strongly reduced to ~5 °C. We use the ratiometric technique to confirm its applicability in the exothermic oxidative coupling of methane (OCM) process at high reaction temperatures, showing an exothermic increase in the local catalyst temperature of up to 100 °C, relative to the constant reactor temperature under inert conditions.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 3","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400044","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582096","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lorenzo Sarasino, Teruhisa Ohno, Maria Cristina Paganini
{"title":"Optimised Synthesis of Rhombic dodecahedral Cu2O Nanoparticles: A Pathway to Superior Morphological Control","authors":"Lorenzo Sarasino, Teruhisa Ohno, Maria Cristina Paganini","doi":"10.1002/cmtd.202400050","DOIUrl":"https://doi.org/10.1002/cmtd.202400050","url":null,"abstract":"<p>Cuprous oxide (Cu<sub>2</sub>O) nanoparticles hold significant promise for photocatalytic applications due to their narrow bandgap and high surface reactivity. This study focuses on the synthesis of rhombic dodecahedral Cu<sub>2</sub>O (RD-Cu<sub>2</sub>O) nanoparticles, totally enclosed by {110} facets, known to exhibit superior photocatalytic performance over the other low-index crystallographic facets. The precise control over the synthesis conditions can significantly enhance the exposure of this highly active face and therefore improve the catalytic performance of Cu<sub>2</sub>O nanoparticles, making them superior for applications in pollutant degradation, organic reactions, and artificial photosynthesis. We systematically optimised the synthesis parameters, including reactants concentration, pH and other reaction conditions, to achieve a significant scale up of well-defined RD- Cu<sub>2</sub>O nanoparticles production, strictly necessary for the use of this photocatalyst on a larger scale. The optimised and scaled up synthesis require 2.0 mmol of CuCl<sub>2</sub>, 6.0 mmol of Sodium dodecyl sulphate (SDS), 9.6 mmol of NH<sub>2</sub>OH ⋅ HCl and 7.0 mmol of NaOH added in this order to 400 ml of water at 25 °C. The optimised nanoparticles demonstrated a narrow size distribution and a high degree of crystallographic control. Characterisation techniques such as FESEM, XRD, EPR, UV-Vis spectroscopy, and XPS confirmed the improved morphological and structural properties of the synthesised RD-Cu<sub>2</sub>O nanoparticles.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 4","pages":""},"PeriodicalIF":6.1,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400050","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143793808","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}