Faraday Discussions最新文献

{"title":"Web-BO: towards increased accessibility of Bayesian optimisation (BO) for chemistry","authors":"Austin M. Mroz, Piotr N. Toka, Ehecatl Antonio del Río Chanona and Kim E. Jelfs","doi":"10.1039/D4FD00109E","DOIUrl":"10.1039/D4FD00109E","url":null,"abstract":"<p >Historically, the chemical discovery process has predominantly been a matter of trial-and-improvement, where small modifications are made to a chemical system, guided by chemical knowledge, with the aim of optimising towards a target property or combination of properties. While a trial-and-improvement approach is frequently successful, especially when assisted by the help of serendipity, the approach is incredibly time- and resource-intensive. Complicating this further, the available chemical space that could, in theory, be explored is remarkably vast. As we are faced with near infinite possibilities and limited resources, we require improved search methods to effectively move towards desired optima, <em>e.g.</em> chemical systems exhibiting a target property, or several desired properties. Bayesian optimisation (BO) has recently gained significant traction in chemistry, where within the BO framework, prior knowledge is used to inform and guide the search process to optimise towards desired chemical targets, <em>e.g.</em> optimal reaction conditions to maximise yield, or optimal catalyst exhibiting improved catalytic activity. While powerful, implementing BO algorithms in practice is largely limited to interfacing <em>via</em> various APIs – requiring advanced coding experience and bespoke scripts for each optimisation task. Further, it is challenging to seamlessly link these with electronic lab notebooks <em>via</em> a graphical user interface (GUI). Ultimately, this limits the accessibility of BO algorithms. Here, we present Web-BO, a GUI to support BO for chemical optimisation tasks. We demonstrate its performance using an open source dataset and associated emulator, and link the platform with an existing electronic lab notebook, <em>datalab</em>. By providing a GUI-based BO service, we hope to improve the accessibility of data-driven optimisation tools in chemistry; https://suprashare.rcs.ic.ac.uk/web-bo/.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"256 ","pages":" 221-234"},"PeriodicalIF":3.4,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/fd/d4fd00109e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141864347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A micropore nanoband electrode array for enhanced electrochemical generation/analysis in flow systems","authors":"Fiona Moore, Ilka Schmueser, Jonathan G. Terry and Andrew R. Mount","doi":"10.1039/D4FD00125G","DOIUrl":"10.1039/D4FD00125G","url":null,"abstract":"<p >Our previous work has established that micron-resolution photolithography can be employed to make microsquare nanoband edge electrode (MNEE) arrays. The MNEE configuration enables systematic control of the parameters (electrode number, cavity array spacing, and nanoelectrode dimensions and placement) that control geometry, conferring a consistent high-fidelity electrode response across the array (<em>e.g.</em>, high signal, high signal-to-noise, low limits of detection and fast, steady-state, reproducible and quantitative response) and allowing the tuning of individual and combined electrode interactions. Building on this, in this paper we now produce and characterise a micropore nanoband electrode (MNE) array designed for flow-through detection, where an MNEE edge electrode configuration is used to form a nanotube electrode embedded in the wall of each micropore, formed as an array of pores of controlled size and placement through an insulating membrane of sub-micrometer thickness. The success of this approach is established by the close correspondence between experiment and simulation and the enhanced and quantitative detection of redox species flowing through the micropores over the very wide range of flow rates relevant, <em>e.g.</em>, to applications in (bio)sensing and chromatography. Quantitative electrochemical reaction with low conversion, suitable for analysis, is demonstrated at high flow, whilst quantitative electrochemical reaction with high conversion, suitable for electrochemical product generation, is enabled at lower flow. The fundamental array response is analysed in terms of established flow theories, demonstrating the additive contributions of within-pore enhanced diffusional (nanoband edge) and advective (Levich-type) currents, the control of the degree of diffusional overlap between pores through pore spacing and flow rate, the control by design across length scales ranging from nanometer through micrometer to a centimetre array, and the ready determination of physicochemical parameters, enabling discussion of the potential of this breakthrough technology to address unmet needs in generation and analysis.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"257 ","pages":" 360-373"},"PeriodicalIF":3.4,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/fd/d4fd00125g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tiled unitary product states for strongly correlated Hamiltonians","authors":"Hugh G. A. Burton","doi":"10.1039/D4FD00064A","DOIUrl":"10.1039/D4FD00064A","url":null,"abstract":"<p >Approximating the electronic wave function for strongly correlated systems remains a major theoretical challenge. Emerging quantum computers can enable new types of wave-function ansatz to be considered, with the potential to overcome the exponential memory storage for strong correlation. I have recently introduced the tiled Unitary Product States (tUPS) ansatz, which successfully combines the preservation of particle-number and spin symmetry with shallow quantum circuits and local qubit connectivity [H. G. A. Burton, <em>Phys. Rev. Res.</em>, 2024, <strong>6</strong>, 023300]. In this contribution, I investigate the accuracy of this tUPS hierarchy for strongly-correlated Hamiltonians. I consider the picket-fence pairing Hamiltonian and the two-dimensional Hubbard lattice, which collectively describe a range of strong correlation mechanisms found in molecules. Numerical results demonstrate that highly accurate energies can be achieved with a compact approximation for both weak and strong correlation in the Hubbard model, and the repulsive pairing regime. These data provide valuable insights into the applicability of the tUPS hierarchy for strong electron correlation.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"254 ","pages":" 157-169"},"PeriodicalIF":3.4,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/fd/d4fd00064a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141755712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Discovery of highly anisotropic dielectric crystals with equivariant graph neural networks†","authors":"Yuchen Lou and Alex M. Ganose","doi":"10.1039/D4FD00096J","DOIUrl":"10.1039/D4FD00096J","url":null,"abstract":"<p >Anisotropy in crystals plays a pivotal role in many technological applications. For example, anisotropic electronic and thermal transport are thought to be beneficial for thermoelectric applications, while anisotropic mechanical properties are of interest for emerging metamaterials, and anisotropic dielectric materials have been suggested as a novel platform for dark matter detection. Understanding and tailoring anisotropy in crystals is therefore essential for the design of next-generation functional materials. To date, however, most data-driven approaches have focused on the prediction of scalar crystal properties, such as the spherically averaged dielectric tensor or the bulk and shear elastic moduli. Here, we adopt the latest approaches in equivariant graph neural networks to develop a model that can predict the full dielectric tensor of crystals. Our model, trained on the Materials Project dataset of <em>c.a.</em> 6700 dielectric tensors, achieves state-of-the-art accuracy in scalar dielectric prediction in addition to capturing the directional response. We showcase the performance of the model by discovering crystals with almost isotropic connectivity but highly anisotropic dielectric tensors, thereby broadening our knowledge of the structure–property relationships in dielectric crystals.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"256 ","pages":" 255-274"},"PeriodicalIF":3.4,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/fd/d4fd00096j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774441","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Accurate predictions of chemical shifts with the rSCAN and r2SCAN mGGA exchange–correlation functionals†","authors":"Jonathan R. Yates and Albert P. Bartók","doi":"10.1039/D4FD00142G","DOIUrl":"10.1039/D4FD00142G","url":null,"abstract":"<p >We benchmark the rSCAN and r<small>²</small>SCAN exchange–correlation functionals by comparing the Nuclear Magnetic Resonance (NMR) magnetic shieldings predicted by Density Functional Theory (DFT) to experimentally observed chemical shifts of halide and oxide inorganic compounds. Significant improvement in accuracy is achieved compared to the Generalised Gradient Approximation (GGA) at a marginally higher computational cost. When using rSCAN or r<small>²</small>SCAN, the correlation coefficient between computationally predicted and experimental values approaches the theoretically expected value of −1 while reducing the deviation, allowing more accurate and reliable spectrum assignments of complex compounds in experimental investigations.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":" 0","pages":" 192-202"},"PeriodicalIF":3.4,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/fd/d4fd00142g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141785205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ion current oscillation of polyelectrolyte modified micropipettes†","authors":"Tianyi Xiong, Wenjie Ma and Ping Yu","doi":"10.1039/D4FD00135D","DOIUrl":"10.1039/D4FD00135D","url":null,"abstract":"<p >Here, we report for the first time that ion current oscillation (ICO) with periodic amplitude and frequency can autonomously occur at polyimidazole brush (PvimB) modified pipettes in an asymmetric solution with a pH gradient (<em>e.g.</em> pH 6.0/pH 8.0). Experimental results demonstrated that under a strong bias voltage, the proton responsive PvimB-modified pipettes exhibited significant current switching behavior under negative bias voltages, which contributed to the periodic oscillating ion current under constant biases. Based on this dynamic, the frequency and amplitude of the ICO phenomenon were regulated by adjusting the pH gradient in the asymmetric solution. ICOs under different bias voltages were further explored to show the voltage-dependent nature of this phenomenon. This observation of ICO phenomena offers a new strategy for designing iontronic devices with dynamic conductivity changes induced by surface chemical interactions within spatial confinements.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"257 ","pages":" 44-50"},"PeriodicalIF":3.4,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774440","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spiers Memorial Lecture: Engineering biocatalysts","authors":"Donald Hilvert","doi":"10.1039/D4FD00139G","DOIUrl":"10.1039/D4FD00139G","url":null,"abstract":"<p >Enzymes are being engineered to catalyze chemical reactions for many practical applications in chemistry and biotechnology. The approaches used are surveyed in this short review, emphasizing methods for accessing reactivities not expressed by native protein scaffolds. The successful generation of completely <em>de novo</em> enzymes that rival the rates and selectivities of their natural counterparts highlights the potential role that designer enzymes may play in the coming years in research, industry, and medicine. Some challenges that need to be addressed to realize this ambitious dream are considered together with possible solutions.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"252 ","pages":" 9-28"},"PeriodicalIF":3.4,"publicationDate":"2024-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/fd/d4fd00139g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141750535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Uniform chi-squared model probabilities in NMR crystallography","authors":"Leonard J. Mueller","doi":"10.1039/D4FD00114A","DOIUrl":"10.1039/D4FD00114A","url":null,"abstract":"<p >A nearly universal component of NMR crystallography is the ranking of candidate structures based on how well their first-principles-predicted NMR parameters align with the results of solid-state NMR experiments. Here, a novel approach for assigning probabilities to candidate models is proposed that quantifies the likelihood that each model is the correct experimental structure. This method employs hierarchical Bayesian inference and leverages explicit prior probabilities derived from a uniform distribution of potential candidate structures with respect to chi-squared values. The resulting uniform chi-squared (UC) model provides a more cautious estimate of candidate probabilities compared to previous approaches, assigning decreased likelihood to the best-fit structure and increased likelihood to alternate candidates. Although developed here within the context of NMR crystallography, the UC model represents a general method for assigning likelihoods based on chi-squared goodness-of-fit assessments.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":" 0","pages":" 203-221"},"PeriodicalIF":3.4,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774442","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multimodal nanoparticle analysis enabled by a polymer electrolyte nanopore combined with nanoimpact electrochemistry†","authors":"Eugene Gyasi Agyemang, Samuel Confederat, Gayathri Mohanan, Mahnaz Azimzadeh Sani, Chalmers Chau, Dylan Charnock, Christoph Wälti, Kristina Tschulik, Martin Andrew Edwards and Paolo Actis","doi":"10.1039/D4FD00143E","DOIUrl":"10.1039/D4FD00143E","url":null,"abstract":"<p >Nanopores are emerging as a powerful tool for the analysis and characterization of nanoparticles at the single entity level. Here, we report that a PEG-based polymer electrolyte present inside the nanopore enables the enhanced detection of nanoparticles at low ionic strength. We develop a numerical model that recapitulates the electrical response of the glass nanopore system, revealing the response to be sensitive to the position of the polymer electrolyte interface. As proof of concept, we demonstrate the multimodal analysis of a nanoparticle sample by coupling the polymer electrolyte nanopore sensor with nanoimpact electrochemistry. This combination of techniques could deliver the multiparametric analysis of nanoparticle systems complementing electrochemical reactivity data provided by nanoimpact electrochemistry with information on size, shape and surface charge provided by nanopore measurements.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"257 ","pages":" 303-315"},"PeriodicalIF":3.4,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/fd/d4fd00143e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141737506","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Accurate and reliable thermochemistry by data analysis of complex thermochemical networks using Active Thermochemical Tables: the case of glycine thermochemistry","authors":"Branko Ruscic and David H. Bross","doi":"10.1039/D4FD00110A","DOIUrl":"10.1039/D4FD00110A","url":null,"abstract":"<p >Active Thermochemical Tables (ATcT) were successfully used to resolve the existing inconsistencies related to the thermochemistry of glycine, based on statistically analyzing and solving a thermochemical network that includes &gt;3350 chemical species interconnected by nearly 35 000 thermochemically-relevant determinations from experiment and high-level theory. The current ATcT results for the 298.15 K enthalpies of formation are −394.70 ± 0.55 kJ mol<small>⁻¹</small> for gas phase glycine, −528.37 ± 0.20 kJ mol<small>⁻¹</small> for solid α-glycine, −528.05 ± 0.22 kJ mol<small>⁻¹</small> for β-glycine, −528.64 ± 0.23 kJ mol<small>⁻¹</small> for γ-glycine, −514.22 ± 0.20 kJ mol<small>⁻¹</small> for aqueous undissociated glycine, and −470.09 ± 0.20 kJ mol<small>⁻¹</small> for fully dissociated aqueous glycine at infinite dilution. In addition, a new set of thermophysical properties of gas phase glycine was obtained from a fully corrected nonrigid rotor anharmonic oscillator (NRRAO) partition function, which includes all conformers. Corresponding sets of thermophysical properties of α-, β-, and γ-glycine are also presented.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"256 ","pages":" 345-372"},"PeriodicalIF":3.4,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141745587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}