Precision Chemistry最新文献

{"title":"Adaptive Reduction of Multicollinearity for Machine Learning Prediction of CO Adsorption Energies on Single Atoms","authors":"Kyoichi Sawabe,&nbsp;Takumi Tsukiyama,&nbsp;Akira Oda,&nbsp;Atsushi Satsuma","doi":"10.1021/prechem.5c00411","DOIUrl":"10.1021/prechem.5c00411","url":null,"abstract":"<p>Data-driven approaches are pivotal for optimizing single-atomcatalysts.However, when the training data size is limited, the prevalence ofmulticollinearity among physicochemical features frequently destabilizesstatistical models and obscures chemical interpretation. To addressthis challenge, we developed a wrapper-based feature selection algorithmtermed adaptive reduction of multicollinearity with retention (ARMR).This method iteratively identifies feature subsets that satisfy strictmulticollinearity constraints while minimizing cross-validated predictionerror. The features selected by ARMR yielded robust predictive performancein both linear and nonlinear models, clearly outperforming baselinesderived from univariate correlations or standard importance rankings.The efficacy of ARMR was validated through machine learning predictionsusing a density functional theory dataset of CO adsorption energieson 11 transition metals embedded as a single atom on three TiO₂ polymorphs (rutile, anatase, and brookite). Specifically,a gradient boosting regression model trained on ARMR-selected featuresachieved high predictive accuracy with a test root-mean-square errorof 0.087 eV. Furthermore, analysis of selected features identifieds-orbital charge density as an important electronic feature correlatingwith CO binding strength. By removing multicollinearity, ARMR eliminatesredundant properties intrinsically correlated with metal-specificcharacteristics like oxidation state, retaining only robust features.ARMR provides valuable insights into metal–support interactionsand offers an effective strategy for accelerating rational designof single-atom catalysts through interpretable structure–propertyrelationships.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 7","pages":"1016–1030"},"PeriodicalIF":7.7,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148621695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"BSr3 Superalkali as a Promising Catalyst for Ambient Nitrogen Reduction: A Pathway toward Efficient Ammonia Synthesis","authors":"Natalia Wiszowska,&nbsp;Natalia Rogoża,&nbsp;Celina Sikorska","doi":"10.1021/prechem.5c00284","DOIUrl":"10.1021/prechem.5c00284","url":null,"abstract":"<p>The transformation of the earth-abundant dinitrogen molecule(N₂) into ammonia (NH₃) under mild conditionsremainsa fundamental challenge in chemistry. The BSr₃ superatomdesigned in our previous work (Wiszowska N, Rogoża N, SikorskaC, <em>Phys. Chem. Chem. Phys.</em> (2025), <strong>27</strong>: 23468–23486) has been used as a catalyst for the conversionof molecular nitrogen into ammonia. Owing to its low ionization energy(4.033 eV), the BSr₃ transfers electron density to adsorbedN₂, partially populating antibonding π* orbitals,lowering the triple N≡N bond order and initiating N–Nbond elongation. Subsequent proton-coupled electron-transfer stepsfurther elongate the N–N distance in a stepwise manner, establishinga correlation between structural distortion and the progressive weakeningof the N≡N bond, ultimately facilitating bond cleavage. Thecatalytic conversion of N₂ to NH₃ catalyzedby BSr₃ proceeds via an associative distal pathway, withinitial hydrogenation at the nitrogen atom coordinated to strontiumatoms (N^Sr), followed by release of the first NH₃ molecule upon N–N bond rupture and subsequent hydrogenationof the second nitrogen (N^B, bound to a boron atom of theBSr₃ cluster). The release of the NH₃ moleculeis the potential-determining step, with a corresponding free energyuphill of 0.28 eV. The preceding exergonic hydrogenation steps helpoffset the energy cost of NH₃ desorption, ensuring overallthermodynamic favorability. These findings position the BSr₃ superalkali cluster as a promising noble-metal-free catalyst forsustainable ammonia synthesis under ambient conditions.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 7","pages":"938–949"},"PeriodicalIF":7.7,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148621705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancing Electrocatalytic CO2 Reduction of Nickel Porphyrin via Sulfur-Coordination and Through-Space Effects","authors":"Zhuo Li,&nbsp;Zhixin Ren,&nbsp;Jing Xie","doi":"10.1021/prechem.5c00429","DOIUrl":"10.1021/prechem.5c00429","url":null,"abstract":"<p>Metalloporphyrin-based complexesfeaturing stable tetrapyrrolestructures and tunable coordination environments are promising electrocatalystsfor CO₂ reduction. Modifying the first-coordination atomsthat bonded with the central metal or changing the outer-sphere functionalgroups was found to affect the catalytic performance. However, thecombined effect of these two strategies remains unexplored. Herein,using nickel tetraphenyl porphyrin (NiN₄-TPP, <strong>1</strong>) as the original catalyst, we first investigated the effect of first-coordinationmodification by replacing one N atom with a S atom, yielding NiN₃S-TPP (<strong>2</strong>). Density functional theory calculationsrevealed that, as an electrocatalyst, NiN₃S-TPP outperformsNiN₄-TPP in converting CO₂ to CO. Notably, theS-substituted catalyst <strong>2</strong> exhibits a positively shiftedreduction potential─a trend consistent with experimental observations.This is attributed to the lowered LUMO energy level after introducingthe S atom. Moreover, the S-substitution stabilizes the [*–COOH]intermediate and shifts the rate-determining step from the protonationof [<strong>1</strong>–CO₂]⁻ to form[<strong>1</strong>–COOH]⁰ to the absorption of CO₂ on [<strong>2</strong>]⁻, reducing the barrier.Charge analysis reveals that the S atom donates electrons to the metalcenter and porphyrin ligands of the catalyst. Then, upon binding toCOOH, these reserved electrons are transferred to COOH, thus facilitatingthe interaction and stabilizing the intermediate. Moreover, peripheralsubstituent modifications with the cationic –N(Me)₃⁺ functional group yield great enhancement in the catalyticperformance. It shifts the reduction potential to be more positiveand further stabilizes the [*–COOH] intermediate via through-spaceelectrostatic interaction. This work demonstrates how first- and peripheral-coordinationmodifications synergistically enhance CO₂ reduction catalysis,offering a strategy for designing efficient porphyrin-based electrocatalyststhrough core coordination environment regulation and through-spaceinteractions.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 7","pages":"1031–1041"},"PeriodicalIF":7.7,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148621682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Predicting Inverted Singlet–Triplet Gaps with XYG3-Type Doubly Hybrid Functionals","authors":"Qinjie Yang,&nbsp;Xin Xu","doi":"10.1021/prechem.5c00432","DOIUrl":"10.1021/prechem.5c00432","url":null,"abstract":"<p>Molecules exhibiting an invertedenergetic ordering of the lowestsinglet and triplet excited states, commonly referred to as havingan inverted singlet–triplet gap (Δ<em>E</em>_ST), have attracted significant interest due to their potentialin enabling next-generation organic light-emitting diode (OLED) materials.Conventional time-dependent density functional theory (TD-DFT) methods,however, often fail to predict such inversions because they cannotadequately account for double excitations. Doubly hybrid functionals(DHs), which incorporate double excitations in a perturbative way,offer a promising alternative. In this work, we demonstrate that XYG3-typedoubly hybrid functionals (xDHs) are able to correctly predict theinverted Δ<em>E</em>_ST. These functionalsprovide a cost-effective approach compared to highly accurate butprohibitively expensive coupled-cluster-based methods. Among the xDHsbenchmarked, the nonempirical XYG2 functional exhibits the best performanceand is strongly recommended for predicting the inverted Δ<em>E</em>_ST. It is anticipated that xDHs hold considerablepromise for future use in the design and discovery of advanced OLEDmaterials.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 7","pages":"1049–1061"},"PeriodicalIF":7.7,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148621676","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"PdYb/CeO2 Catalyst for Efficient Hydroaminocarbonylation of Alkenes","authors":"Rongrong Fan,&nbsp;Ce Liu,&nbsp;Xiaoshun Huang,&nbsp;Yanxin Liu,&nbsp;Shujuan Liu,&nbsp;Xinjiang Cui,&nbsp;Feng Shi","doi":"10.1021/prechem.5c00384","DOIUrl":"10.1021/prechem.5c00384","url":null,"abstract":"<p>The hydroaminocarbonylation of alkenes is one of themost promisingmethods for economically utilizing carbon monoxide (CO) to form high-valueorganic molecules. Here, we reported that a dual-atom catalyst namedPdYb/CeO₂ was prepared by impregnation method for the onestep synthesis of amides from CO, alkenes with amines. Compared withPd/CeO₂, PdYb/CeO₂ nearly doubled the amideyield. And the latter exhibited improved chemical selectivity andfunctional group tolerance toward diverse olefin and amine substrates.Characterization indicated that Pd and Yb species were embedded intothe CeO₂ support in a doped form. The incorporation ofYb optimized the electronic state of Pd through electronic regulation,which enhanced the catalytic activity. Mechanistic analysis revealedthat the Lewis acid activated trace water in this system, providinga hydrogen source for the reaction. This heterogeneous catalytic systemavoided the separation challenges of traditional homogeneous catalystsand the dependence on corrosive Brønsted acids, offering a strategyfor the development of efficient carbonylation.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 7","pages":"985–996"},"PeriodicalIF":7.7,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148621733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and Structure of PtPdCuNiCo Nanoparticles on a Carbon Support as Electrocatalysts for Low-Temperature Fuel Cells","authors":"Sergey V. Belenov,&nbsp;Anna A. Gavrilova,&nbsp;Egor R. Beskopylny,&nbsp;Mikhail I. Tolstunov,&nbsp;Egor E. Aydakov,&nbsp;Evgeny Yu. Gerasimov,&nbsp;Dmitry K. Mauer","doi":"10.1021/prechem.5c00304","DOIUrl":"10.1021/prechem.5c00304","url":null,"abstract":"<p>The aim of this work was the two-stage wet synthesisof highlyefficient PtPdCuNiCo/C catalysts for low-temperature fuel cells. Thesynthesis was based on a metal oxide-carbon support and used eitherethylene glycol or formaldehyde in the second stage. In combinationwith HRTEM, element mapping, XRD, and XPS data, these results confirmthe successful synthesis of five-component PtPdCuNiCo nanoparticleson the surface of the carbon support, achieved using both formaldehydeand ethylene glycol during the second synthesis stage. The obtainedmaterials are characterized by a high surface area of up to 57 m²/g(PGM) and a high specific oxygen reduction reaction activityof approximately 300 A/g(PGM) at 0.9 V vs RHE when ethylene glycolwas used in the second synthesis stage. The proposed synthetic strategyopens a new pathway for obtaining promising five-component nanoparticlesof various compositions for application in catalysis.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 7","pages":"964–972"},"PeriodicalIF":7.7,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148621691","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Intermolecular Aza Paternò-Büchi Reaction of N-(Fluorosulfonyl)imines and Triplet-State Aromatic Alkenes","authors":"Hiroto Kimura,&nbsp;Yasuhiro Yamauchi,&nbsp;Takuya Hashimoto","doi":"10.1021/prechem.5c00426","DOIUrl":"10.1021/prechem.5c00426","url":null,"abstract":"<p>Intermolecular aza Paternò-Büchi reactionbetween <em>N</em>-(fluorosulfonyl)imines and aromatic alkeneshas been developedthrough the photoinduced generation of a triplet state of the aromaticalkene. The <em>N</em>-fluorosulfonyl group proved crucialin enabling this transformation to furnish azetidines, as no productformation was observed in the reaction using <em>N</em>-tosylimines.Theoretical studies revealed that the highly electrophilic fluorosulfonyl-substitutednitrogen facilitates efficient nitrogen–carbon bond formationwith triplet-state styrenes. Furthermore, by taking advantage of facilederivatization of the fluorosulfonyl group, we demonstrated its reductivedeprotection to generate unprotected azetidines.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 7","pages":"1042–1048"},"PeriodicalIF":7.7,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148621743","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Atomic-Site Coordination Tuning for Precise CO2 Electroconversion","authors":"Tianshang Shan,&nbsp;Gengxian Zhou,&nbsp;Hongpan Rong,&nbsp;Jiatao Zhang","doi":"10.1021/prechem.5c00434","DOIUrl":"10.1021/prechem.5c00434","url":null,"abstract":"<p>Electrochemical carbon dioxide reduction(ECR) presentsa promisingavenue for achieving carbon neutrality by converting greenhouse gasesinto high-value fuels and chemicals. However, the advancement of ECRhinges on the precise design and synthesis of catalysts that exhibithigh activity, selectivity, and stability. Single-atom site catalysts(SASCs), benefiting from their maximum atom-utilization efficiency,uniform and tunable active sites, and unique electronic propertiesarising from strong metal–support interactions, have emergedas a powerful platform for investigating the structure–activityrelationship of ECR. By tuning coordination environments (e.g., coordinationtypes and numbers) of isolated metal atoms, the electronic structureof metal active sites can be precisely modified for governing theselective synthesis of ECR products. Herein, this review systematicallysummarizes the precise synthesis strategies, advanced characterizationtechniques, and structure–activity relationships of SASCs invarious coordination environments. Furthermore, the limitations andnecessary precautions associated with the current characterizationtechniques are also discussed. Finally, we outline the future challengesand potential research directions of SASCs in the field of ECR.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 6","pages":"741–767"},"PeriodicalIF":7.7,"publicationDate":"2026-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148333375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Precise Synthesis of Star-Shaped Redox-Responsive Segmented Polyurethanes with Controlled Arm Sequences for Drug Delivery","authors":"Yuan-Qing Song,&nbsp;Ni-Jia Song,&nbsp;Chen-Xu Tian,&nbsp;Hao Ming,&nbsp;Nan He,&nbsp;Xiao-Lei Guo,&nbsp;Wen-Kai Liu,&nbsp;Xue-Ling He,&nbsp;Ming-Ming Ding,&nbsp;Feng Luo,&nbsp;Jie-Hua Li,&nbsp;Hong Tan","doi":"10.1021/prechem.5c00383","DOIUrl":"10.1021/prechem.5c00383","url":null,"abstract":"<p>The elegant hierarchical structures of biomacromoleculeshave promotedthe pursuits of synthetic polymers with ordered monomer sequencesand diverse topological architectures, which are in the initial stage.Here, a four-arm star-shaped segmented polyurethane (PU) with a controlledblock sequence of amphiphilic seven-segment multifunctional arms containinga disulfide bond was prepared via a grafting-onto strategy, wherethe sequence-defined arms were synthesized by a diisocyanate-basedliquid-phase iterative methodology and then conjugated onto four alkyne-functionalizedpentaerythritol cores through click chemistry. The star-shaped PUcan self-assemble into micelles in aqueous solution as the lineararm. Moreover, the four-arm star-shaped architecture endows self-assembledmicelles with higher stability under various physiological conditionsand enhanced redox-responsive performance, making them promising candidatesfor drug delivery. The experiments show that drug-loaded star-shapedPU micelles possess accelerated stimuli-responsive release profiles,optimized tissue distribution, and improved anticancer efficacy <em>in vitro</em> and <em>in vivo</em> in comparison withlinear polymer micelles. This work demonstrates that advanced architecturesof precise linear polymers hold tremendous potential for the structuralregulation and performance adjustment of aggregation structures, openingthe perspectives for the structural and functional design of next-generationmaterials.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 6","pages":"831–840"},"PeriodicalIF":7.7,"publicationDate":"2026-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148333555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Imaging Multistep s-Triazine Oligomerization via Cobalt-Assisted Deamination and Selective C–C Coupling","authors":"Chunxiao Li,&nbsp;Jiaxi Liu,&nbsp;Haoyu Zhao,&nbsp;Zhiwen Zhao,&nbsp;Xueqing Yang,&nbsp;Jiyuan Zhang,&nbsp;Zhihao Liu,&nbsp;Li Wang,&nbsp;Yangfan Wu,&nbsp;Mengxi Liu,&nbsp;Lixian Sun,&nbsp;Zhaolong Chen,&nbsp;Pengru Huang,&nbsp;Bingkai Yuan,&nbsp;Gaolei Zhan","doi":"10.1021/prechem.5c00262","DOIUrl":"10.1021/prechem.5c00262","url":null,"abstract":"<p>Polymerizing monomer precursors to form monolayer carbonnitrideswith determined C/N stoichiometries and tailored properties is intimatelyrelated to an in-depth understanding of the reaction paths. However,fundamental details related to molecular-level mechanisms remain largelyunexplored because of the challenges associated with real-space visualizationof early-stage polymerization processes involving C/N/H activation,stabilization, and evolution of intermediate states. Herein, we characterizethe multistep reactions of melamine in the presence of coadsorbedcobalt on Au(111), using bond-resolved scanning probe microscopy (SPM)combined with density functional theory (DFT) calculations. Step-by-stepevolution of on-surface-generated intermediate states have been monitoredin real space; i.e., the initial step involves the condensation ofmelamine monomers to afford s-triazine tetramers, which further transforminto C–C-linked octamers and longer oligomers. Furthermore,we demonstrate how the formation of the Au–Co–N motifinfluences the coplanar and out-of-plane configurations of reactionintermediates, therefore affecting C–N cleavage and C–Ccoupling. Our findings provide mechanistic insights into the preparationof monolayer carbon nitrides with predictable structures.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 6","pages":"774–781"},"PeriodicalIF":7.7,"publicationDate":"2026-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148333455","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}