Precision ChemistryPub Date : 2026-08-24Epub Date: 2026-07-10DOI: 10.1021/prechem.6c00016
Patrick F. Strobel, Lucas Laventure, Priyanshu Chandra, Mark Del Campo, Pierre LeMagueres, Lauren Aheran, Jing Jin, Nathan J. Oldenhuis, David Punihaole, Aylin Aykanat
{"title":"Solvent-Directed Phase Control in Disulfide-Linked Metal–Organic Frameworks Revealed by Microcrystal Electron Diffraction","authors":"Patrick F. Strobel, Lucas Laventure, Priyanshu Chandra, Mark Del Campo, Pierre LeMagueres, Lauren Aheran, Jing Jin, Nathan J. Oldenhuis, David Punihaole, Aylin Aykanat","doi":"10.1021/prechem.6c00016","DOIUrl":"https://doi.org/10.1021/prechem.6c00016","url":null,"abstract":"<p>Precise control over phase, topology, and reactivityin metal–organicframeworks (MOFs) is critical for translating chemical responsivenessinto predictable function. Disulfide-linked coordination networksare attractive flexible materials, yet their strong sensitivity tosynthesis conditions has hindered mechanistic understanding of howthe structure governs reactivity. Here, we achieve phase control ina zinc disulfide MOF system by tuning solvent coordination and wateractivity, enabling access to a microcrystalline open-pore structure(Zn-MOF-α) and a dense, topologically distinct isomer (Zn-MOF-β)from the same disulfide linker. Microcrystal electron diffraction(MicroED) studies determined both structures directly from micro-and nanocrystalline particles, revealing distinct secondary buildingunits (SBUs), connectivity, and pore architecture. Systematic solventstudies identify water as a driver of α → β transformation,while the reverse transformation (β → α) is accessiblein solutions of <em>N</em>,<em>N</em>-dimethylformamidein water (DMF/H<sub>2</sub>O). Time-resolved experiments reveal aclear time and solvent dependence between the α- and β-phases,supporting distinct assembly pathways. By correlating topology, morphology,Brunauer–Emmett–Teller (BET), thermal gravimetric analysis(TGA), and spectroscopic signatures including electron paramagneticresonance (EPR), we show that the open α-framework provideshigher sulfur-centered radical populations and lower thermal robustnessrelative to the dense β-phase. Together, these results providedesign rules for predictable phase outcomes and topology-dependentdisulfide activation in flexible MOFs, enabling rational control ofstructure–function relationships in responsive porous materials.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 8","pages":"1225–1235"},"PeriodicalIF":7.7,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810335","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":"Photocatalytic Radical Functionalization of Alkenylammonium Salts","authors":"Aoi Yoshita, Kohiro Shimozawa, Tomohiro Fukushima, Yota Sakakibara, Kei Murakami","doi":"10.1021/prechem.6c00029","DOIUrl":"https://doi.org/10.1021/prechem.6c00029","url":null,"abstract":"<p>Alkenylammonium salts are introduced as an underdevelopedclassof electron-deficient radical acceptors. Under visible-light photoredoxcatalysis combined with halogen atom transfer (XAT) or hydrogen atomtransfer (HAT) activation modes, these cationic alkenes react witha broad range of alkyl radical precursors. The transformation enablesthe modular construction of structurally diverse quaternary ammoniumcompounds under mild conditions. The synthetic utility of the protocolis demonstrated through cyclopropanation, late-stage functionalization,and one-pot demethylation to access tertiary amines. This work establishesalkenylammonium salts as versatile building blocks in catalytic radicalchemistry, thereby expanding the synthetic strategies for the preparationof quaternary ammonium salts and tertiary alkylamines.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 8","pages":"1134–1140"},"PeriodicalIF":7.7,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810356","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":"Lithium Recovery from Brines: A Comprehensive Review of Advanced Separation Technologies","authors":"Hemant Mittal, Syed Nasir Shah, Maryam Alsuwaidi, Akram Alfantazi","doi":"10.1021/prechem.5c00264","DOIUrl":"https://doi.org/10.1021/prechem.5c00264","url":null,"abstract":"<p>The increasing lithium (Li) demand, attributable to itsessentialfunction in energy storage applications, has necessitated the advancementin Li extraction and recovery methods. Brine-based Li extraction presentsa cost-effective and scalable solution; however, challenges such ashigh magnesium-to-Li (Mg/Li) ratios and environmental concerns necessitateinnovative approaches. This review comprehensively examines variousLi recovery techniques from brine, focusing on precipitation, adsorptionand ion exchange, membrane separation, electrochemical separation,solvent extraction, and hybrid technologies. Precipitation methods,including carbonate and aluminate precipitation, offer straightforwardprocessing but face selectivity challenges in high Mg/Li ratio brines.Adsorption and ion exchange techniques, particularly Li-ion sievesand layered double hydroxides, have demonstrated high selectivityand efficiency. Electrochemical methods present promising low-energyalternatives for Li separation. Furthermore, solvent extraction andadvanced membrane-based techniques provide additional pathways forLi recovery, enhancing the yield and purity. This Perspective highlightsrecent advancements, process optimizations, and emerging strategiesaimed at improving Li recovery while reducing environmental impact.Comparative assessment of these techniques is provided, consideringfactors such as the Mg/Li ratio, operational feasibility, energy consumption,and scalability. Special emphasis is placed on emerging strategiessuch as engineered sorbents, electrochemical separation, and advancedmembrane filtration, which offer sustainable alternatives to traditionalmethods. Additionally, this review bridges the gap between laboratory-scaleresearch and industrial applications, outlining key challenges andpotential solutions for Li extraction. This Review provides a roadmapfor developing more efficient, sustainable, and scalable Li extractionprocesses. The insights presented here aid researchers, industry professionals,and policymakers in advancing Li recovery technologies to meet growingglobal demand.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 8","pages":"1103–1133"},"PeriodicalIF":7.7,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810272","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":"Boron Amidate as a Modular Anionic Catalyst for Sequential Electron-Donor/Hydrogen-Atom-Transfer Catalysis","authors":"Bumpei Maeda, Nao Kojima, Raizo Inaba, Kohsuke Ohmatsu","doi":"10.1021/prechem.6c00045","DOIUrl":"https://doi.org/10.1021/prechem.6c00045","url":null,"abstract":"<p>Electron donor–acceptor (EDA) complex excitationhas emergedas a powerful strategy for generating reactive radical species withoutexternal photocatalysts. However, the rational design of catalyststhat integrate electron transfer with hydrogen atom transfer (HAT)remains underdeveloped. Herein, we report a modular anionic boronamidate that functions as a dual electron-donor/HAT catalyst withina single molecular framework. The π-conjugated anionic structureenables efficient donor–acceptor assembly, while structuralmodification at the nitrogen center allows systematic tuning of thedonor strength, Brønsted acidity, and N–H bond dissociationfree energy (BDFE). This catalyst enables EDA-driven radical generationfollowed by productive HAT, as demonstrated in Giese-type C(sp<sup>3</sup>)–H functionalization. Furthermore, a Minisci-typereaction is achieved through modulation of the proton-donating abilityof the boron amide, which proceeds under oxidant-free conditions andis presumably sustained by aerobic oxidation. These results establisha modular design strategy for anionic molecular catalysts that orchestrateelectron transfer and HAT processes, thereby providing a frameworkfor EDA-based catalytic transformations.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 8","pages":"1245–1250"},"PeriodicalIF":7.7,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810277","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}
Precision ChemistryPub Date : 2026-08-24Epub Date: 2026-06-09DOI: 10.1021/prechem.5c00467
Xiao Xu, Guangshuai Han, Tianhao Li, Jiayue Hu, Guotao Qiu, Shao-Yu Tseng, Gyeong Ho Han, Alexander D. Dupuy, Anthony Shoji Hall, Corey Oses
{"title":"Stabilizing Iodine in Pyrochlore: Toward New Nuclear Waste Forms","authors":"Xiao Xu, Guangshuai Han, Tianhao Li, Jiayue Hu, Guotao Qiu, Shao-Yu Tseng, Gyeong Ho Han, Alexander D. Dupuy, Anthony Shoji Hall, Corey Oses","doi":"10.1021/prechem.5c00467","DOIUrl":"https://doi.org/10.1021/prechem.5c00467","url":null,"abstract":"<p>The long-term immobilization of iodine-129, a key radionuclidein nuclear waste, remains a major challenge for sustainable nuclearenergy. Pyrochlore ceramics, which can be integrated into glass-ceramicwaste forms, are widely recognized for their chemical durability andtheir capacity to immobilize actinides and other long-lived wasteelements, but have not previously been demonstrated for iodine. Here,we show iodine can be accommodated into the pyrochlore structure bypartial substitution for fluorine in a known oxyfluoride pyrochlore.Structural characterization reveals a solubility limit and associatedlattice distortion upon iodine incorporation. To address these constraints,we introduce a high-entropy design strategy and computationally screenover 40,000 multication pyrochlore compositions, identifying candidateswith the potential for substantially increased iodine loading. Manycandidates exceed 33 wt % iodine, outperforming most existing ceramics,and in principle, iodine loadings as high as 74 wt % are accessible.These results highlight high-entropy pyrochlores as a promising andtunable materials platform for advancing safe and effective immobilizationof iodine radionuclides in nuclear waste management.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 8","pages":"1211–1224"},"PeriodicalIF":7.7,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810366","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}
Precision ChemistryPub Date : 2026-08-24Epub Date: 2026-04-22DOI: 10.1021/prechem.6c00021
Haruka Morizumi, Yoshikazu Kitano, Yohei Okada
{"title":"TiO2-Mediated Enamine Radical Cation Cycloadditions: Divergent [4 + 2] and [2 + 2] Reactivity","authors":"Haruka Morizumi, Yoshikazu Kitano, Yohei Okada","doi":"10.1021/prechem.6c00021","DOIUrl":"https://doi.org/10.1021/prechem.6c00021","url":null,"abstract":"<p>Enamine radical cation cycloadditionswere developed under TiO<sub>2</sub>-mediated photochemical conditionsto enable net redox-neutralbond formation in nitrogen-involving reaction systems. Substrateswere analyzed by subdividing them into two classes based on whetheran aryl unit was directly attached to nitrogen (<em>N</em>-aryl vs non-<em>N</em>-aryl enamines). Their oxidizabilitywas quantified by cyclic voltammetry in LiClO<sub>4</sub>/CH<sub>3</sub>NO<sub>2</sub>, which revealed that enamine oxidizability could betuned cooperatively by aromatic substituents and <em>N</em>-protecting groups. Under TiO<sub>2</sub>-mediated interfacial photochemicalsingle-electron activation, [4 + 2] cycloadditions with 2,3-dimethyl-1,3-butadieneshowed a strong dependence on oxidation potential within the <em>N</em>-aryl class and were also efficient for non-<em>N</em>-aryl enamines. In contrast, [2 + 2] cycloadditions exhibited a narrowerreactivity window and were more strongly influenced by partner reactivityand steric and conformational constraints than by oxidation potentialsalone. These results establish enamines in both classes as viableplatforms for TiO<sub>2</sub>-enabled radical cation cycloadditionsand provide insight into distinct control elements governing [4 +2] versus [2 + 2] manifolds.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 8","pages":"1236–1244"},"PeriodicalIF":7.7,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810236","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":"An Orally Available Derivative of a Specific CK2 Inhibitor for Regulating Circadian Rhythms and Acute Myeloid Leukemia","authors":"Tsuyoshi Oshima, Daiki Setoyama, Akiko Sugiyama, Kazuma Amaike, Ikumi Yamanaka, Kentaro Hosokawa, Kazuto Nunomura, Kiyoshi Kawamura, Ashutosh Srivastava, Mui Iida, Kazuhito Gotoh, Bangzhong Lin, Mikio Morita, Masashi Ohmi, Takeshi Uchiumi, Fumio Arai, Junichi Haruta, Masaki Sudo, Florence Tama, Yuya Kunisaki, Kenichiro Itami, Tsuyoshi Hirota","doi":"10.1021/prechem.5c00288","DOIUrl":"https://doi.org/10.1021/prechem.5c00288","url":null,"abstract":"<p>The protein kinase CK2 controls cell cycle, apoptosis,and circadianrhythms. The CK2 inhibitor CX-4945 is in clinical trials for cancertreatment, but it has many off-target proteins. Therefore, the developmentof a bioavailable and specific CK2 inhibitor has been awaited. Wepreviously discovered a specific CK2 inhibitor, GO289, from cell-basedphenotypic screening of circadian clock modulators. However, the lowwater solubility and metabolic stability of GO289 have limited <em>in vivo</em> applications. Here, we developed GO289 derivativeswith higher water solubility and metabolic stability. A derivative,GO847, changed the period length of cellular circadian rhythms similarto GO289 and inhibited the growth of acute myeloid leukemia (AML)cells. A proteomic profiling suggested the effects of GO847 and GO289on pathways related to mitochondrial function, in addition to well-knownCK2 targets: cell cycle, apoptosis, RNA metabolism, and protein synthesis.Consistent with this observation, both compounds impaired the metabolicflexibility of mitochondria in AML cells. After oral administrationto mice, GO847 was detected in the plasma, liver, spleen, and bonemarrow but not in the brain. Together, the findings show that GO847is a promising candidate for targeting AML, a malignant blood cancerthat requires effective treatment.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 8","pages":"1171–1179"},"PeriodicalIF":7.7,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810279","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}
Precision ChemistryPub Date : 2026-08-24Epub Date: 2026-04-23DOI: 10.1021/prechem.5c00344
Leizhi Zheng, Mengyue Li, Bin He, Qiang Liu, Chengbao Liu
{"title":"Tailoring Edge Sites of B-Doped g-C3N4 To Promote Edge-Enriched Amine Functionalities for Enhanced CO2 Cycloaddition","authors":"Leizhi Zheng, Mengyue Li, Bin He, Qiang Liu, Chengbao Liu","doi":"10.1021/prechem.5c00344","DOIUrl":"https://doi.org/10.1021/prechem.5c00344","url":null,"abstract":"<p>The utilization of CO<sub>2</sub> gas is highly valuablefor cycliccarbonates. A boron-doped carbon nitride (BPCN-NH<sub>2</sub>) materialfunctionalized with edge-enriched -NH<sub>2</sub> groups was developedfor efficient CO<sub>2</sub> cycloaddition to synthesize cyclic carbonates.B-doped graphitic carbon nitride (BPCN) was first prepared using NaBH<sub>4</sub> as the boron source, and was subsequently subjected to insitu hydrolysis. This second step constructed a nitrogen-rich microenvironmentand endowed the material with edge-enriched amine (−NH<sub>2</sub>) functional groups, leading to a 0.58% increase in theiratomic content by XPS analysis. This design integrated boron dopingand -NH<sub>2</sub> functionalization within the CN framework, synergisticallyenhancing CO<sub>2</sub> adsorption and activation through dual activesites. The BPCN-NH<sub>2</sub>-1 catalyst demonstrated remarkableperformance (99% yield, 99.0% selectivity) under specific conditions(110 °C, 1 MPa, 50 mg catalyst, 12 h). This superior efficiencyis attributed to the synergistic interplay between the Lewis acidicboron dopant and the hydrogen-bond-donating amine moieties. Specifically,the boron centers act as Lewis acids, effectively activating the epoxidesubstrates toward nucleophilic attack. Concurrently, the amine groups,acting as basic hydrogen bond donors, facilitate the adsorption andactivation of CO<sub>2</sub>, thereby promoting the formation of keycarbamate intermediates. This boron–nitrogen hybrid with aminefunctionalities provides a robust, recyclable platform for greenerchemical synthesis.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 8","pages":"1180–1189"},"PeriodicalIF":7.7,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810238","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}
Precision ChemistryPub Date : 2026-08-24Epub Date: 2026-03-17DOI: 10.1021/prechem.5c00240
Yong Han, Shen Chen, Marek Kolmer, Michael C. Tringides, Lin-Lin Wang
{"title":"Coverage-Dependent Phase Stability of Pb-Intercalated Buffer-Layer Graphene on SiC(0001)","authors":"Yong Han, Shen Chen, Marek Kolmer, Michael C. Tringides, Lin-Lin Wang","doi":"10.1021/prechem.5c00240","DOIUrl":"https://doi.org/10.1021/prechem.5c00240","url":null,"abstract":"<p>Understanding the atomic-scale structureand stability of intercalatedtwo-dimensional (2D) metals requires precise theoretical insight.Here, we present an extensive first-principles density functionaltheory (DFT) investigation of Pb monolayers intercalated beneath abuffer-layer graphene on a SiC(0001) substrate. To minimize lattice-mismatchstrain between graphene and SiC, we employ a slightly rotated<span><span></span><math><msqrt><mn>61</mn></msqrt><mo>×</mo><msqrt><mn>61</mn></msqrt></math></span> SiC supercell, 3.67° off the commonlyused <span><span></span><math><msqrt><mrow><mn>3</mn></mrow></msqrt><mo>×</mo><msqrt><mrow><mn>3</mn></mrow></msqrt></math></span>model. This approach resolves key interfacialmotifs, most notably a 10 × 10 hexagonal-like phase with alternatingcompressive and tensile regions, that cannot be captured with smalleror unrotated models. Systematic exploration over a Pb coverage rangeof 0.4 < θ ≤ 1.0 reveals a chemical potential landscapefeaturing diverse thermodynamically stable phases, including periodic10 × 10 hexagonal, distorted hexagonal, elongated hexagonal,and stripe-like motifs, each associated with distinct out-of-planecorrugations in the decoupled graphene layer. At θ ≈0.79, multiple nearly degenerate hexagonal configurations emerge,differing only in Pb arrangements within the intercalated layer, consistentwith recent scanning tunneling microscopy (STM) observations. In theintermediate coverage range 0.49 < θ < 0.71, stripe-likemotifs exhibit small energy differences (< 20 meV) among themselvesand lie only 5–11 meV above the hexagonal phases, explainingthe coexistence of multiple patterns in experiments. These findingsprovide theoretical support for the observed coexistence of distinctinterfacial phases and highlight the intricate, atomically precise,coverage-dependent phase stability of Pb-intercalated graphene onSiC(0001).</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"4 8","pages":"1155–1170"},"PeriodicalIF":7.7,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810389","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}