Journal of Chemical Sciences最新文献

{"title":"[Cu]-Catalyzed cascade self-condensation/cyclization of 2-propargylic alcohols: Access to dihydro-indenopyran and cyclopenta[b]naphthalene scaffolds via cooperative Cu(OTf)2/p-TsOH catalysis","authors":"Suraj,&nbsp;Anasuyamma Uruvakili,&nbsp;K C Kumara Swamy","doi":"10.1007/s12039-026-02546-3","DOIUrl":"10.1007/s12039-026-02546-3","url":null,"abstract":"<div><p>A [Cu]-catalyzed cascade reaction involving self-condensation and cyclization of <i>tert</i>-propargylic alcohols affording 1<i>H</i>-cyclopenta[b]naphthalenes and dihydro-indenopyrans has been developed. While the 2-methyl substituted propargylic alcohols led to 1<i>H</i>-cyclopenta[b]naphthalenes, 2-diaryl substituted propargylic alcohols furnished dihydro-indenopyrans in moderate to good yields. The transformation proceeded under mild conditions using Cu(OTf)₂ and <i>p</i>-toluenesulfonic acid (<i>p</i>-TsOH) as cooperative catalysts. The scope, mechanism, and synthetic potential of this cyclization are discussed.</p><h3>Graphical abstract</h3><p><i>Tert</i>-propargyl alcohols bearing a 2-methyl or 2-diaryl group undergo self-condensation to afford cyclopenta[b]naphthalenes or dihydro-indenopyrans.</p>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613668","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}

{"title":"Quantum-mechanical weak values in qubits: Inflation, deflation and average values","authors":"Kamal Bhattacharyya","doi":"10.1007/s12039-026-02556-1","DOIUrl":"10.1007/s12039-026-02556-1","url":null,"abstract":"<div><p>The standard paradigm of ‘weak values’ is outlined, and examples leading to several pathological situations are summarized. A few apparently disturbing features are rationalized via explicit links with eigenvalues and the average values. Specifically, we have found it expedient to choose a complete orthonormal set of post-selected states, and hence a full set of weak values, for discussion in a stationary framework. As an illustrative example, a qubit is chosen to avoid any complex number.</p><h3>Graphical abstract</h3><p>Inflation and deflation of quantum ‘weak’ values, respectively beyond the highest and lowest eigen values of a Hermitian operator, are studied for qubits with fixed post-selected and varying preselected states to enrich our understanding.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613742","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}

{"title":"Induced chirality in a binary complex of trifluoroacetic acid with camphor","authors":"Anwesha Datta,&nbsp;Indrani Bhattacharya,&nbsp;Tapas Chakraborty","doi":"10.1007/s12039-026-02547-2","DOIUrl":"10.1007/s12039-026-02547-2","url":null,"abstract":"<div><p>Reported here are the infrared absorption and infrared vibrational circular dichroism (VCD) spectra of a binary complex of trifluoroacetic acid (TFAA) with two enantiomers of camphor in carbon tetrachloride (CCl₄) solution. The spectral analysis reveals formation of two distinct isomeric complexes in the liquid at room temperature. The measured VCD spectra of the binary complex shows distinct transitions with respect to selected vibrational modes of the TFAA moiety. The observations have been corroborated by the predictions of density functional theory (DFT) calculations. The results demonstrate the occurrence of chirality induction in an achiral counterpart in the non-covalent complex of a chiral molecule.</p><h3>Graphical abstract</h3><p><i>Synopsis</i>. The graphical abstract illustrates that due to the formation of a hydrogen-bonded binary complex between trifluoroacetic acid and the two enantiomers of camphor, chirality is induced in the otherwise achiral trifluoroacetic acid molecule. This induced chirality is evidenced by both experimental and theoretical vibrational circular dichroism spectra of the complex.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148466347","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}

{"title":"Enhanced chemosensing activity of Schiff base ligand through quantum dot hybridization: Silver and zinc quantum dot-based hybrid receptors for lanthanum ion detection","authors":"Vaishali Yadav,&nbsp;Rohitash Kumar,&nbsp; Rishu,&nbsp;Vimal K Bhardwaj","doi":"10.1007/s12039-026-02549-0","DOIUrl":"10.1007/s12039-026-02549-0","url":null,"abstract":"<div><p>A previously reported Schiff base receptor (<b>H</b>_<b>2</b><b>L</b>) showed strong sensitivity for lanthanum ions (<i>K</i>_<i>a</i> = 2.09×10⁷ M⁻¹, LOD = 5.89×10⁻⁸ M). To improve performance, <b>H</b>_<b>2</b><b>L</b> was hybridized with silver (Ag) and zinc (Zn) nanoparticles, forming <b>Ag@H</b>_<b>2</b><b>L</b> and <b>Zn@H</b>_<b>2</b><b>L</b>. These hybrids were characterized by TEM, DLS, UV-vis, fluorescence, and optical analysis. <b>Ag@H</b>_<b>2</b><b>L</b> displayed exceptional sensitivity and selectivity (<i>K</i>_<i>a</i> = 2×10⁹ M⁻¹, LOD = 2.8×10⁻¹⁰ M), surpassing both <b>H</b>_<b>2</b><b>L</b> and <b>Zn@H</b>_<b>2</b><b>L</b> (<i>K</i>_a = 1.47×10⁷ M⁻¹, LOD = 1.41×10⁻⁷ M). Results confirm that nanoparticle hybridization, especially with Ag, greatly enhances chemosensory efficiency for lanthanum ion detection.</p><h3>Graphical abstract</h3><p>A Schiff base receptor (H₂L) and its nanoparticle-based hybrids, <b>Ag@H</b>_<b>2</b><b>L</b> and <b>Zn@H</b>_<b>2</b><b>L</b>, were developed for selectivelanthanum (La³⁺) ion sensing. Hybridization with Ag nanoparticles significantly enhanced fluorescence intensity, binding affinity, and detection sensitivity due to π-conjugation and surface effects, resulting in superior sensingperformance (<i>K</i>_<i>a</i> = 2×10⁹ M⁻¹, LOD = 2.8×10⁻¹⁰ M) compared to H₂L and <b>Zn@H</b>_<b>2</b><b>L</b>.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148466379","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}

{"title":"Zinc oxide as reusable heterogeneous catalyst for oxazoline synthesis: A kinetic and reusability study","authors":"Anusree Suresh,&nbsp;Gorachand Badaraita,&nbsp;Akhila Mekha,&nbsp;Santhana Gopal Ramkumar","doi":"10.1007/s12039-026-02543-6","DOIUrl":"10.1007/s12039-026-02543-6","url":null,"abstract":"<p>The synthesis of 2-oxazolines typically relies on homogeneous zinc salts, which offer high activity but suffer from poor recyclability and metal contamination. Here, we demonstrate that commercially available zinc oxide (ZnO) functions as an efficient and reusable heterogeneous catalyst for the cyclodehydration of amino alcohols with nitriles under solvent-free conditions. Time-resolved ¹H NMR kinetics were recorded for the formation of five products (MeOx, EtOx, iPrOx, BuOx, PhOx), revealing a characteristic sigmoidal conversion profile. Classical kinetic models, including first-order, power-law and Langmuir-type expressions, failed to describe the data, while a logistic kinetic model provided excellent fits for all the product formation, capturing the induction phase, rapid cooperative acceleration and late-stage saturation. This behavior is rationalized by progressive surface activation, evolving adsorption equilibria, and partial ZnO site blocking during the course of the reaction. Scanning electron microscopy and powder X-ray diffraction analyses confirm that the catalyst retains its wurtzite structure and morphology and can be reused without loss of integrity. This work highlights logistic kinetics as a useful descriptor for heterogeneous Lewis-acid catalysis and establishes ZnO as a low-cost, recyclable platform for oxazoline synthesis.</p><p>Graphical abstract illustrates the solvent-free cyclodehydration of nitriles and amino alcohols to synthesize 2-oxazolines using a reusable heterogeneous zinc oxide catalyst. Time-resolved ¹H NMR kinetics demonstrate a distinct sigmoidal conversion profile accurately described by a logistic kinetic model rather than classical rate expressions.</p>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148466020","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}

{"title":"Non-equilibrium thermodynamics of Phosphorylation–dephosphorylation ultrasensitive transition and critical behavior of MAPK cascade circuits","authors":"Pallabi Roy,&nbsp;Gautam Gangopadhyay","doi":"10.1007/s12039-026-02528-5","DOIUrl":"10.1007/s12039-026-02528-5","url":null,"abstract":"<div><p>We have presented a unified theoretical framework for the turnover of stochastic kinetics and non-equilibrium thermodynamics of phosphorylation–dephosphorylation cycles (PdPc) and their extension to cascade signaling networks. Starting from the chemical master equation, we have employed a large deviation ansatz to recast the dynamics into the Hamilton–Jacobi formalism, yielding an explicit Hamiltonian with species concentrations and their conjugate momenta as canonical variables. This formulation provides a systematic evaluation of reaction velocities, fluctuation-induced diffusion, and entropy production rates (EPR). Our results reveal hallmark features of ultrasensitivity: in PdPc, sharp switch-like transitions are reflected in the slope of the EPR, which steepens with increasing chemical potential difference. In a typical PdPc cascade circuits within mitogen-activated protein kinase (MAPK), cooperative enzymatic interactions amplify these effects, optimized at a critical size of the cycle number.</p><h3>Graphical abstract</h3><p>An unidirectional signaling cascade is illustrated where receptor activation triggers sequential downstream cycles. Time-series and steady-state analyses show a sharp transition beyond the third cycle, highlighting cycle three as optimal. Increasing cycle numbers enhance cooperativity, sharpening transitions in system velocity and entropy production, indicating critical behavior in the cascade dynamics.</p>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148466019","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}

{"title":"Interaction and dynamics of newly prepared multi-component molten mixture: An alternative reaction medium","authors":"Ejaj Tarif,&nbsp;Jayanta Mondal,&nbsp;Ranjit Biswas","doi":"10.1007/s12039-026-02545-4","DOIUrl":"10.1007/s12039-026-02545-4","url":null,"abstract":"<p>We developed a transparent, low-viscosity molten mixture employing sorbitol, urea and water, and investigated its physical properties, molecular-level interactions and dynamics through different experiments. The measured viscosity coefficient (<span>(eta)</span>) of the molten mixture varies from ~73 to 8 cP within the temperature range 288 K <span>(le Tle)</span> 338 K. Temperature dependent (303 K <span>(le Tle)</span> 343 K) dielectric relaxation (DR) measurements in the frequency window <span>(0.2le nu /{rm GHz}le 50)</span> reveals presence of multi-Debye relaxation dynamics in this medium with average relaxation time spanning from ~400 to 100 ps within this temperature range. The high static dielectric constant <span>(({varepsilon}_{s} sim 80))</span> of the molten mixture, like water, makes it excellent at dissolving things, even though its dynamics are much slower than water. Steady-state emission studies using fluorescent dyes coumarin 153 (C153) and coumarin 343 (C343) demonstrate spatial homogeneity in the medium, though signs of mild dynamic heterogeneity are evident from the fractional viscosity dependency of the rotational dynamics of the dye molecules (<span>({tau}_{r} propto {left[frac{eta }{T}right]}^{p}text{w}text{i}text{t}text{h} , papprox 0.7))</span>. In contrast, DR dynamics captures less dynamical heterogeneity of the system, with <span>({tau}_{r} propto {left[frac{eta }{T}right]}^{p} text{w}text{h}text{e}text{r}text{e})</span> <span>(p approx 0.87)</span>. Further, the rotational dynamics exhibit an Arrhenius-type temperature dependence. The obtained activation energy for C153 and C343 rotation are ~30 kJ mol^–1 and 26 kJ mol^–1, respectively, whereas the viscosity and average DR times activation energies are ~36 kJ mol^–1 and ~32 kJ mol^–1. These results indicate that the reorientation of dipolar molecules of the molten mixture felt higher friction than the rotation of C153 and C343 in the same medium.</p><p>The graphical abstract presents the dielectric relaxation response of the (sorbitol + urea + water) molten mixture over a frequency range <span>(0.2le nu /{rm GHz}le 50)</span> at various temperatures. The spectra reveal multiple relaxation modes arising from complex molecular motions and hydrogen-bond rearrangements. Decomposition of the dielectric loss profiles highlights cooperative dipolar dynamics, while the medium maintains high polarity together with comparatively low viscosity.</p>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148465645","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}

{"title":"Thermodynamic origin of azeotropic condition: Composition dependent enthalpic signature in water–ethanol mixtures","authors":"Rik N Mukherjee,&nbsp;Pradip K Ghorai,&nbsp;Ranjit Biswas","doi":"10.1007/s12039-026-02550-7","DOIUrl":"10.1007/s12039-026-02550-7","url":null,"abstract":"<div><p>Azeotropes are constant-boiling mixtures in which the liquid and vapor phases share the same composition. Previous work on the water–ethanol system proposed that, at the azeotropic condition, water and ethanol exhibit identical diffusion distributions as a dynamical signature. However, whether this dynamical behavior plays a causal role in azeotrope formation remains unresolved. In this work, we performed computational estimations of key thermodynamic quantities to probe the origin of the azeotropic behavior in the water–ethanol mixture at the azeotropic composition and temperature. We examined the composition dependence of the total Gibbs free energy of mixing (<span>(Delta {overline{G} }_{text{m}text{i}text{x}})</span>) and found no distinctive feature at the azeotropic composition. A similar non-unique trend is observed for the entropic contribution (<span>(Delta {overline{S} }_{text{m}text{i}text{x}})</span>). In contrast, the enthalpy of mixing (<span>(Delta {overline{H} }_{text{m}text{i}text{x}})</span>) exhibits a distinctive signature at the azeotropic point compared to other compositions at the same temperature (<span>({T}_{text{a}text{z}text{e}}= 351 , text{K})</span>). It is observed that, <span>(Delta {overline{H} }_{text{m}text{i}text{x}})</span> remains negative until the azeotropic composition is crossed, after which it abruptly changes to become positive. This enthalpic signature underscores the critical importance of intermolecular interactions in establishing the unique azeotropic condition for water–ethanol mixture, though the universality of this feature is not tested.</p><h3>Graphical abstract</h3><p>In search of any thermodynamic signature at the azeotropic condition (<i>X</i>_aze, <i>T</i>_aze), computational calculation of <span>(Delta {overline{{G}} }_{text{m}text{i}text{x}})</span>, <span>(Delta {overline{{S}} }_{text{m}text{i}text{x}})</span> and <span>(Delta {overline{{H}} }_{text{m}text{i}text{x}})</span> is carried out. Neither <span>(Delta {overline{{G}} }_{text{m}text{i}text{x}})</span> nor <span>(Delta {overline{{S}} }_{text{m}text{i}text{x}})</span> exhibited any anomalous behavior. Interestingly, <span>(Delta {overline{{H}} }_{text{m}text{i}text{x}})</span> gives composition-dependent signature as it shows abrupt change on crossing <i>X</i>_aze, suggesting crucial role of intermolecular interactions.</p>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148465964","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}

{"title":"Chemical dynamics simulations on the association and ensuing dissociation of the benzene–hexachlorobenzene complex and comparison with benzene dimer and benzene–hexafluorobenzene complexes","authors":"Basudha Deb,&nbsp;Nabam Yal,&nbsp;Himashree Mahanta,&nbsp;Amit Kumar Paul","doi":"10.1007/s12039-026-02541-8","DOIUrl":"10.1007/s12039-026-02541-8","url":null,"abstract":"<div><p>Chemical dynamics simulations were carried out to investigate the association and dissociation of the benzene–hexachlorobenzene (Bz–HCB) complex at 1000–2000 K with impact parameters up to 10 Å. Two classes of complexes, short- and long-lived, were identified based on distance and lifetime criteria. Association probability decreased from ~40% at 1000 K to ~10% at 2000 K, with lifetimes of 1.7–26.6 ps. Arrhenius analysis of association rate constants showed reduced stability of the complexes at higher temperatures. Dissociation rates increased with temperature at finite impact parameters, while remaining nearly invariant at <i>b</i> = 0.0 Å. Comparison with benzene dimers and Bz–hexafluorobenzene (Bz–HFB) showed stronger stability of Bz–HCB due to π–π interactions. Rice–Ramsperger–Kassel (RRK)-based analysis indicated incomplete vibrational energy randomization in all the complexes. However, Bz–HCB exhibited the highest effective degrees of freedom, consistent with enhanced mode–mode coupling leading to back-and-forth energy transfer among its vibrational modes that slows its dissociation relative to Bz–HFB and Bz₂.</p><h3>Graphical abstract</h3><p>The graphical abstract compares benzene dimer (Bz₂), benzene–hexafl uorobenzene (Bz–HFB), and benzene–hexachlorobenzene (Bz–HCB) complexes. Complex stability increases from Bz₂ to Bz–HCB. Association probability decreases with increasing temperature, whereas the ensuing dissociation rate increases. Additionally, the association rate increases from Bz₂ to Bz–HCB, while the ensuing dissociation rate follows the opposite trend, indicating enhanced intermolecular stability in halogenated complexes.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148380642","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}

{"title":"Enhancing the sensing performance of magnesium oxide nanocages for resorcinol drug detection through Ag decoration: A density functional theory study","authors":"Farideh Zargarzadeh Dezfoli,&nbsp;Zohreh Saadati,&nbsp;Mahboobeh Salehpour,&nbsp;Fereydoon Khazali","doi":"10.1007/s12039-026-02509-8","DOIUrl":"10.1007/s12039-026-02509-8","url":null,"abstract":"<div><p>This density functional theory (DFT) study investigates the enhancement of resorcinol (RES) detection capabilities in magnesium oxide (MgO) nanocages through Ag decoration. Using the M06-2X functional with 6-311+G(d,p)/LANL2DZ basis sets, we systematically analyzed the structural, electronic, and thermodynamic properties of pristine and Ag-decorated Mg₁₂O₁₂ nanocages. Results demonstrate that Ag-decoration reduces the HOMO-LUMO gap by 50.5% (from 7.57 to 3.74 eV), significantly improving charge transfer characteristics. The Ag–MgO system exhibits superior RES adsorption (<i>E</i>_ads = –21.7 kcal.mol^–1) with a 25.4% reduction in energy gap upon RES binding, compared to only 5.9% for pristine MgO. Natural bond orbital analysis reveals enhanced charge transfer (0.28 |<i>e</i>|) mediated by Ag orbitals, while conceptual DFT parameters show decreased electronegativity (4.70 → 3.06 eV) and electronic hardness (4.70 → 2.50 eV), indicating improved reactivity. The sensor's recovery time is tunable from 7.8×10³ s (visible light) to 0.78 s (UV irradiation) through modulation of desorption barriers. These findings establish Ag-decorated MgO nanocages as promising platforms for selective RES detection, combining high sensitivity with adjustable response dynamics.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"138 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148323784","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}