Dalton Trans [JOURNAL]
Sun
200 papers
Structure-activity relationships of ATCUN-based Cu(II) complexes with large chelate rings: interplay of ROS generation, DNA binding, and nuclease activity.
Heinrich J, Lück J, Varlakhanov D … +3 more , Kumar R, Stein M, Kulak N
Dalton Trans · 2026 Jun · PMID 42171319 · Publisher ↗
Since the discovery of DNA cleavage and anticancer activity of the simplest Cu(II) ATCUN complex (peptide ligand: Gly-Gly-His, GGH) in 1983, systematic biological enhancements by derivatives have not been achieved. The s...
Since the discovery of DNA cleavage and anticancer activity of the simplest Cu(II) ATCUN complex (peptide ligand: Gly-Gly-His, GGH) in 1983, systematic biological enhancements by derivatives have not been achieved. The stable 5,5,6-chelate ring structure provided by the original GGH ligand hampers efficient ROS production Cu redox cycling (Cu(II/I)). In this work, we demonstrate that the incorporation of 7,5,6- and 7,6,6-chelates (Gly or β-alanine in the second peptide position, respectively) in combination with N-terminal design elements, such as γ-aminobutyric acid (GABA), 3,5-substituted (CF-, CH-) pyrazolyl and triazolyl units, provides an effective strategy to reinstate biological activity regarding ROS generation (determined fluorescence spectroscopy and gel electrophoresis), DNA cleavage (gel electrophoresis) and DNA binding (fluorescence, UV/VIS and CD spectroscopy). Among the series of studied Cu(II) complexes, the metallopeptide with an amine group at the N-terminus (GABA) combined with a 7,6,6-chelate (β-alanine) system exhibits the highest overall biological activity, whereas a triazolyl moiety, independent of the chelate ring size (Gly: 7,5,6 and β-alanine: 7,6,6), leads to efficient hydroxyl radical generation. Computational studies based on an extensive conformational search of the metallopeptides, followed by an energy refinement at the level of Density Functional Theory (DFT), were used to elucidate the structure-activity relationship.
Synthesis of silver nanoparticles and their attachment to a zinc oxide-iron oxide hybrid structure: analyte-mediated enhanced peroxidase-like activity for colorimetric detection.
Alula MT, Vetr F, Mligo MG … +1 more , Lemmens P
Dalton Trans · 2026 Jun · PMID 42171303 · Publisher ↗
Natural and human activities, such as mining for gold, coal-fired power stations, coal burning, and different industrial processes, have contributed to the emission of mercury into the environment. This necessitates regu...
Natural and human activities, such as mining for gold, coal-fired power stations, coal burning, and different industrial processes, have contributed to the emission of mercury into the environment. This necessitates regular monitoring of mercury in the environment. The requirement of skilled personnel, high costs, and time-consuming processes make the conventional techniques used in the detection of mercury unsuitable for routine analysis. Colorimetric methods overcome these limitations. In this study, silver nanoparticle (AgNP)-loaded ZnO/FeO (ZMN) composites (AgZMN) with peroxidase-like activity are produced. Ferrous sulphate is used to reduce Ag to Ag because of the difference in the reduction potentials of the two reacting species. Surface-enhanced Raman spectroscopy (SERS) is used indirectly to investigate the formation of AgNPs. Using 3,3',5,5'-tetramethylbenzidine (TMB) as a chromogenic peroxidase substrate, a colorimetric method for the detection of Hg is developed. The sensing relies on the enhancement of the peroxidase-like activity of AgZMN upon the addition of Hg to the catalytic oxidation reaction system. By relating the absorbance of oxTMB and the concentration of Hg, a relation that fits a linear equation in the concentration range of 0-65 μM is obtained. The limit of detection (LOD) is predicted from the calibration curve and found to be 0.937 μM. The assay exhibits a high selectivity towards Hg detection. The applicability of this method for the determination of Hg from tap and borehole ground water shows its practicality for real sample analysis. The green reduction method and deposition of AgNPs could be generalized to other metal ions with different reduction potentials from those of ferrous ions that favor reduction.
DTSA ligand engineering of CoWO: a robust peroxymonosulfate activator for benzophenone-3 and tetracycline degradation.
He Y, Liu Y, Wang X … +5 more , Li B, Li B, Zhang Y, Feng Y, Li W
Dalton Trans · 2026 Jun · PMID 42171300 · Publisher ↗
Pharmaceuticals and personal care products (PPCPs) are pervasive aquatic micropollutants that raise growing concerns due to their phytotoxic, carcinogenic and endocrine-disrupting effects. Herein, we report an ligand-mo...
Pharmaceuticals and personal care products (PPCPs) are pervasive aquatic micropollutants that raise growing concerns due to their phytotoxic, carcinogenic and endocrine-disrupting effects. Herein, we report an ligand-modulated cobalt tungstate, DTSA/CoWO, prepared by incorporating 2,2'-dithiosalicylic acid (DTSA) into CoWO to regulate its interfacial coordination environment and redox behavior toward peroxymonosulfate (PMS) activation. Comprehensive characterization (SEM, XRD, XPS and FT-IR) confirms the successful construction of DTSA-modified CoWO. Relative to pristine CoWO, DTSA/CoWO exhibits markedly enhanced catalytic activity for the oxidative removal of representative PPCPs, achieving >90% degradation of benzophenone-3 (BP-3) within 30 min ( = 0.12 min) and 99% degradation of tetracycline (TC) within 20 min ( = 0.214 min), corresponding to 3.29-fold and 2.19-fold rate enhancements. Mechanistic studies, combining quenching experiments and electron paramagnetic resonance (EPR) analysis, identified superoxide anion (O˙) and singlet oxygen (O) as the dominant reactive species, whereas the involvement of sulfate radicals (SO˙) and hydroxyl radicals (˙OH), although suggested by quenching results, could not be directly confirmed under the current aqueous EPR conditions. LC-MS/MS analysis showed that BP-3 could be effectively converted into smaller products, and ECOSAR-based toxicity prediction indicated that the overall toxicity of the converted products was reduced after treatment. Notably, DTSA/CoWO retains its activity over four repeated cycles, and quantitative analysis ICP-MS reveals that the leaching of cobalt and tungsten is negligible. These results indicate that ligand engineering of CoWO is an effective strategy for obtaining promising persulfate activators for the degradation of personal care products and pharmaceuticals.
Multimodal stimulus responsive luminescence in MgGaO:Bi phosphors thermal-assisted energy transfer.
Kong X, Wei G, Ma J … +3 more , Liu P, Xu Y, Zhou M
Dalton Trans · 2026 Jun · PMID 42171295 · Publisher ↗
Multimodal stimulus-responsive luminescent materials have shown great promise in advanced anti-counterfeiting due to their dynamic and reversible optical changes under multiple external stimuli. Here, a Bi-activated trap...
Multimodal stimulus-responsive luminescent materials have shown great promise in advanced anti-counterfeiting due to their dynamic and reversible optical changes under multiple external stimuli. Here, a Bi-activated trap depth engineering strategy in MgGaO:Bi is proposed to achieve excitation-wavelength-dependent dual-mode luminescence: thermochromic and anti-thermal quenching. The selective occupation of Bi ions on octahedral [GaO] and tetrahedral [GaO] sites in MgGaO results in bimodal emission at 408 and 705 nm. Crucially, Bi doping reduces trap depth, effectively regulating the intrinsic energy level luminescence at 502 nm of the traps. Based on the thermal assisted energy transfer from traps to the intrinsic energy levels and Bi in tetrahedral sites, high-sensitivity temperature sensing and anti-thermal quenching luminescence dependent on excitation wavelength have been achieved. Upon the ultraviolet (UV) irradiation of 250 nm, the fluorescence intensity ratios (FIRs) of / for MgGaO:1.5%Bi showed excellent temperature-dependent enhancement behavior in the temperature range of 283 to 393 K, and the maximum relative temperature sensitivity () for the FIR is 4.15% K at 283 K. Under 280 nm UV excitation, the PL intensities ( and ) of MgGaO:1.5%Bi at 393 K retained 90.5% and 95.9% of the initial intensities, respectively, demonstrating remarkable anti-thermal quenching performance. More importantly, by utilizing the dynamic changes in luminescence color and intensity under different excitation wavelengths and temperatures, the application of dynamic anti-counterfeiting has been successfully achieved.
Synthesis, structure & diphenylacetylene reduction reactivity of a carbide-supported FeMo carbonyl cluster: a higher Fe-valence hydride intermediate for enhanced selectivity.
Dick E, Joseph C, Lynch VM … +1 more , Rose MJ
Dalton Trans · 2026 Jun · PMID 42171294 · Publisher ↗
The novel four-iron, two-molybdenum cluster [(µ-C)FeMo(CO)] (2) containing an interstitial carbide has been structurally characterized and prepared from the corresponding Fe dianion [(µ-C)Fe(CO)] (1) supported by two cro...
The novel four-iron, two-molybdenum cluster [(µ-C)FeMo(CO)] (2) containing an interstitial carbide has been structurally characterized and prepared from the corresponding Fe dianion [(µ-C)Fe(CO)] (1) supported by two crowned alkali units in [K(benzo-18-crown-6)]. In the X-ray structure of 2, the two molybdenum atoms share an internal geometry of a orientation about the central carbide, which indicates the stability of the well-known 'butterfly' FeC core found in the precursor 1, and this finding is consistent with other bis-heterometal variants of general formula [FeM] (M = Ni, Cu, Rh, Au). Reactivity studies monitoring the reduction of diphenylacetylene (DPA) catalyzed by 2 showed selective reduction to -diphenylethylene. The effect of proton source p and steric bulk on DPA reduction demonstrated that product selectivity is enhanced with increased steric bulk near the protonation site, and that conversion increases with more acidic proton sources. Overall, increased selectivity is observed with 2 compared with catalyst-free reactions, Fe-only clusters and the FeMo variant. We attribute the beneficial reactivity profile of cluster 2 to the electronic effect of the two Mo(0) centers, which lead to higher valent iron sites in the hydride intermediate cluster(s), thus decreasing non-specific reduction and increasing selectivity.
Modulating the energy transfer processes XPh (X = Si, Ge, Sn) substitution in luminescent Eu β-diketonate complexes.
Varaksina EA, Ferulev AI, Korshunov VM … +3 more , Stankevich TS, Gontcharenko VE, Taydakov IV
Dalton Trans · 2026 Jun · PMID 42171288 · Publisher ↗
A series of novel Eu complexes with group 14 element-containing β-diketone ligands were synthesized and their photoluminescence properties were studied in detail. The introduction of electron-donating XPh groups (X = Si,...
A series of novel Eu complexes with group 14 element-containing β-diketone ligands were synthesized and their photoluminescence properties were studied in detail. The introduction of electron-donating XPh groups (X = Si, Ge, Sn) into the phenyl ring of the well-known BTFA β-diketone ligand was found to lower the energy of the ligand triplet excited state T. Along the Si-Ge-Sn series, this results in a progressively reduced energy gap between the excited triplet state T and ligand-to-metal charge transfer (LMCT) states. This provides an efficient channel for quenching the ligand excitation the LMCT channel. As a result, a gradual decrease in the overall luminescence quantum yield is observed, identifying the Si-based derivative as the most efficient luminescent complex among substituted derivatives. The experimental findings were supported by theoretical calculations using the TD-DFT method.
Engineering a 1D/1D WO/FeWO S-scheme heterostructure for enhanced photocatalytic hydrogen evolution.
Liu S, Li J, Huang J … +3 more , Shi H, Zhang L, Qiu R
Dalton Trans · 2026 Jun · PMID 42171267 · Publisher ↗
Maximizing the spatial separation of photogenerated charge carriers while maintaining their strong redox potential remains the primary challenge in sustainable solar driven hydrogen production. In this study, a novel 1D/...
Maximizing the spatial separation of photogenerated charge carriers while maintaining their strong redox potential remains the primary challenge in sustainable solar driven hydrogen production. In this study, a novel 1D/1D WO/FeWO S-scheme heterostructure was synthesized a facile two-step hydrothermal method. The morphological characterization studies confirm that 1D FeWO nanowires are tightly anchored onto 1D WO nanorods, forming a layered architecture that exposes abundant active sites and establishes continuous longitudinal charge transfer channels. Therefore, the optimized WO/FeWO heterostructure exhibits a photocatalytic hydrogen evolution rate of 1602 µmol g h, representing an approximately 3.6-fold enhancement compared to pristine FeWO, while pristine WO demonstrates negligible activity. Density functional theory calculations combined with surface analysis suggest that the intrinsic work function difference between WO and FeWO promotes spontaneous interface electron redistribution. This creates a strong internal electric field that is proposed to facilitate the S-scheme charge transfer pathway under illumination, thereby suppressing photocarriers with weak redox ability while retaining the strongly reducing electrons on FeWO. This work provides a viable approach for combining dimensional engineering with interfacial electric field modulation to construct efficient S-scheme photocatalysts.
Dense inorganic-organic sodium-gadolinium sulfite-oxalate networks constructed from short bridging ligands: synthesis, structures and magnetic refrigeration behaviour.
Tiwari RK, Rout AA, Behera JN
Dalton Trans · 2026 Jun · PMID 42171255 · Publisher ↗
Two new inorganic-organic hybrid, three-dimensional heterometallic gadolinium-sulfite-oxalate coordination polymers, (1) and (2), featuring densely packed network architectures, have been successfully synthesized under...
Two new inorganic-organic hybrid, three-dimensional heterometallic gadolinium-sulfite-oxalate coordination polymers, (1) and (2), featuring densely packed network architectures, have been successfully synthesized under mild hydrothermal conditions. The structures were comprehensively characterized by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). To maximize the metal-to-ligand ratio and enhance magnetic density, short bridging sulfite (SO) and oxalate (CO) linkers were strategically incorporated, enabling the formation of compact frameworks suitable for magnetic refrigeration applications. Magnetic measurements reveal weak antiferromagnetic interactions between Gd(III) centers in both compounds, which contribute to pronounced magnetocaloric effects. Compound 1 exhibits a maximum magnetic entropy change (Δ) of -41.58 J kg K, while compound 2 shows -32.84 J kg K under an applied field 7 T at 3 K. These results highlight the potential of densely packed Gd-based coordination polymers as efficient low-temperature magnetic cooling materials.
Synergistic effect of electrolyte and intercalation engineering: comprehensive enhancement of the electrochemical performance of a mixed proton-electron conducting layered vanadate cathode for aqueous zinc-ion batteries.
Wang C, Zeng Z, Wang K … +5 more , Ma D, Zou Y, Qiao Q, Yao Z, Ren X
Dalton Trans · 2026 Jun · PMID 42171177 · Publisher ↗
This study synthesized a layered vanadate cathode, (HN(CH)NH)[VO] (C4N2-VO), for aqueous zinc-ion batteries (AZIBs) through an intercalation strategy using 1,4-butanediamine cations. These cations effectively expand the...
This study synthesized a layered vanadate cathode, (HN(CH)NH)[VO] (C4N2-VO), for aqueous zinc-ion batteries (AZIBs) through an intercalation strategy using 1,4-butanediamine cations. These cations effectively expand the interlayer spacing and form a dense hydrogen-bonding network with the vanadium oxide layers. At a relative humidity of 98%, C4N2-VO exhibits mixed proton and electron conductivity, with maximum proton and electron conductivities of 1.18 × 10 S cm and 7.36 × 10 S cm at 358 K, respectively. Owing to its unique structural and conductive properties, the C4N2-VO cathode exhibits excellent capacity performance in an aqueous Zn(CFSO) electrolyte. Nevertheless, the structural collapse of the C4N2-VO cathode during charge-discharge processes degrades its cycling stability. To address this issue, this study introduced a polyethylene glycol (PEG) additive into the original aqueous electrolyte. PEG effectively suppresses the structural collapse of the cathode; however, it concurrently increases resistance to ion migration, thereby causing a decline in capacity performance. When the PEG volume fraction in the electrolyte is optimised to 20%, the C4N2-VO cathode exhibits a significant improvement in cycling stability while maintaining a high specific capacity. Moreover, the distinct lattice planes of the C4N2-VO cathode exhibit opposing expansions (positive negative expansion) during charge-discharge processes, effectively minimising volume changes. This research not only confirms that a layered vanadate incorporating organic amine cations can serve as a potential mixed proton-electron conductor but also provides an innovative strategy to comprehensively enhance the electrochemical performance of layered vanadate cathodes for AZIBs.
Pt(II) single sites in mixed-metal ZIF-8/67 PtAuCo@ZIF-67 for electrocatalytic methanol oxidation in fuel cells.
Habibagahi B, Hoseini SJ, Bahrami M … +5 more , De Giglio E, Sportelli MC, Mastrorilli P, Nabavizadeh SM, Chen W
Dalton Trans · 2026 Jun · PMID 42171137 · Publisher ↗
This work presents an advanced method for fabricating zeolitic imidazolate framework-67 (ZIF-67) and Pt(II) single sites in mixed-metal ZIF-8/67 (Pt(II)-MM-ZIF-8/67) films at a liquid-liquid interface, where encapsulatio...
This work presents an advanced method for fabricating zeolitic imidazolate framework-67 (ZIF-67) and Pt(II) single sites in mixed-metal ZIF-8/67 (Pt(II)-MM-ZIF-8/67) films at a liquid-liquid interface, where encapsulation of PtAuCo nanoalloys was achieved exclusively within ZIF-67. Four PtAuCo-based catalysts-unsupported PtAuCo, PtAuCo on reduced graphene oxide (PtAuCo/r-GO), as well as ZIF-stabilized variants (PtAuCo@ZIF-67 and Pt(II)-MM-ZIF-8/67)-were systematically compared for methanol oxidation in both acidic and alkaline media. Results demonstrate that Pt(II)-MM-ZIF-8/67 exhibits outstanding stability and catalytic performance in alkaline environments, a benefit attributed to synergistic charge modulation by Pt(II), Co, and Zn ions. In contrast, the PtAuCo/r-GO catalyst proved most effective under acidic conditions. X-ray photoelectron spectroscopy revealed that platinum in the Pt(II)-MM-ZIF-8/67catalyst remains predominantly in the Pt(II) oxidation state, stabilized through coordination with 2-methylimidazole ligands in the metal-organic framework (MOF) structure, thereby resisting reduction to metallic Pt(0) even in reducing environments. The incorporation of multiple metal ions within the MOF matrix substantially alters the electronic properties of Pt(II), potentially reducing the activation barrier for oxidative-addition reactions and maximizing catalytic activity. Ultimately, this study provides the first effective demonstration of a platinum-based MOF with structurally integrated Pt(II) centers, highlighting the critical influence of mixed-metal frameworks in promoting electrocatalytic efficiency for energy conversion applications through precise structural and electronic engineering.
Mechanistic implications of excited high-spin states, spin-spin coupling, and differential [2Fe-2S] cluster temperature relaxations in the electron-bifurcating NfnABC from .
Vansuch GE, Wang S, Schut GJ … +2 more , Adams MWW, Lubner CE
Dalton Trans · 2026 Jun · PMID 42171125 · Publisher ↗
Electron bifurcation (EB) is a mechanism of biological energy transduction in which multiple oxidation-reduction (redox) reactions are thermodynamically coupled within a single enzyme, enabling the enzyme to harness the...
Electron bifurcation (EB) is a mechanism of biological energy transduction in which multiple oxidation-reduction (redox) reactions are thermodynamically coupled within a single enzyme, enabling the enzyme to harness the excess free energy from an exergonic process to drive an endergonic process. Because of this unprecedented chemistry, there is interest to translate EB principles to artificial and bioengineered systems, but a hurdle is that knowledge pertaining to the fundamental design principles of EB enzymes remains scarce. Here, we investigated the fundamental physical and electronic properties of electron transfer sites in a spectroscopically uncharacterized member of the BfuABC family of EB enzymes, the NADH-dependent reduced-ferredoxin:NADP oxidoreductase from ( NfnABC). Cryo-EM structures of NfnABC previously demonstrated that it contains twelve redox cofactors: two flavins (one FAD and one FMN), eight [4Fe-4S] clusters, and two [2Fe-2S] clusters. The FMN, one [4Fe-4S] cluster, and one [2Fe-2S] cluster comprise the bifurcating active site termed the electron-bifurcating flavobicluster (BF-FBC), which is found in all BfuABC family members. By using electron paramagnetic resonance spectroscopy, we identified spectral signatures originating from interactions between the FMN radical and [4Fe-4S] cluster in the BF-FBC and observed temperature dependent behavior of the BF-FBC's [2Fe-2S] cluster indicative of moderately slow spin-lattice relaxation. Additionally, we uncovered numerous spectral features corresponding to half-integer, > ½ spin states of [4Fe-4S] clusters, including one attributable to the consequences of lysine-ligation of a [4Fe-4S] cluster unique to NfnABC. We contextualize these findings to electron transfer theory and NfnABC's structure. Our insights further the understanding of how enzymes are designed to exert control over electron transfer to conduct thermodynamically challenging reactions.
Photochromic BiWO/BiOBr ultrathin nanosheet heterojunctions for the efficient photocatalytic synthesis of imine toluene and aniline coupling.
Han J, Ji G, Dou Y … +4 more , Qin Y, Liu X, Zhang Y, Wang W
Dalton Trans · 2026 Jun · PMID 42171095 · Publisher ↗
The photocatalytic activation of inert C-H bonds, followed by cross-coupling reactions driven by semiconductors, represents an important strategy in organic synthesis. However, the photocatalytic synthesis of imines tol...
The photocatalytic activation of inert C-H bonds, followed by cross-coupling reactions driven by semiconductors, represents an important strategy in organic synthesis. However, the photocatalytic synthesis of imines toluene and aniline coupling over semiconductor photocatalysts remains a significant challenge owing to the high C-H bond dissociation energy of toluene and poor charge separation and transfer efficiency of photocatalysts. Herein, we report BiWO/BiOBr ultrathin nanosheet heterojunctions (UNHs) with photochromic behaviors for the photocatalytic oxidation of toluene, followed by coupling with aniline to synthesize imines. The heterojunctions achieve a 99% imine yield, which is 7 and 5 times higher than that of pure BiWO (14%) and BiOBr (20%) nanosheets, respectively. The BiWO/BiOBr UNHs exhibit outstanding photocatalytic performance owing to the synergistic effect of the photochromism-induced W/W species and heterojunction engineering that expedites the separation and transfer of photogenerated charges, provides active sites for O adsorption and activation to form superoxide radicals (O˙), and promotes the photooxidation of toluene to benzaldehyde and then cross-coupling with aniline to produce imines under 405 nm light irradiation. The present investigation offers a promising approach to the development of high-performance photocatalysts the combination of photochromism and heterojunction engineering.
Incorporation of isophthalate ion derivatives into octacalcium phosphate for enhanced diagnostic bioimaging applications.
Trithipchatsakul S, Yoshizaki M, Wang Y … +5 more , Shimabukuro M, Matsuda A, Kawashita M, Viphavakit C, Yokoi T
Dalton Trans · 2026 Jun · PMID 42171060 · Publisher ↗
Octacalcium phosphate (OCP) with incorporated aromatic dicarboxylate ions exhibits visible-light and near-infrared (NIR) fluorescence, making it a promising platform for the development of diagnostic materials for bone r...
Octacalcium phosphate (OCP) with incorporated aromatic dicarboxylate ions exhibits visible-light and near-infrared (NIR) fluorescence, making it a promising platform for the development of diagnostic materials for bone repair and bioimaging. In this study, isophthalate ion (IP) derivatives, , 5-methylisophthalate ions (MeIP), 5-aminoisophthalate ions (AmIP), 5-hydroxyisophthalate ions (HyIP), and 5-sulfoisophthalate ions (SuIP), were incorporated with OCP a wet chemical method, and the effects of different functional groups in IP on the fluorescence properties were explored. MeIP, AmIP, and HyIP were successfully incorporated into the OCP crystal structure, whereas SuIP remained adsorbed onto the surface of the OCP, as confirmed by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and UV-VIS diffuse reflectance spectroscopy (DRS). Thermal analysis revealed that SuIP-OCP exhibited the highest thermal stability, surpassing that of pure OCP, while MeIP-OCP demonstrated the lowest thermal stability. AmIP-OCP and HyIP-OCP emitted visible fluorescence when excited with UV light. Interestingly, MeIP-OCP exhibited broad fluorescence, with strong emission in the UV region and continuous emission extending into the visible range, indicating its potential as an advanced material for applications requiring fluorescence across both the UV and visible regions. This study offers an approach for designing fluorescent OCP that provides fluorescence for diagnostic applications in bioimaging.
Rational design of novel organometallic -acylhydrazones with potent antiparasitic activity on and .
Toro-Sánchez PM, Lucero A, Villaman D … +7 more , Moncada-Basualto M, Arancibia R, Wilkinson SR, Levín P, Cisterna J, Brito I, López C
Dalton Trans · 2026 Jun · PMID 42149050 · Publisher ↗
This work describes the synthesis and characterization of organometallic -acylhydrazones (NAHs) of general formula R-C(O)-NH-NC(R)(4- or 5-nitrothienyl) (4a,b-7a,b), where R = ferrocenyl (a) or cyrhetrenyl (b) and R = H...
This work describes the synthesis and characterization of organometallic -acylhydrazones (NAHs) of general formula R-C(O)-NH-NC(R)(4- or 5-nitrothienyl) (4a,b-7a,b), where R = ferrocenyl (a) or cyrhetrenyl (b) and R = H or Me. The X-ray crystal structures of 4b, 5a, 5b, and 6b are described. UV-Vis studies confirmed that the compounds remained stable in DMSO/buffer mixtures for 24 h. studies of the biological activities of 4a,b-7a,b against () and () showed that the organometallic derivatives were more active against (EC = 0.18-12.9 μM) than against (EC = 4.24-78.8 μM). Except for 5b, cyrhetrenyl derivatives were more potent than their ferrocenyl analogs, showing up to a 7-fold increase in antiparasitic activity. In all cases, the 5-nitrothiophene derivatives (6a,b-7a,b) also outperformed their 4-nitro analogs (4a,b-5a,b), underscoring the strong impact of nitro-group positioning on biological activity. Compound 6b proved to be the most promising anti- agent due to its potency (EC = 0.47 μM) and selectivity (SI = 110). Comparison of data for 6a and 6b and their isomers 8a and 8b [R-C(H)N-NH-C(O)(5-nitrothienyl)] revealed that antiparasitic activity and cytotoxicity are strongly influenced by the position of the acylhydrazone group linking the organometallic fragment and the nitroheterocycle. Evaluation of susceptibility showed that the 5-nitro derivatives undergo Type I nitroreductase-dependent activation (-/+ ratios: 4.2-5.6), while the 4-nitro counterparts exhibited only minor shifts (1.5-2.0). These results indicate that small structural modifications in NAHs can significantly affect their antiparasitic properties.
An approach for ultrafast growth of zinc oxide nanorods microwave irradiation.
Sourav S, Abdul Aziz A, Ali Dheyab M
Dalton Trans · 2026 Jun · PMID 42149048 · Publisher ↗
A sealed-vessel approach produced high-purity wurtzite hexagonal ZnO nanorods (63, JCPDS 00-36-1451) with an exceptionally rapid holding duration of 50 s at 150 °C, utilizing microwave radiation from a Monowave 400 react...
A sealed-vessel approach produced high-purity wurtzite hexagonal ZnO nanorods (63, JCPDS 00-36-1451) with an exceptionally rapid holding duration of 50 s at 150 °C, utilizing microwave radiation from a Monowave 400 reactor. The process is more rapid than prior microwave methods, which require 2-7 min, and is significantly quicker than hydrothermal and sol-gel techniques that take hours to days, utilizing less than 10 Wh of energy compared to the energy-intensive hydrothermal method (energy savings exceeding 95%). The XRD study indicated a Scherrer crystallite size of 25.22 nm, a crystallinity of 48.5%, and a microstrain, as per the Williamson-Hall equation, of × 10 = 3.39. The results are consistent with a highly organized hexagonal wurtzite structure characterized by cell parameters = = 3.2494 Å and = 5.2066 Å. A TEM study of 100 nanorods revealed a uniform morphology with an average diameter of 22.4 ± 3.2 nm, a length of 185 ± 25 nm, and an aspect ratio of 8.3 ± 1.4, indicating preferential development along the -axis attributable to microwave coupling. The UV-Vis spectrophotometer yielded a cutoff absorption wavelength of = 374 nm, which corresponds to a band gap energy of 3.318 eV. The Fourier transformed infrared (FTIR) spectra validated the lattice vibrations of Zn-O bonds at 436 and 630 cm. Energy dispersive X-ray (EDX) revealed a near-stoichiometric composition (Zn = 51.48% and O = 48.52%), with no detected contaminants.
Beyond layer stacking: molecular RuO dimer correlations in pressure-synthesized BaNbRuO.
Peng C, Xu M, Li J … +1 more , Xie W
Dalton Trans · 2026 Jun · PMID 42149005 · Publisher ↗
Ruthenium-based oxides featuring face-sharing octahedra provide a powerful chemical platform for tuning correlated electronic states through direct metal-metal interactions and valence control. Here we report the high-pr...
Ruthenium-based oxides featuring face-sharing octahedra provide a powerful chemical platform for tuning correlated electronic states through direct metal-metal interactions and valence control. Here we report the high-pressure, high-temperature synthesis and comprehensive characterization of BaNbRuO, a previously unreported 6H-type hexagonal perovskite. Single-crystal and powder X-ray diffraction measurements confirm a fully ordered structure composed of face-sharing RuO dimers separated by corner-sharing NbO octahedra, crystallizing in the 6/ space group. Charge balance analysis reveals an unusually low mixed Ru/Ru oxidation state (nominal Ru), representing a reduced Ru valence realized within the BaMRuO family. Magnetic susceptibility measurements show Curie-Weiss behavior at high temperatures with an effective magnetic moment of 2.39 per formula unit and a negative Curie-Weiss temperature, indicating predominant antiferromagnetic interactions. Below ∼15 K, a bifurcation between zero-field-cooled and field-cooled susceptibilities emerges, while the absence of a frequency-dependent shift in AC susceptibility and the lack of a λ-type anomaly in specific heat down to 1.8 K indicate a frozen spin state with short-range correlations rather than long-range magnetic order or a canonical spin-glass transition. Electrical transport measurements reveal a broad resistivity maximum near 35 K followed by a low-temperature upturn and pronounced positive magnetoresistance. Remarkably, the temperature dependence of resistance closely resembles that of the nine-layer BaRuO polytype, despite the structural similarity of BaNbRuO to the four-layer phase. These results demonstrate that the electronic and magnetic properties of BaNbRuO are governed primarily by the molecular electronic state of the RuO dimers rather than by crystallographic stacking alone, underscoring the central role of dimer-based correlations in low-valence ruthenates.
Rhodacarborane complexes with a triphenylphosphonium substituent as efficient catalysts for on-water transfer hydrogenation of carbonyl compounds.
Vinogradov MM, Nelyubina YV, Godovikov IA … +4 more , Godovikova MI, Kharitonov VB, Podyacheva ES, Rodionov AN
Dalton Trans · 2026 Jun · PMID 42148998 · Publisher ↗
Two isomeric rhodacarborane chloride complexes [1,8-Bn-2,2-Cl--PPh-2,1,8--RhCBH] ( = 7 and 11) were synthesized. One of them ( = 7) exhibits high catalytic activity in the on-water reduction of aromatic and aliphatic ald...
Two isomeric rhodacarborane chloride complexes [1,8-Bn-2,2-Cl--PPh-2,1,8--RhCBH] ( = 7 and 11) were synthesized. One of them ( = 7) exhibits high catalytic activity in the on-water reduction of aromatic and aliphatic aldehydes and ketones with ammonium formate to the corresponding alcohols with a 0.2 mol% loading. The enantiopure form of a planar chiral catalyst was obtained isolation of a cyclometallated complex with ()-proline. The enantiopure form of the catalyst affords alcohols with enantiomeric excess when prochiral ketones are used in the reaction. The same catalyst is active in the Oppenauer-type oxidation of (±)-1-phenylethanol with acetone in the presence of KCO. The transfer hydrogenation is accompanied by reversible cyclometallation of the catalytic species engaging the -CH bonds of PPh.
Synthesis of Lewis acid-base adducts between trimesityltrieles and potassium cyanate and its heavier homologues.
Dollberg K, Lochte M, Weiß P … +4 more , Nitzsche J, Mészáros K, von Hänisch C, Tambornino F
Dalton Trans · 2026 May · PMID 42148982 · Publisher ↗
Lewis acid-base adducts between trimesityltrieles (MMes; Mes = 2,4,6-trimethylbenzene, M = Al-In) and potassium cyanate homologues (KNCE; E = O, S, Se) were synthesised in the presence of 18-crown-6 as an encapsulating a...
Lewis acid-base adducts between trimesityltrieles (MMes; Mes = 2,4,6-trimethylbenzene, M = Al-In) and potassium cyanate homologues (KNCE; E = O, S, Se) were synthesised in the presence of 18-crown-6 as an encapsulating agent. A series of compounds of the general composition [K(18c6)(thf)ECN(MMes)] was obtained and comprehensively characterised by multinuclear NMR spectroscopy, infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Structural analyses reveal systematic trends across both the triel and chalcogen series, while spectroscopic data provide insight into the electronic consequences of Lewis acid coordination. Complementary solubility studies demonstrate that adduct formation enhances the solubility of the otherwise poorly soluble potassium salts in selected solvents. The results highlight a class of Lewis acid-base adducts involving negatively charged cyanate and chalcogenocyanate fragments that has remained largely unexplored.
Tuning the crystal structure, optical band gap and persistent luminescence performance of a Cr-doped LiGaO spinel by adding aluminium and indium.
Karabut A, Zhydachevska H, Wachnicki Ł … +8 more , Hreb V, Vasylechko L, Hizhnyi Y, Shevtsova T, Luchechko A, Pieniążek A, Berkowski M, Zhydachevskyy Y
Dalton Trans · 2026 Jun · PMID 42148976 · Publisher ↗
The possibility of tuning the optical band gap, crystal structure and persistent luminescence performance of a Cr-doped LiGaO spinel by partially replacing Ga with Al and/or In has been studied extensively. For this purp...
The possibility of tuning the optical band gap, crystal structure and persistent luminescence performance of a Cr-doped LiGaO spinel by partially replacing Ga with Al and/or In has been studied extensively. For this purpose, a series of Cr-doped Li(GaAlIn)O ( = 0…0.5; = 0…0.1) microcrystalline phosphors were synthesised using a conventional solid-state reaction method and characterised using powder X-ray diffraction, SEM-EDX and luminescence techniques. DFT-based electronic structure calculations were carried out for the same Li(GaAlIn)O compositions, and the results were compared with the experimental ones. Based on the studies performed, the mechanism of Al and In incorporation into the LiGaO spinel structure as well as the tuning of the crystal lattice parameters, the local structure of M (M = Ga, Al, and In) cations and the optical band gap of the material have been established. The multicentre structure and the broadening of the local structural disorder of the octahedrally coordinated Cr centres observed in this case have been confirmed by high-resolution, low-temperature photoluminescence measurements. Band gap engineering through alterations in the chemical composition of the LiGaO spinel, as well as the depth of the native point defects responsible for charge trapping, allows for the efficient tuning of the thermoluminescence and persistent luminescence properties of Li(GaAlIn)O:Cr phosphors. Thus, the room-temperature persistent luminescence performance of the phosphors modified by the addition of Al and annealing under an oxygen-free atmosphere was increased threefold compared to the pristine LiGaO:Cr phosphor synthesised under the same conditions.
Hollow N-doped carbon nanocages anchoring Ni-Ru bimetallic nanoparticles for enhanced peroxidase-like activity.
Li Y, Chen Y, Han S … +3 more , Xu J, Yin XB, Zhang M
Dalton Trans · 2026 Jun · PMID 42148973 · Publisher ↗
Hollow structured composites with various elemental compositions and complex shell architectures exhibit great potential in application of heterogeneous catalysis. However, the synthesis of bimetallic alloy nanoparticles...
Hollow structured composites with various elemental compositions and complex shell architectures exhibit great potential in application of heterogeneous catalysis. However, the synthesis of bimetallic alloy nanoparticles (NPs) supported by hollow carbon nanocages is a serious challenge. Herein, we report a streamlined synthesis of hollow spherical Ni/Ru bimetallic NPs embedded in N-doped hollow carbon nanocages (Ni/Ru@HNCs) a carbonized organic polymer-mediated hard-templating strategy. Core-shell structured SiO@polydopamine-Ni (PDA-Ni) composites are firstly prepared through a one-pot method. Subsequent high-temperature carbonization and KOH etching generate Ni@HNCs featuring a hollow architecture, high specific surface area, abundant active sites, and efficient mass transport. Ru species are then introduced hydrothermally, where a spontaneous galvanic replacement reaction between metallic Ni and Ru ions drives the formation and uniform anchoring of Ni-Ru alloy NPs on the N-doped carbon framework. The resultant Ni/Ru@HNCs exhibit exceptional peroxidase-mimicking activity, efficiently catalyzing the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to yield a vivid blue product (oxTMB). Capitalizing on this robust catalytic performance, a sensitive colorimetric sensing platform is established for the rapid and selective detection of tea polyphenols (TP). This work not only demonstrates a rational design of high-performance bimetallic nanozymes with precisely controlled structure and composition but also provides a versatile, scalable strategy for developing advanced enzyme-mimetic materials for biosensing and food safety applications.
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