Integration of morphology and electronic structure modulation on cobalt phosphide nanosheets to boost photocatalytic hydrogen evolution from ammonia borane hydrolysis

The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.

Synthesis, Structural Characterization and Antimicrobial Activity of a Novel Cobalt(II) Complex Based on 3-Methyl-1-Phenyl-4-(2-Thienoyl)-Pyrazol-5-One

New cobalt(II) complex, [Co(O2C15H11N2S)2(OH2)2]∙2H2O (1∙2H2O), has been synthesized upon reaction of cobalt chloride hexahydrate (Co(Cl)2∙6H2O) with 3-methyl-1-Phenyl-4-(2-thienoyl)-pyrazol-5-one (referred as HL) in ethanol at room temperature. Single crystal X-ray diffraction (XRD), spectroscopic methods, and microelemental analyses were used to characterize 1∙2H2O. Compound 1∙2H2O crystallizes in the orthorhombic crystal system with a Pbca space group and with the cobalt atom being pseudo-octahedral coordinated. The broth microdilution technique was used to screen the free ligand (HL) and the complex (1∙2H2O) for antimicrobial activities. HL has a low activity (MIC > 100 μg/mL) on all microorganisms, whereas compound 1∙2H2O displayed moderate activity (10 ∙2H2O exhibited bactericidal and fungicidal activity respectively on all the bacteria and yeasts tested. These findings reveal that the antimicrobial activity of HL was enhanced upon coordination to Co(II) ion against all microorganisms (bacteria and fungus).

Structures and magnetism of dinuclear Co complexes based on imine derivatives

This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives:bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether(L1),bis-[4-(2-pyridylmethyleneamino)-phenyl]ether(L2),and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane(L3).Single-crystal X-ray diffraction analysis reveals that the complexes[Co_(2)(L1)3](ClO_(4))4·2CH_(3)CN(1),[Co_(2)(L2)3](ClO_(4))4·2CH_(3)OH(2),and[Co_(2)(L3)3](ClO_(4))4·2CH_(3)OH(3)all exhibit a dinuclear structure.Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K,with the average Co-N bond length increasing from 0.2139(3)to 0.2153(3)nm.Meanwhile,the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2.Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.CCDC:2347354,1(120 K);2347355,2(120 K);2347356,3(120 K);2347357,3(400 K).

Modeling time-dependent mechanical behavior of hard rock considering excavation-induced damage and complex 3D stress states

To investigate the long-term stability of deep rocks,a three-dimensional(3D)time-dependent model that accounts for excavation-induced damage and complex stress state is developed.This model comprises three main components:a 3D viscoplastic isotropic constitutive relation that considers excavation damage and complex stress state,a quantitative relationship between critical irreversible deformation and complex stress state,and evolution characteristics of strength parameters.The proposed model is implemented in a self-developed numerical code,i.e.CASRock.The reliability of the model is validated through experiments.It is indicated that the time-dependent fracturing potential index(xTFPI)at a given time during the attenuation creep stage shows a negative correlation with the extent of excavationinduced damage.The time-dependent fracturing process of rock demonstrates a distinct interval effect of the intermediate principal stress,thereby highlighting the 3D stress-dependent characteristic of the model.Finally,the influence of excavation-induced damage and intermediate principal stress on the time-dependent fracturing characteristics of the surrounding rocks around the tunnel is discussed.

Saturation Estimation with Complex Electrical Conductivity for Hydrate-Bearing Clayey Sediments:An Experimental Study

Clays have considerable influence on the electrical properties of hydrate-bearing sediments.It is desirable to understand the electrical properties of hydrate-bearing clayey sediments and to build hydrate saturation(S_(h))models for reservoir evaluation and monitoring.The electrical properties of tetrahydrofuran-hydrate-bearing sediments with montmorillonite are characterized by complex conductivity at frequencies from 0.01 Hz to 1 kHz.The effects of clay and Sh on the complex conductivity were analyzed.A decrease and increase in electrical conductance result from the clay-swelling-induced blockage and ion migration in the electrical double layer(EDL),respectively.The quadrature conductivity increases with the clay content up to 10%because of the increased surface site density of counterions in EDL.Both the in-phase conductivity and quadrature conductivity decrease consistently with increasing Sh from 0.50 to 0.90.Three sets of models for Sh evaluation were developed.The model based on the Simandoux equation outperforms Archie’s formula,with a root-mean-square error(E_(RMS))of 1.8%and 3.9%,respectively,highlighting the clay effects on the in-phase conductivity.The fre-quency effect correlations based on in-phase and quadrature conductivities exhibit inferior performance(E_(RMS)=11.6%and 13.2%,re-spectively)due to the challenge of choosing an appropriate pair of frequencies and intrinsic uncertainties from two measurements.The second-order Cole-Cole formula can be used to fit the complex-conductivity spectra.One pair of inverted Cole-Cole parameters,i.e.,characteristic time and chargeability,is employed to predict S_(h) with an E_(RMS) of 5.05%and 9.05%,respectively.

Extraction and recycling technologies of cobalt from primary and secondary resources:A comprehensive review

Cobalt has excellent electrochemical,magnetic,and heat properties.As a strategic resource,it has been applied in many hightech products.However,the recent rapid growth of the battery industry has substantially depleted cobalt resources,leading to a crisis of cobalt resource supply.The paper examines cobalt ore reserves and distribution,and the recent development and consumption of cobalt resources are summarized as well.In addition,the principles,advantages and disadvantages,and research status of various methods are discussed comprehensively.It can be concluded that the use of diverse sources(Cu-Co ores,Ni-Co ores,zinc plant residues,and waste cobalt products)for cobalt production should be enhanced to meet developmental requirements.Furthermore,in recovery technology,the pyro-hydrometallurgical process employs pyrometallurgy as the pretreatment to modify the phase structure of cobalt minerals,enhancing its recovery in the hydrometallurgical stage and facilitating high-purity cobalt production.Consequently,it represents a promising technology for future cobalt recovery.Lastly,based on the above conclusions,the prospects for cobalt are assessed regarding cobalt ore processing and sustainable cobalt recycling,for which further study should be conducted.

Synthesis, Structural Characterization and Antimicrobial Activity of a Novel Cobalt(II) Complex Based on 3-Methyl-1-Phenyl-4-(2-Thienoyl)-Pyrazol-5-One

New cobalt(II) complex, [Co(O2C15H11N2S)2(OH2)2]∙2H2O (1∙2H2O), has been synthesized upon reaction of cobalt chloride hexahydrate (Co(Cl)2∙6H2O) with 3-methyl-1-Phenyl-4-(2-thienoyl)-pyrazol-5-one (referred as HL) in ethanol at room temperature. Single crystal X-ray diffraction (XRD), spectroscopic methods, and microelemental analyses were used to characterize 1∙2H2O. Compound 1∙2H2O crystallizes in the orthorhombic crystal system with a Pbca space group and with the cobalt atom being pseudo-octahedral coordinated. The broth microdilution technique was used to screen the free ligand (HL) and the complex (1∙2H2O) for antimicrobial activities. HL has a low activity (MIC > 100 μg/mL) on all microorganisms, whereas compound 1∙2H2O displayed moderate activity (10 ∙2H2O exhibited bactericidal and fungicidal activity respectively on all the bacteria and yeasts tested. These findings reveal that the antimicrobial activity of HL was enhanced upon coordination to Co(II) ion against all microorganisms (bacteria and fungus).

A novel complex-high-order graph convolutional network paradigm:ChyGCN

In recent years,there has been a growing interest in graph convolutional networks(GCN).However,existing GCN and variants are predominantly based on simple graph or hypergraph structures,which restricts their ability to handle complex data correlations in practical applications.These limitations stem from the difficulty in establishing multiple hierarchies and acquiring adaptive weights for each of them.To address this issue,this paper introduces the latest concept of complex hypergraphs and constructs a versatile high-order multi-level data correlation model.This model is realized by establishing a three-tier structure of complexes-hypergraphs-vertices.Specifically,we start by establishing hyperedge clusters on a foundational network,utilizing a second-order hypergraph structure to depict potential correlations.For this second-order structure,truncation methods are used to assess and generate a three-layer composite structure.During the construction of the composite structure,an adaptive learning strategy is implemented to merge correlations across different levels.We evaluate this model on several popular datasets and compare it with recent state-of-the-art methods.The comprehensive assessment results demonstrate that the proposed model surpasses the existing methods,particularly in modeling implicit data correlations(the classification accuracy of nodes on five public datasets Cora,Citeseer,Pubmed,Github Web ML,and Facebook are 86.1±0.33,79.2±0.35,83.1±0.46,83.8±0.23,and 80.1±0.37,respectively).This indicates that our approach possesses advantages in handling datasets with implicit multi-level structures.

The component-activity interrelationship of cobalt-based bifunctional electrocatalysts for overall water splitting:Strategies and performance

Cobalt-based electrocatalysts take advantage of potentially harmonizable microstructure and flexible coupling effects compared to commercial noble metal-based catalytic materials.However,conventional water electrolysis systems based on cobalt-based monofunctional hydrogen evolution reaction(HER)or oxygen evolution reaction(OER)catalysts have certain shortcomings in terms of resource utilization and universality.In contrast,cobalt-based bifunctional catalysts(CBCs)have attracted much attention in recent years for overall water splitting systems because of their practicality and reduced preparation cost of electrolyzer.This review aims to address the latest development in CBCs for total hydrolysis.The main modification strategies of CBCs are systematically classified in water electrolysis to provide an overview of how to regulate their morphology and electronic configuration.Then,the catalytic performance of CBCs in total-hydrolysis is summarized according to the types of cobalt-based phosphides,sulfides and oxides,and the mechanism of strengthened electrocatalytic ability is emphasized through combining experiments and theoretical calculations.Future efforts are finally suggested to focus on exploring the dynamic conversion of reaction intermediates and building near-industrial CBCs,designing advanced CBC materials through micro-modulation,and addressing commercial applications.

Structural and magnetic properties of micropolycrystalline cobalt thin films fabricated by direct current magnetron sputtering

Pure cobalt(Co)thin films were fabricated by direct current magnetron sputtering,and the effects of sputtering power and pres-sure on the microstructure and electromagnetic properties of the films were investigated.As the sputtering power increases from 15 to 60 W,the Co thin films transition from an amorphous to a polycrystalline state,accompanied by an increase in the intercrystal pore width.Simultaneously,the resistivity decreases from 276 to 99μΩ·cm,coercivity increases from 162 to 293 Oe,and in-plane magnetic aniso-tropy disappears.As the sputtering pressure decreases from 1.6 to 0.2 Pa,grain size significantly increases,resistivity significantly de-creases,and the coercivity significantly increases(from 67 to 280 Oe),which can be attributed to the increase in defect width.Corres-pondingly,a quantitative model for the coercivity of Co thin films was formulated.The polycrystalline films sputtered under pressures of 0.2 and 0.4 Pa exhibit significant in-plane magnetic anisotropy,which is primarily attributable to increased microstress.

MOF-Derived Iron-Cobalt Phosphide Nanoframe as Bifunctional Electrocatalysts for Overall Water Splitting

Transition metal phosphides(TMPs)have emerged as an alternative to precious metals as efficient and low-cost catalysts for water electrolysis.Elemental doping and morphology control are effective approaches to further improve the performance of TMPs.Herein,Fe-doped CoP nanoframes(Fe-CoP NFs)with specific open cage configuration were designed and synthesized.The unique nano-framework structured Fe-CoP material shows overpotentials of only 255 and 122 mV at 10 mA cm^(−2)for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER),respectively,overwhelming most transition metal phosphides.For overall water splitting,the cell voltage is 1.65 V for Fe-CoP NFs at a current density of 10 mA cm^(−2),much superior to what is observed for the classical nanocubic structures.Fe-CoP NFs show no activity degradation up to 100 h which contrasts sharply with the rapidly decaying performance of noble metal catalyst reference.The superior electrocatalytic performance of Fe-CoP NFs due to abundant accessible active sites,reduced kinetic energy barrier,and preferable*O-containing intermediate adsorption is demonstrated through experimental observations and theoretical calculations.Our findings could provide a potential method for the preparation of multifunctional material with hollow structures and offer more hopeful prospects for obtaining efficient earth-abundant catalysts for water splitting.

High-Voltage and Fast-Charging Lithium Cobalt Oxide Cathodes: From Key Challenges and Strategies to Future Perspectives

Lithium-ion batteries(LIBs)with the“double-high”characteristics of high energy density and high power density are in urgent demand for facilitating the development of advanced portable electronics.However,the lithium ion(Li+)-storage performance of the most commercialized lithium cobalt oxide(LiCoO_(2),LCO)cathodes is still far from satisfactory in terms of high-voltage and fast-charging capabilities for reaching the double-high target.Herein,we systematically summarize and discuss high-voltage and fast-charging LCO cathodes,covering in depth the key fundamental challenges,latest advancements in modification strategies,and future perspectives in this field.Comprehensive and elaborated discussions are first presented on key fundamental challenges related to structural degradation,interfacial instability,the inhomogeneity reactions,and sluggish interfacial kinetics.We provide an instructive summary of deep insights into promising modification strategies and underlying mechanisms,categorized into element doping(Li-site,cobalt-/oxygen-site,and multi-site doping)for improved Li+diffusivity and bulkstructure stability;surface coating(dielectrics,ionic/electronic conductors,and their combination)for surface stability and conductivity;nanosizing;combinations of these strategies;and other strategies(i.e.,optimization of the electrolyte,binder,tortuosity of electrodes,charging protocols,and prelithiation methods).Finally,forward-looking perspectives and promising directions are sketched out and insightfully elucidated,providing constructive suggestions and instructions for designing and realizing high-voltage and fast-charging LCO cathodes for next-generation double-high LIBs.

Discovery of nano organo-clay complex pore-fractures in shale and its scientific significance:A case study of Cretaceous Qingshankou Formation shale,Songliao Basin,NE China

A new pore type,nano-scale organo-clay complex pore-fracture was first discovered based on argon ion polishing-field emission scanning electron microscopy,energy dispersive spectroscopy and three-dimensional reconstruction by focused ion-scanning electron in combination with analysis of TOC,R_(o)values,X-ray diffraction etc.in the Cretaceous Qingshankou Formation shale in the Songliao Basin,NE China.Such pore characteristics and evolution study show that:(1)Organo-clay complex pore-fractures are developed in the shale matrix and in the form of spongy and reticular aggregates.Different from circular or oval organic pores discovered in other shales,a single organo-clay complex pore is square,rectangular,rhombic or slaty,with the pore diameter generally less than 200 nm.(2)With thermal maturity increasing,the elements(C,Si,Al,O,Mg,Fe,etc.)in organo-clay complex change accordingly,showing that organic matter shrinkage due to hydrocarbon generation and clay mineral transformation both affect organo-clay complex pore-fracture formation.(3)At high thermal maturity,the Qingshankou Formation shale is dominated by nano-scale organo-clay complex pore-fractures with the percentage reaching more than 70%of total pore space.The spatial connectivity of organo-clay complex pore-fractures is significantly better than that of organic pores.It is suggested that organo-complex pore-fractures are the main pore space of laminar shale at high thermal maturity and are the main oil and gas accumulation space in the core area of continental shale oil.The discovery of nano-scale organo-clay complex pore-fractures changes the conventional view that inorganic pores are the main reservoir space and has scientific significance for the study of shale oil formation and accumulation laws.

Modification,application and expansion of electrode materials based on cobalt telluride

Metal(Li,Na,K,Al)-ion batteries and lithium-sulfur and lithium-tellurium batteries are gaining recognition for their eco-friendly characteristics,substantial energy density,and sustainable attributes.However,the overall performance of rechargeable batteries heavily depends on their electrode materials.Transition metal tellurides have recently gained significant attention due to their high electrical conductivity and density.Cobalt telluride has received the most extensive research due to its catalytic activity,unique magnetic properties,and diverse composition and crystal structure.Nevertheless,its limited conductivity and significant volume variation contribute to electrode structural deterioration and rapid capacity decline.This review comprehensively summarizes recent advances in rational design and synthesis of modified cobalt telluride-based electrodes,encompassing defect engineering(Te vacancies,cation vacancies,heterointerfaces,and homogeneous interfaces)and composite engineering(derived carbon from precursors,carbon fibers,Mxene,graphene nanosheets,etc.).Particularly,the intricate evolution mechanisms of the conversion reaction process during cycling are elucidated.Furthermore,these modified strategies applied to other transitional metal tellurides,such as iron telluride,nickel telluride,zinc telluride,copper telluride,molybdenum telluride,etc.,are also thoroughly summarized.Additionally,their application extends to emerging aqueous zinc-ion batteries.Finally,potential challenges and prospects are discussed to further propel the development of transition metal tellurides electrode materials for next-generation rechargeable batteries.

Assessing the dynamics of O_(2) desorption from cobalt phthalocyanine by in situ electrochemical scanning tunneling microscopy

We report here the in situ electrochemical scanning tunneling microscopy(ECSTM) study of cobalt phthalocyanine(CoPc)-catalyzed O_(2) evolution reaction(OER) and the dynamics of CoPc-O_(2) dissociation.The self-assembled CoPc monolayer is fabricated on Au(111) substrate and resolved by ECSTM in 0.1 M KOH electrolyte.The OH^(-)adsorption on CoPc prior to OER is observed in ECSTM images.During OER,the generated O_(2) adsorbed on Co Pc is observed in the CoPc monolayer.Potential step experiment is employed to monitor the desorption of OER-generated O_(2) from CoPc,which results in the decreasing surface coverage of CoPc-O_(2) with time.The rate constant of O_(2) desorption is evaluated through data fitting.The insights into the dynamics of Co-O_(2) dissociation at the molecular level via in situ imaging help understand the role of Co-O_(2) in oxygen reduction reaction(ORR) and OER.

Nano-Au-decorated hierarchical porous cobalt sulfide derived from ZIF-67 toward optimized oxygen evolution catalysis:Important roles of microstructures and electronic modulation

Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.

Complexity Considerations in the Heisenberg Uncertainty Principle

This work introduces a modification to the Heisenberg Uncertainty Principle (HUP) by incorporating quantum complexity, including potential nonlinear effects. Our theoretical framework extends the traditional HUP to consider the complexity of quantum states, offering a more nuanced understanding of measurement precision. By adding a complexity term to the uncertainty relation, we explore nonlinear modifications such as polynomial, exponential, and logarithmic functions. Rigorous mathematical derivations demonstrate the consistency of the modified principle with classical quantum mechanics and quantum information theory. We investigate the implications of this modified HUP for various aspects of quantum mechanics, including quantum metrology, quantum algorithms, quantum error correction, and quantum chaos. Additionally, we propose experimental protocols to test the validity of the modified HUP, evaluating their feasibility with current and near-term quantum technologies. This work highlights the importance of quantum complexity in quantum mechanics and provides a refined perspective on the interplay between complexity, entanglement, and uncertainty in quantum systems. The modified HUP has the potential to stimulate interdisciplinary research at the intersection of quantum physics, information theory, and complexity theory, with significant implications for the development of quantum technologies and the understanding of the quantum-to-classical transition.

Photocatalyst/metal-free sequential C-N/C-S bond formation:Synthesis of S-arylisothioureas via photoinduced EDA complex activation

A photocatalyst-free visible-light-promoted three-component reaction of thianthrenium salts,isothiocyanates,and amines is presented,which affords a rapid and efficient approach to S-arylisothioureas under mild conditions.This developed method exhibits the advantages of readily available raw materials,broad substrate scope,good functional tolerance,and operational simplicity.It is worth mentioning that the byproduct thianthrene can be recycled in quantity,ultimately maximizing the atomic economy of the reaction and avoiding chemical waste.Mechanism investigations support the strategy involving a photoinduced EDA complex.

Three-dimensional magnetic reconnection in complex multiple X-point configurations in an ancient solar-lunar terrestrial system

Magnetic reconnection processes in three-dimensional(3D)complex field configurations have been investigated in different magneto-plasma systems in space,laboratory,and astrophysical systems.Two-dimensional(2D)features of magnetic reconnection have been well developed and applied successfully to systems with symmetrical property,such as toroidal fusion plasmas and laboratory experiments with an axial symmetry.But in asymmetric systems,the 3D features are inevitably different from those in the 2D case.Magnetic reconnection structures in multiple celestial body systems,particularly star-planet-Moon systems,bring fresh insights to the understanding of the 3D geometry of reconnection.Thus,we take magnetic reconnection in an ancient solar-lunar terrestrial magneto-plasma system as an example by using its crucial parameters approximately estimated already and also some specific applications in pathways for energy and matter transports among Earth,ancient Moon,and the interplanetary magnetic field(IMF).Then,magnetic reconnection of the ancient lunar-terrestrial magnetospheres with the IMF is investigated numerically in this work.In a 3D simulation for the Earth-Moon-IMF system,topological features of complex magnetic reconnection configurations and dynamical characteristics of magnetic reconnection processes are studied.It is found that a coupled lunar-terrestrial magnetosphere is formed,and under various IMF orientations,multiple X-points emerge at distinct locations,showing three typical magnetic reconnection structures in such a geometry,i.e.,the X-line,the triple current sheets,and the A-B null pairs.The results can conduce to further understanding of reconnection physics in 3D for plasmas in complex magnetic configurations,and also a possible mechanism for energy and matters transport in evolutions of similar astrophysical systems.

Synthesis and Physico-Chemical Characterizations of Novel Hydrazone Ligands and Their Metal Complexes against Hormone-Dependent and Independent Cancers

This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.