Generic and facile mechanochemical access to versatile lattice-confined Pd(ii)-based heterometallic sites.

Metal-organic frameworks (MOFs) show remarkable potential in a broad array of applications given their physical and chemical versatility. Classical synthesis of MOFs is performed using solution chemistry at elevated temperatures to achieve reversible metal-ligand bond formation. These harsh conditions may not be suitable for chemical species sensitive to high temperature or prone to deleterious reactions with solvents. For instance, Pd(ii) is susceptible to reduction under solvothermal conditions and is not a common metal node of MOFs. We report a generic and facile mechanochemical strategy that directly incorporates a series of Pd(ii)-based heterobimetallic clusters into MOFs as metal nodes without Pd(ii) being reduced to Pd(0). Mechanochemistry features advantages of short reaction time, minimum solvent, high reaction yield, and high degree of synthetic control. Catalytic performances of lattice-confined heterobimetallic sites are examined for nitrene transfer reactions and we demonstrate that the chemoselectivity for allylic amination versus olefin aziridination is readily tuned by the identity of the first-row metal ion in Pd(ii)-based heterobimetallic clusters.

Bifunctional Metal-Organic Nanoballs Featuring Lewis Acidic and Basic Sites as a New Platform for One-Pot Tandem Catalysis.

The design and synthesis of polyhedra using coordination-driven self-assembly has been an intriguing research area for synthetic chemists. Metal-organic polyhedra are a class of intricate molecular architectures that have garnered significant attention in the literature due to their diverse structures and potential applications. Hereby, we report Cu-MOP, a bifunctional metal-organic cuboctahedra built using 2,6-dimethylpyridine-3,5-dicarboxylic acid and copper acetate at room temperature. The presence of both Lewis basic pyridine groups and Lewis acidic copper sites imparts catalytic activity to Cu-MOP for the tandem one-pot deacetalization-Knoevenagel/Henry reactions. The effect of solvent system and time duration on the yields of the reactions was studied, and the results illustrate the promising potential of these metal-organic cuboctahedra, also known as nanoballs for applications in catalysis.

Facile mechanochemical synthesis of MIL-53 and its isoreticular analogues with a glance at reaction reversibility.

MIL-53 represents one of the most notable metal-organic frameworks given its unique structural flexibility and remarkable thermal stability. In this study, a shaker-type ball milling method has been developed into a facile and generalizable synthetic strategy to access a family of MIL-53 type materials under ambient conditions. During the explorations of [M(OH)(fumarate)] (M = Al, Ga, and In), we report a positive correlation between the metal-ligand (M-L) bond reversibility and the size of resultant crystallites under the mechanochemical process. The more kinetically labile the M-L bond is, the larger the afforded crystallite size is.

Integrating porphyrin-based nanoporous organic polymers with electrochemical aptasensors for ultratrace detection of kanamycin.

The synthesis and characterization of two new porphyrin-based porous organic polymers (POPs) via Sonogashira cross-coupling reaction and leverage the two obtained POPs is reported for the fabrication of electrochemical aptasensors to detect kanamycin at an ultratrace level. The resultant electrochemical aptasensor demonstrates a high linear relationship with the logarithmic value of kanamycin concentration in the range 5 × 10-5-5 µg/L with the limit of detection of 17.6 pg/L or 36.3 fM. During the analysis of real samples from milk and river, a relative standard deviation of less than 4.39%, and good recovery values in the range 97.0-105% were obtained.

Mechanochemical Access to Catechol-Derived Metal-Organic Frameworks.

Mechanochemistry, a resurging synthetic approach, has been developed into an effective and controllable method to access a family of crystalline porous catechol-derived metal-organic frameworks (MOFs) for the first time. We have identified that the obtained crystalline phase is readily tunable by precursors and the addition of solvents or drying agents. The described mechanochemistry allows us to synthesize these materials in a highly sustainable manner. Thus, mechanochemistry is expected to pave a promising avenue to access a broader class of MOF materials, in addition to those based on the motifs of carboxylic acid or imidazole.

Universal machine-learning algorithm for predicting adsorption performance of organic molecules based on limited data set: Importance of feature description.

Adsorption of organic molecules from aqueous solution offers a simple and effective method for their removal. Recently, there have been several attempts to apply machine learning (ML) for this problem. To this end, polyparameter linear free energy relationships (pp-LFERs) were employed, and poor prediction results were observed outside model applicability domain of pp-LFERs. In this study, we improved the applicability of ML methods by adopting a chemical-structure (CS) based approach. We used the prediction of adsorption of organic molecules on carbon-based adsorbents as an example. Our results show that this approach can fully differentiate the structural differences between any organic molecules, while providing significant information that is relevant to their interaction with the adsorbents. We compared two CS feature descriptors: 3D-coordination and simplified molecular-input line-entry system (SMILES). We then built CS-ML models based on neural networks (NN) and extreme gradient boosting (XGB). They all outperformed pp-LFERs based models and are capable to accurately predict adsorption isotherm of isomers with similar physiochemical properties such as chiral molecules, even though they are trained with achiral molecules and racemates. We found for predicting adsorption isotherm, XGB shows better performance than NN, and 3D-coordinations allow effective differentiation between organic molecules.

Modelling and simulation of borehole seismoelectric response with an impermeable wall.

In this paper, we construct a borehole model with an impermeable/permeable wall and study the seismoelectric responses. First, we define the boundary conditions at the borehole wall, then the acoustic field and electric field are simulated by the real axis integral method. In order to have a comprehensive analysis of the body wave components, we use the secant integral method to simulate the body waves and give the excitation intensity spectrum in the frequency domain. The results show that the impermeability of the borehole wall significantly increases the amplitude of the acoustic field generated by Stoneley waves. This is because the closed pores at the boundary make Stoneley waves energy leak more slowly and hence attenuating less. The impermeable borehole wall weakens the electromagnetic interface response. Besides, both P wave and S wave and their accompanying electric field properties are affected by boundary connectivity. This investigation provides a theoretical basis for qualitatively judging borehole wall permeability by the seismoelectric signals.

Mechanochemistry of Group 4 Element-Based Metal-Organic Frameworks.

Mechanochemical synthesis is emerging as an environmentally friendly yet efficient approach to preparing metal-organic frameworks (MOFs). Herein, we report our systematic investigation on the mechanochemical syntheses of Group 4 element-based MOFs. The developed mechanochemistry allows us to synthesize a family of Hf4O4(OH)4(OOC)12-based MOFs. Integrating [Zr6O4(OH)4(OAc)12]2 and [Hf6O4(OH)4(OAc)12]2 under the mechanochemical conditions leads to a unique family of cluster-precise multimetallic MOFs that cannot be accessed by the conventional solvothermal synthesis. Extensive efforts have not yielded an effective pathway for preparing TiIV-derived MOFs, tentatively because of the relatively low Ti-O bond dissociation energy.

A porous supramolecular ionic solid.

We report a synthetic strategy to integrate discrete coordination cages into extended porous materials by decorating opposite charges on the singular cage, which offers multidirectional electrostatic forces among cages and leads to a porous supramolecular ionic solid. The resulting material is non-centrosymmetric and affords a piezoelectric coefficient of 8.19 pC N-1, higher than that of the wurtzite ZnO.

Ego-Resiliency and Perceived Social Support in Late Childhood: A Latent Growth Modeling Approach.

This study explored the change trajectory of schoolchildren's ego-resiliency and perceived social support and investigated the effect of perceived social support on ego-resiliency across four time points. A sample of 437 children aged 8-13 years (M = 10.99, SD = 0.70, 51.5% boys) completed assessments at four time points. The results indicated that ego-resiliency showed an increasing linear trend and perceived social support showed a declining linear trend. Perceived social support had a positive effect on ego-resiliency over time. In addition, the initial status of perceived social support negatively predicted the growth trend of ego-resiliency, and the initial status of ego-resiliency negatively predicted the declining trend of perceived social support. The implications for theory and practice are discussed.

A Mixed-Metal Porphyrinic Framework Promoting Gas-Phase CO2 Photoreduction without Organic Sacrificial Agents.

A photoactive porphyrinic metal-organic framework (MOF) has been prepared by exchanging Ti into a Zr-based MOF precursor. The resultant mixed-metal Ti/Zr porphyrinic MOF demonstrates much-improved efficiency for gas-phase CO2 photoreduction into CH4 and CO under visible-light irradiation using water vapor compared to the parent Zr-MOF. Insightful studies have been conducted to probe the photocatalysis processes. This work provides the first example of gas-phase CO2 photoreduction into methane without organic sacrificial agents on a MOF platform, thereby paving an avenue for developing MOF-based photocatalysts for application in CO2 photoreduction and other types of photoreactions.

Synthesis of atomically precise single-crystalline Ru2-based coordination polymers.

Methods to incorporate kinetically inert metal nodes and highly basic ligands into single-crystalline metal-organic frameworks (MOFs) are scarce, which prevents synthesis and systematic variation of many potential heterogeneous catalyst materials. Here we demonstrate that metallopolymerization of kinetically inert Ru2 metallomonomers via labile Ag-N bonds provides access to a family of atomically precise single-crystalline Ru2-based coordination polymers with varied network topology and primary coordination sphere.

Machine learning-based operation skills assessment with vascular difficulty index for vascular intervention surgery.

An accurate assessment of surgical operation skills is essential for improving the vascular intervention surgical outcome and the performance of endovascular surgery robots. In existing studies, subjective and objective assessments of surgical operation skills use a variety of indicators, such as the operation speed and operation smoothness. However, the vascular conditions of particular patients have not been considered in the assessment, leading to deviations in the evaluation. Therefore, in this paper, an operation skills assessment method including the vascular difficulty level index for catheter insertion at the aortic arch in endovascular surgery is proposed. First, the model describing the difficulty of the vascular anatomical structure is established with characteristics of different aortic arch branches based on machine learning. Afterwards, the vascular difficulty level is set as an objective index combined with operating characteristics extracted from the operations performed by surgeons to evaluate the surgical operation skills at the aortic arch using machine learning. The accuracy of the assessment improves from 86.67 to 96.67% after inclusion of the vascular difficulty as an evaluation indicator to more objectively and accurately evaluate skills. The method described in this paper can be adopted to train novice surgeons in endovascular surgery, and for studies of vascular interventional surgery robots. Graphical abstract Operation skill assessment with vascular difficulty for vascular interventional surgery.

Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization.

Atomistic control of the coordination environment of lattice ions and the distribution of metal sites within crystalline mixed-metal coordination polymers remain significant synthetic challenges. Herein is reported the mechanochemical synthesis of a reticular family of crystalline heterobimetallic metal-organic frameworks (MOFs) is now achieved by polymerization of molecular Ru2 [II,III] complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc)2 . The resulting crystalline heterobimetallic MOFs are solid solutions of Ru2 and Cu2 sites housed within [M3 L2 ] phases. The developed mechanochemical strategy is modular and allows for systematic control of the primary coordination sphere of the Ru2 sites within an isoreticular family of materials. This strategy is anticipated to provide a rational approach to atomically precise mixed-metal materials.

Perceived Teacher Autonomy Support and School Engagement of Tibetan Students in Elementary and Middle Schools: Mediating Effect of Self-Efficacy and Academic Emotions.

School engagement (SE) refers to the intensity and quality of emotions experienced by students when commencing and carrying out learning activities, and includes behavioral, emotional, and cognitive engagement. A high SE level promotes academic achievement, reduces students' behavioral problems, and prevents school dropout. This study, whose participants were 819 students from Tibetan areas, explored the impact of teacher autonomy support (TAS) on students' SE and the mechanisms involved in this relationship. The results showed that TAS had a positive impact on SE, while students' self-efficacy had a mediating effect between TAS and SE. On the one hand, TAS affected self-efficacy through academic interest and ultimately influenced SE; moreover, TAS negatively affected academic anxiety, indirectly inhibiting the negative effect of academic anxiety on SE through self-efficacy. The theoretical and practical implications of the study findings are discussed.

Measuring and Modulating Substrate Confinement during Nitrogen-Atom Transfer in a Ru2-Based Metal-Organic Framework.

The porosity and synthetic tunability of metal-organic frameworks (MOFs) has motivated interest in application of these materials as designer heterogeneous catalysts. While understanding substrate mobility in these materials is critical to the rational development of highly active catalyst platforms, experimental data are rarely available. Here we demonstrate kinetic isotope effect (KIE) analysis enables direct evaluation of the extent of substrate confinement as a function of material mesoporosity. Further, we provide evidence that suggests substrate confinement within a microporous Ru2-based MOF gives rise to quantum tunneling during interstitial C-H amination. The reported data provide the first evidence for tunneling during interstitial MOF chemistry and illustrate an experimental strategy to evaluate the impact of material structure on substrate mobility in porous catalysts.

How Leaders' Psychological Capital Influence Their Followers' Psychological Capital: Social Exchange or Emotional Contagion.

Using a sample of 32 work teams (32 work team leaders and their 321 followers) in Chinese cultural context, this study investigated the relationships between leaders' and their followers' psychological capital and the multilevel multiple mediation effects of social exchange and emotional contagion. PsyCap questionnaire (PCQ), leader-member exchange scale, and the positive affect scale in the positive and negative affect scale (PANAS) were adopted to measure variables. A total of 430 questionnaires were distributed in 2014 and the response rates were 90.2%. Structural equation model and hierarchical linear model were applied to analyze the survey data. The results revealed that leaders' psychological capital had a positive influence on their followers' psychological capital. Leader-member exchange was the cross-level mediator between leaders' psychological capital and their followers'. The cross-level mediating effect of leaders' positive emotions perceived by followers was not significant. The results of this study extended the social exchange theory and enriched researches on leadership. The implication was discussed in details.

Iodosylbenzene Coordination Chemistry Relevant to Metal-Organic Framework Catalysis.

Hypervalent iodine compounds formally feature expanded valence shells at iodine. These reagents are broadly used in synthetic chemistry due to the ability to participate in well-defined oxidation-reduction processes and because the ligand-exchange chemistry intrinsic to the hypervalent center allows hypervalent iodine compounds to be applied to a broad array of oxidative substrate functionalization reactions. We recently developed methods to generate these compounds from O2 that are predicated on diverting reactive intermediates of aldehyde autoxidation toward the oxidation of aryl iodides. Coupling the aerobic oxidation of aryl iodides with catalysts that effect C-H bond oxidation would provide a strategy to achieve aerobic C-H oxidation chemistry. In this Forum Article, we discuss the aspects of hypervalent iodine chemistry and bonding that render this class of reagents attractive lynchpins for aerobic oxidation chemistry. We then discuss the oxidation processes relevant to the aerobic preparation of 2-(tert-butylsulfonyl)iodosylbenzene, which is a popular hypervalent iodine reagent for use with porous metal-organic framework (MOF)-based catalysts because it displays significantly enhanced solubility as compared with unsubstituted iodosylbenzene. We demonstrate that popular synthetic methods to this reagent often provide material that displays unpredictable disproportionation behavior due to the presence of trace impurities. We provide a revised synthetic route that avoids impurities common in the reported methods and provides access to material that displays predictable stability. Finally, we describe the coordination chemistry of hypervalent iodine compounds with metal clusters relevant to MOF chemistry and discuss the potential implications of this coordination chemistry to catalysis in MOF scaffolds.

Templating metastable Pd2 carboxylate aggregates.

Evaluation of the potential for metal-metal (M-M) cooperation to enable catalysis requires access to specific polynuclear aggregates that display appropriate geometry and size. In many cases, exerting synthetic control over the aggregation of simple metal salts is a challenge. For example, Pd(ii) acetate self assembles as a trimer (i.e. Pd3(OAc)6) both in the solid state and in solution and does not feature close Pd-Pd interactions. Related carboxylate-supported Pd2 aggregates (i.e. Pd2(OAc)4), which would feature close Pd-Pd interactions, are thermodynamically metastable in solution phase and thus largely unavailable. Here we demonstrate ion metathesis within pre-formed metal-organic frameworks (MOFs) to prepare metastable Pd2 tetracarboxylates sites. The newly synthesized materials are characterized by elemental analysis, PXRD, SCXRD, EXAFS, XANES, and gas adsorption analysis. In addition, the critical role of network solvation on the kinetics of ion metathesis was revealed by coupled TGA-MS and ICP-MS experiments. The demonstration of templated ion metathesis to generate specific metastable coordination sites that are inaccessible in solution phase chemistry represents a new opportunity to interrogate the chemistry of specific polynuclear metal aggregates.

In Operando Analysis of Diffusion in Porous Metal-Organic Framework Catalysts.

The potential to exert atomistic control over the structure of site-isolated catalyst sites, as well as the topology and chemical environment of interstitial pore spaces, has inspired efforts to apply porous metal-organic frameworks (MOFs) as catalysts for fine chemical synthesis. In analogy to enzyme-catalyzed reactions, MOF catalysts have been proposed as platforms in which substrate confinement could be used to achieve chemo- and stereoselectivities that are orthogonal to solution-phase catalysts. In order to leverage the tunable pore topology of MOFs to impact catalyst selectivity, catalysis must proceed at interstitial catalyst sites, rather than at solvent-exposed interfacial sites. This Minireview addresses challenges inherent to interstitial MOF catalysis by 1) describing the diffusional processes available to sorbates in porous materials, 2) discussing critical factors that impact the diffusion rate of substrates in porous materials, and 3) presenting in operando experimental strategies to assess the relative rates of substrate diffusion and catalyst turnover in MOF catalysis. It is anticipated that the continued development of in operando tools to evaluate substrate diffusion in porous catalysts will advance the application of these materials in fine chemical synthesis.