MOF-Derived Zn/N-Doped Porous Carbon Film on a Carbon Nanotube for High-Performance Supercapacitors.

Designing high-performance binder-free electrochemical electrodes is crucially important toward supercapacitors. In this paper, a Zn/N-doped porous carbon film coating on flexible carbon nanotubes (ZIF-8@CT-800) derived from the epitaxial Zn-MOF film growth on cotton textile was successfully fabricated via a combination of the liquid-phase epitaxial (LPE) method and calcination treatments. The ZIF-8@CT-800 serves directly as a self-supported electrode for supercapacitors and exhibits a high areal capacitance of 930 mF·cm-2 at a current density of 1 mA·cm-2 and a good recyclability of 86% after 2000 cycles. The excellent supercapacitor property is ascribed to the unique structural design of ZIF-8@CT-800, which provides appropriate channels for enhanced electronic and ionic transport as well as increased surface area for accessing more electrolyte ions. This work will provide significant guidance for designing MOF-derived porous carbon to construct flexible binder-free electrode materials with high electrochemical performance.

Asthma prediction via affinity graph enhanced classifier: a machine learning approach based on routine blood biomarkers.

BACKGROUND: Asthma is a chronic respiratory disease affecting millions of people worldwide, but early detection can be challenging due to the time-consuming nature of the traditional technique. Machine learning has shown great potential in the prompt prediction of asthma. However, because of the inherent complexity of asthma-related patterns, current models often fail to capture the correlation between data samples, limiting their accuracy. Our objective was to use our novel model to address the above problem via an Affinity Graph Enhanced Classifier (AGEC) to improve predictive accuracy. METHODS: The clinical dataset used in this study consisted of 152 samples, where 24 routine blood markers were extracted as features to participate in the classification due to their ease of sourcing and relevance to asthma. Specifically, our model begins by constructing a projection matrix to reduce the dimensionality of the feature space while preserving the most discriminative features. Simultaneously, an affinity graph is learned through the resulting subspace to capture the internal relationship between samples better. Leveraging domain knowledge from the affinity graph, a new classifier (AGEC) is introduced for asthma prediction. AGEC's performance was compared with five state-of-the-art predictive models. RESULTS: Experimental findings reveal the superior predictive capabilities of AGEC in asthma prediction. AGEC achieved an accuracy of 72.50%, surpassing FWAdaBoost (61.02%), MLFE (60.98%), SVR (64.01%), SVM (69.80%) and ERM (68.40%). These results provide evidence that capturing the correlation between samples can enhance the accuracy of asthma prediction. Moreover, the obtained [Formula: see text] values also suggest that the differences between our model and other models are statistically significant, and the effect of our model does not exist by chance. CONCLUSION: As observed from the experimental results, advanced statistical machine learning approaches such as AGEC can enable accurate diagnosis of asthma. This finding holds promising implications for improving asthma management.

Fabrication of Two-Dimensional Homo-Bimetallic Porphyrin Framework Thin Films for Optimizing Nonlinear Optical Limiting.

Developing efficient metal-organic framework (MOF) optical devices with tunable third-order nonlinear optical (NLO) properties is an important challenge for scientific research and practical application. Herein, 2D monometallic and hetero/homo-bimetallic porphyrin MOF thin films (ZnTCPP(M) M = H2, Fe, Zn) were fabricated using the liquid-phase epitaxial (LPE) layer-by-layer (LBL) method to investigate the metal substitution dependent third-order NLO behavior. The prepared homo-bimetallic ZnTCPP(Zn) thin film exhibited enhanced third-order NLO performance with a higher third-order nonlinear susceptibility of ∼4.21 × 10-7 esu compared to monometallic and hetero-bimetallic counterparts. Additionally, theoretical calculations were performed to complement the experimental findings and revealed that the enhanced NLO effect of the ZnTCPP(Zn) thin film is mainly attributed to the enhanced local excitation. These findings not only provide a comprehensive understanding of the relationship between metal types and the NLO behavior of porphyrin MOF thin films but also offer valuable insights into the design and optimization of NLO devices.

Optimizing Photodetectors in Two-Dimensional Metal-Metalloporphyrinic Framework Thin Films.

Two-dimensional (2D) metalloporphyrin-based MOF thin films possessing abundant π-π interactions are promising materials for photoelectronic devices, but no reports on fabrication of photodetectors are available so far. Herein, a series of 2D MOF Zn2[TCPP(M)] (named ZnTCPP(M); TCPP = 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin; M = Zn, Mn, Fe, and H2) films with [001] orientation are fabricated on SiO2/Si substrates by the liquid-phase epitaxial (LPE) layer-by-layer (lbl) approach and further assembled to photodetectors. The obtained ZnTCPP(M)-based photodetectors exhibit an excellent photoresponse due to abundant π-π stacking between the MOF layers. Moreover, the metalloporphyrinic groups in ZnTCPP(M) have a significant influence on modulating the photoresponse of the photodetectors, among which the prepared ZnTCPP(Zn) film-based device exhibits the best photodetection performance with a high on/off ratio of 2.3 × 104, responsivity (Rλ, up to 10.3 A W-1), short rise/fall times (0.09/0.07 s), and a large detectivity (D*) of 8.1 × 1013 Jones. Density functional theory (DFT) calculations reveal that the perturbation of the ring π-electron system and the introduction of low-lying states as well as the large delocalization of the metalloporphyrinic group will adjust the photodetection performance of ZnTCPP(M) films. These results will provide a new understanding of the modulation of 2D metalloporphyrinic MOFs toward photodetection performance and perspective for the fabrication of photoelectronic devices.

Black Titanium-Oxo Clusters with Ultralow Band Gaps and Enhanced Nonlinear Optical Performance.

A series of catecholate-functionalized titanium-oxo clusters (TOCs), PTC-271 to PTC-277, with atomically precise structures were synthesized and characterized, including distinctive "boat" and "chair" conformations in PTC-273 and PTC-274, respectively. These cluster compounds are prominent for their ultralow optical band gaps, as is visually evident from the rather unusual black TOCs (B-TOCs), PTC-272 to PTC-277. The cluster structures were found to be ultrastable with respect to air, water, organic solvents, and even acidic or basic aqueous solutions in a wide pH range (pH 0-13), owing to the stabilizing effects of catecholate and its derivatives, as well as the carboxylate ligands. Another prominent feature is the occurrence of third-order nonlinear optical (NLO) performance, which has previously been unreported in the field of homometallic titanium-oxo clusters. Open-aperture Z-scan experiments show significant solid-state optical limiting (OL) applications of these B-TOCs, with high laser irradiation stability and low minimum normalized transmittance (Tmin) of PTC-273 as ∼0.17. Meanwhile, theoretical calculations indicate that the smaller band gaps of B-TOCs were beneficial for strengthening the NLO response. This work not only represents a significant milestone in the construction of stable low-band gap black titanium oxide materials but also contributes to the mechanism insights into their optical applications.

Silver-Templated γ-Keggin Alkyltin-Oxo Cluster: Electronic Structure and Optical Limiting Effect.

As one of the most representative polyoxometalate (POM) structures, Keggin clusters have attracted considerable attention. Nevertheless, the noble-metal-templated Keggin structure has not been reported to date. In this work, for the first time, a Ag atom was successfully incorporated to template the formation of a γ-Keggin alkytin-oxo cluster. Moreover, the central Ag atom has brought a significant heavy atom effect, showing the important influence on the electronic structure and optical properties. Theoretical calculations demonstrate that the Ag atom affects the frontier molecular orbitals and excited states of the AgSn12 cluster, and also the process of electron transfer. The solid structure of the AgSn12 cluster exhibits a significant third-order nonlinear optical (NLO) response, and an excellent optical limiting effect has been experimentally verified. The success of this work opens the way for the construction and optical properties modulation of noble metal templated Keggin structures.

Heterometallic Al6Zn12 nano-plate with π-conjugated ligand: synthesis and nonlinear absorption properties.

Presented herein is the synthesis, structure, and optical properties of the aluminum(III)-zinc(II) heterometallic compound AlOC-57. This compound was found to form a large unit cell (approximately sixteen thousand atoms) and a three-shell nano-plate structure. Based on the Z-scan patterns, the third-order nonlinear optical response of the heterometallic nano-plate was mainly attributed to its nonlinear absorption (reverse saturable absorption).

Oriented Assembly of 2D Metal-Pyridylporphyrinic Framework Films for Giant Nonlinear Optical Limiting.

The development of metal-organic frameworks (MOFs) with nonlinear optical (NLO) properties is of pronounced significance for optical devices. Herein, a series of 2D MOFs ZnTPyP(M) (TPyP = 5,10,15,20-tetrakis(4-pyridyl)porphyrin, M = Cu, Ni, Mn, H2) films with [010]-orientation growth composed of ultrathin nanosheets from a pyridylporphyrinic ligand are first obtained by using a liquid-phase epitaxial (LPE) layer-by-layer (lbl) growth approach. ZnTPyP(M) films show a giant nonlinear optical limiting (OL) response and can be modulated by tuning the type of metalloporphyrinic ligands. As a result, ZnTPyP(Cu) film exhibits the highest nonlinear absorption coefficient of 5.7 × 10-6 m/W compared to other reported NLO materials. Density functional theory calculations were consistent with the experimental results, revealing that the tunable π-π* local excitation and the increased delocalization of the metalloporphyrinic group regulate the NLO performance of ZnTPyP(M) films. These findings provide new insight into the effect of 2D porphyrinic MOFs toward the NLO response and offer new film candidates for nonlinear OL application.

Interpenetrated Metal-Porphyrinic Framework for Enhanced Nonlinear Optical Limiting.

Structural interpenetration in metal-organic frameworks (MOFs) significantly impacts on their properties and functionalities. However, understanding the interpenetration on third-order nonlinear optics (NLO) of MOFs have not been reported to date. Herein, we report two 3D porphyrinic MOFs, a 2-fold interpenetrated [Zn2(TPyP)(AC)2] (ZnTPyP-1) and a noninterpenetrated [Zn3(TPyP)(H2O)2(C2O4)2] (ZnTPyP-2), constructed from 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP(H2)) and Zn(NO3)2 (AC = acetate, C2O4 = oxalate). ZnTPyP-1 achieves excellent optical limiting (OL) performance with a giant nonlinear absorption coefficient (3.61 × 106 cm/GW) and large third-order susceptibility (7.73 × 10-7 esu), which is much better than ZnTPyP-2 and other reported OL materials. The corresponding MOFs nanosheets are dispersed into a polydimethylsiloxane (PDMS) matrix to form highly transparent and flexible MOFs/PDMS glasses for practical OL application. In addition, the OL response optimized by adjusting the MOFs concentration in the PDMS matrix and the type of metalloporphyrin are discussed in the ZnTPyP-1 system. The theoretical calculation confirmed that the abundant π-π interaction from porphyrinic groups in the interpenetrated framework increased the electron delocalization/transfer and boosted the OL performance. This study opens a new avenue to enhance OL performance by the construction of interpenetrated structures and provides a new approach for the preparation of transparent and flexible MOF composites in nonlinear optical applications.

Threefold Collaborative Stabilization of Ag14 -Nanorods by Hydrophobic Ti16 -Oxo Clusters and Alkynes: Designable Assembly and Solid-State Optical-Limiting Application.

Ag nanoclusters have received increasing attention due to their atomically precise and diverse structures and intriguing optical properties. Nevertheless, the inherent instability of Ag nanoclusters has seriously hindered their practical application. In this work, for the first time, Ag clusters are collaboratively protected by hydrophobic Ti-oxo clusters and alkyne ligands. Initially, a pyramidal Ag5 cluster terminated with t BuC≡C- and CH3 CN was inserted into the cavity of a Ti8 -oxo nanoring to form Ag5 @Ti8 . To overcome the instability of acetonitrile-terminated silver site, such two Ag5 @Ti8 clusters could sandwich an Ag4 unit to form Ag14 -nanorod@Ti16 -oxo-nanoring (Ag14 @Ti16 ), which is peripherally protected by fluorophenyl groups and alkyne caps. This threefold protected (hydrophobic fluorinated organic layer, Ti-O shell, and terminal alkyne ligands) Ag14 @Ti16 exhibits superhydrophobicity and excellent ambient stability, endowing it with solid-state optical limiting characteristics.

Experimental and Theoretical Studies on Effects of Structural Modification of Tin Nanoclusters for Third-Order Nonlinear Optical Properties.

Tin oxide based materials have attracted much attention as new sources for nonlinear optical (NLO) devices, while the electronic mechanism behind the structure and nonlinearity is still unclear. In this work, by precisely controlling different functionalization ligands, here a series of binuclear [(nBuSn)2(TEOA)2L2] (L = monocarboxylic acid ligand) complexes have been synthesized and characterized; we also adopted a new method to make the metal clusters and PMMA blend together for NLO testing. Importantly, the electronic structure, static third-order NLO properties, sum over states (SOS) have been studied by both experimental and density function theory (DFT) analysis. The effects for general NLO polarizability under various conditions, including different substitutions ligands and replacement of the metal cores, have been further investigated. The results indicate the static second hyperpolarizabilities (γ) is inversely proportional to the band gap decreases. Notably, the theory predicts that the third-order nonlinear coefficient will double through the synergistic effects of pull-push groups. The hole-electron analysis of the main excited states indicates the simultaneous introduction of pull-push electron groups into the system cause the excitation of the valence layer from LE to LLCT, which also leads to significant increase in the γ value of complex 13. This work demonstrates that an efficient adjustment for the intensity of NLO polarizability can be achieved by regulating the substitutions and the material structures, providing a new potential for the application of tin-oxo clusters in the field of nonlinear optics.

The Lisu people's traditional natural philosophy and its potential impact on conservation planning in the Laojun Mountain region, Yunnan Province, China.

In this study, we explored a conservation process from an ethnoprimatological perspective for the management of national parks and nature reserves. We accumulated attitude and knowledge data on the traditional culture, religion, and current attitudes to conservation of rural and urban groups of ethnic Lisu people, who live in the village of Liju or have migrated to urban areas, respectively. The data clearly indicated that most of the interviewees had similar feelings and attitudes toward the conservation of Yunnan snub-nosed monkeys (Rhinopithecus bieti) and Laojun Mountain National Park (LMNP), irrespective of whether they live in or have moved away from their home village, or if their educational background differs. Both the rural (96.6%) and urban (100%) interviewees expressed their deep affection for Yunnan snub-nosed monkeys and supported (90.3% and 89.0%, respectively) the seasonal closure of mountainous areas for conservation purposes. The Lisu peoples culture, history, and traditions were evaluated with regards to the developing trend for environmentalism, and their advanced attitudes toward environmental protection and resource utilization exceeded our expectations. The results of this study show huge potential for the optimal mitigation of human-animal conflict in the context of conservation planning not only for LMNP but also for other national parks and nature reserves.

Designable Al32 -Oxo Clusters with Hydrotalcite-like Structures: Snapshots of Boundary Hydrolysis and Optical Limiting.

The hydrolysis of earth-abundant AlIII has implications in mineral mimicry, geochemistry and environmental chemistry. Third-order nonlinear optical (NLO) materials are important in modern chemistry due to their extensive optical applications. The assembly of AlIII ions with π-conjugated carboxylate ligands is carried out and the hydrolysis and NLO properties of the resultant material are studied. A series of Al32 -oxo clusters with hydrotalcite-like cores and π-conjugated shells are isolated. X-ray diffraction revealed boundary hydrolysis occurs at the equatorially unsaturated coordination sites of AlIII ions. Charge distribution analysis and DFT calculations support the proposed boundary substitution. The Al32 -oxo clusters possess a significant reverse saturable absorption (RSA) response with a minimal normalized transmittance up to 29 %, indicating they are suitable candidates for optical limiting (OL) materials. This work elucidates the hydrolysis of AlIII and provides insight into layered materials that also have strong boundary activity at the edges or corners.

Combining a Titanium-Organic Cage and a Hydrogen-Bonded Organic Cage for Highly Effective Third-Order Nonlinear Optics.

Many metal-organic cages (MOCs) and a few hydrogen-bonded organic cages (HOCs) have been investigated, but little is reported about cooperative self-assembly of MOCs and HOCs. Herein, we describe an unprecedented MOC&HOC co-crystal composed of tetrahedral Ti4 L6 (L=embonate) cages and in-situ-generated [(NH3 )4 (TIPA)4 ] (TIPA=tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine) cages. Chiral transfer is observed from the enantiopure Ti4 L6 cage to enantiopure [(NH3 )4 (TIPA)4 ] cage. Two homochiral supramolecular frameworks with opposite handedness (PTC-235(Δ) and PTC-235(Λ)) are formed. Such MOC&HOC co-crystal features high stability in water and other solvents, affording single-crystal-to-single-crystal transformation to trap CH3 CN molecules and identify disordered NH4 + cations. A tablet pressing method is developed to test the third-order nonlinear optical property of KBr-based PTC-235 thin film. Such a thin film exhibits an excellent optical limiting effect.

Self-Assembly of a Ti4(embonate)6 Cage toward Silver.

Herein we report a variety of supramolecular architectures that are self-assembled by the highly charged anionic Ti4L6 (L = embonate) cages and noble-metal Ag+ ions in the presence of the different ligands, including six Ti4L6-Ag(PPh3) cages in whose structures the Ti4L6 cage catches various in situ formed [Ag(PPh3)]+ moieties by a coordination bond and one cocrystal superstructure of a Ti4L6 cage with an in situ generated [Ag2(Ph2P(CH2)5PPh2)3]2+ cage via supramolecular interactions. In addition, the third-order nonlinear-optical properties of these compounds are investigated in detail.

Tetrahedral Geometry Induction of Stable Ag-Ti Nanoclusters by Flexible Trifurcate TiL3 Metalloligand.

A series of increasingly large silver nanoclusters with a varied combination of Archimedean and/or Platonic solid arrangements was constructed using a flexible trifurcate TiL3 (L = Salicylic acid or 5-fluorosalicylic acid) metalloligand: Ag4@Ag4@Ti4 (PTC-85), Ag12@Ti4 (PTC-86), Ag4@Ag6@Ag12@Ti4 (PTC-87), Ag6@Ag24@Ag12@Ti4 (PTC-88), and Ag12@Ag24@Ti4 (PTC-89). The silver nanoclusters are each capped by four TiL3 moieties, thereby forming {Ti4} supertetrahedra with average edge lengths ranging from ∼8.12 Å to ∼17.37 Å. Such {Ti4} moieties further induce the tetrahedral geometry of the encapsulated silver nanoclusters. These atomically precise metallic clusters were found to be ultrastable with respect to air for several months, and to water for more than 3 days, due to the stabilizing effects of the TiL3 metalloligand. Moreover, the obtained clusters exhibit nonlinear optical (NLO) effects in optical limiting tests and also temperature-dependent photoluminescent properties. This work provides an interesting metalloligand method not only to induce the spatial growth of metallic clusters to achieve highly symmetric structures, but also to enhance their stability which is crucial for future application.

Auto-controlled fabrication of a metal-porphyrin framework thin film with tunable optical limiting effects.

Metal-organic frameworks (MOFs) with third-order nonlinear optical (NLO) properties are still in their infancy but are very important. In this work, we first develop a layer by layer autoarm immersion method for preparing porphyrin-based MOF (PIZA-1) thin films with third-order NLO properties. By precisely controlling the thickness, the nonlinear absorption of PIZA-1 thin films can be switched continuously between reverse saturable absorption (RSA) and saturable absorption (SA) by using the Z-scan technique. In addition, the optical limiting effect could be further optimized by loading C60 in the pores of the PIZA-1 thin film. These findings not only open a new route for the exploitation of third-order NLO thin film materials, but also offer an insightful understanding of porphyrin-based MOF thin films for future broad practical applications.

Single molecule magnetic behaviour in lanthanide naphthalenesulfonate complexes.

The use of 2-naphthalenesulfonate (NAS) ligand in lanthanide chemistry afforded a family of isostructural mononuclear lanthanide complexes with the formula [Ln(NAS)2(H2O)6](NAS)·3H2O [Ln = Tb (1), Dy (2), Er (3), Yb (4)]. Crystallographic studies determined a square antiprismatic geometry (D4d) for the Ln centre and crystallization in an unprecedented chiral space group. The latter was further confirmed by the observation of Cotton effects in single crystal circular dichroism (CD) spectra. Static and dynamic magnetic measurements identified weak intermolecular dipolar interactions in 2, and such effects can be waived by dilution, which was noted by the detection of zero-field single molecule magnet (SMM) behaviour and hysteresis loop in a magnetically diluted sample (5). Compounds 2-4 exhibit SMM behaviours with energy barriers of 53, 32, and 45 K, respectively. To the best of our knowledge, these complexes are the first examples of pure 4f sulfonate-based SMMs.

Helical carbon tubes derived from epitaxial Cu-MOF coating on textile for enhanced supercapacitor performance.

The design and development of the supercapacitors containing metal oxides and carbon materials is very important for energy-storage devices in laboratory and industry. In this study, we report a helical carbon tube material derived from epitaxial Cu-MOF coating on textile by calcination treatment. The electrochemical performance obtained from the cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and cyclic stability measurements indicates that such a hybrid carbon material with a unique structure has a very high areal capacitance of 1812 mF cm-2 at a current density of 1 mA cm-2, and the material also has a good recyclability of 90% after 2000 cycles. This study combines the advantages of MOF- and cotton textile-derived carbon materials, and this study can serve as a guidance to improve the capacitance performance of supercapacitors.

A Multifunctional Nanocage-based MOF with Tri- and Tetranuclear Zinc Cluster Secondary Building Units.

A new Zn-cluster based MOF, [Zn21(BTC)11(µ3-OH)3(µ4-O)3(H2O)18]·21EtOH (1) (H3BTC = 1,3,5-benzenetricarboxylic acid), with two different types of cluster nodes has been successfully synthesized from Zn2+ and H3BTC under the solvothermal conditions. Single crystal X-ray diffraction studies reveal that 1 is a 3D trinodal (3,5,6)-c framework which features a large octahedral cage organized by nine Zn3O and nine Zn4O clusters SBUs and twenty-four triangular BTC3- linkers. The Eu3+/Tb3+-incorporated derivative of 1 with 0.251% Eu3+ and 0.269% Tb3+ exhibits tunable luminescence from yellow to white and then to blue-green by changing the excitation wavelength from 308 to 315 nm. Metal ion exchange with Cu2+ affords isomorphous Cu-based MOF with enhanced N2 and CO2 adsorption capacity. In addition, 1 can act as a selective luminescent sensor for Cu2+ and Al3+ ions.