Metamagnetism and canted antiferromagnetic ordering in two monomeric CoII complexes with 1-(2-pyrimidyl)piperazine. Hirshfeld surface analysis and theoretical studies.

Here we present the magnetic properties of two cobalt complexes formulated as: [Co(SCN)2(L)2] (1) and (H2L)2[Co(SCN)4]·H2O (2) (L = 1-(2-pyrimidyl)piperazine). The two compounds contain isolated tetrahedral CoII complexes with important intermolecular interactions that lead to the presence of a canted antiferromagnetic order below 11.5 and 10.0 K, with coercive fields at 2 K of 38 and 68 mT, respectively. Theoretical calculations have been used to explain this behaviour. Hirshfeld surface analysis shows the presence of strong intermolecular interactions in both compounds. The crystal geometries were used for geometry optimization using the DFT method. From the topological properties, electrostatic potential maps and molecular orbital analysis, information about the noncovalent interaction and chemical reactivity was obtained.

Heptanuclear Mixed-Valence Co4IIICo3II Molecular Wheel─A Molecular Analogue of Layered Double Hydroxides with Single-Molecule Magnet Behavior and Electrocatalytic Activity for Hydrogen Evolution Reactions.

We present a bifunctional heptanuclear cobalt(II)/cobalt(III) molecular complex formulated as [Co7(µ3-OH)4(H2L1)2(HL2)2](NO3)6·6H2O (1) (where H5L1 is 2,2'-(((1E,1'E)-((2-hydroxy-5-methyl-1,3-phenylene)bis(methanylylidene))bis(azanylylidene))bis(propane-1,3-diol)) and H2L2 is 2-amino-1,3-propanediol). Compound 1 has been characterized by single-crystal X-ray diffraction analysis along with other spectral and magnetic measurements. Structural analysis indicates that 1 contains a mixed-valence Co7 cluster where a central Co(II) ion is connected to six different Co centers (four CoIII and two CoII ions) by four µ3-OH groups, giving rise to a planar heptanuclear cluster that resembles a molecular fragment of a layered double hydroxide (LDH). Two triply deprotonated (H2L1)3- ligands form the outer side of the cluster while two singly deprotonated (HL2)- ligands are located at the top and bottom of the central heptanuclear core. Variable temperature magnetic measurements indicate the presence of weak ferromagnetic CoII···CoII interactions (J = 3.53(6) cm-1) within the linear trinuclear CoII cluster. AC susceptibility measurements show that 1 is a field-induced single-molecule magnet (SMM) with τ0 = 8.2(7) × 10-7 s and Ueff = 11.3(4) K. The electrocatalytic hydrogen evolution reaction (HER) activity of 1 in homogeneous phase shows an overpotential of 455 mV, with a Faradaic efficiency of 81% and a TOF of 8.97 × 104 µmol H2 h-1 mol-1.

Anilato-Based Coordination Polymers with Slow Relaxation of the Magnetization: Role of the Synthetic Method and Anilato Ligand.

We have prepared and characterized three coordination polymers formulated as [Dy2(C6O4Cl2)3(fma)6] ⋅ 4.5fma (1) and [Dy2(C6O4X2)3(fma)6] ⋅ 4fma ⋅ 2H2O with X=Br (2) and Cl (3), where fma=formamide and C6O4X2 2-=3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone dianion with X=Cl (chloranilato) and Br (bromanilato). Compounds 1 and 3 are solvates obtained with slow and fast precipitation methods, respectively. Compounds 2 and 3 are isostructural and only differ in the X group of the anilato ligand. The three compounds present (6,3)-gon two-dimensional hexagonal honey-comb structures. Magnetic measurements indicate that the three compounds show slow relaxation of the magnetization at low temperatures when a continuous magnetic field is applied, although with different relaxation times and energy barriers depending on X and the crystallisation molecules. Compounds 1-3 represent the first examples of anilato-based lattices with formamide and field-induced slow relaxation of the magnetization.

Metal vs Ligand Oxidation: Coexistence of Both Metal-Centered and Ligand-Centered Oxidized Species.

A series of two-electron-oxidized cobalt porphyrin dimers have been synthesized upon controlled oxidations using halogens. Rather unexpectedly, X-ray structures of two of these complexes contain two structurally different low-spin molecules in the same asymmetric unit of their unit cells: one is the metal-centered oxidized diamagnetic entity of the type CoIII(por), while the other one is the ligand-centered oxidized paramagnetic entity of the type CoII(por•+). Spectroscopic, magnetic, and DFT investigations confirmed the coexistence of the two very different electronic structures both in the solid and solution phases and also revealed a ferromagnetic spin coupling between Co(II) and porphyrin π-cation radicals and a weak antiferromagnetic coupling between the π-cation radicals of two macrocycles via the bridge in the paramagnetic complex.

Strategies to Improve Electrical Conductivity in Metal-Organic Frameworks: A Comparative Study.

Metal-organic frameworks (MOFs), formed by the combination of both inorganic and organic components, have attracted special attention for their tunable porous structures, chemical and functional diversities, and enormous applications in gas storage, catalysis, sensing, etc. Recently, electronic applications of MOFs like electrocatalysis, supercapacitors, batteries, electrochemical sensing, etc., have become a major research topic in MOF chemistry. However, the low electrical conductivity of most MOFs represents a major handicap in the development of these emerging applications. To overcome these limitations, different strategies have been developed to enhance electrical conductivity of MOFs for their implementation in electronic devices. In this review, we outline all these strategies employed to increase the electronic conduction in both intrinsically (framework-modulated) and extrinsically (guests-modulated) conducting MOFs.

Nav1.8-expressing neurons control daily oscillations of food intake, body weight and gut microbiota in mice.

Recent evidence suggests a role of sensory neurons expressing the sodium channel Nav1.8 on the energy homeostasis control. Using a murine diphtheria toxin ablation strategy and ad libitum and time-restricted feeding regimens of control or high-fat high-sugar diets, here we further explore the function of these neurons on food intake and on the regulation of gastrointestinal elements transmitting immune and nutrient sensing.The Nav1.8+ neuron ablation increases food intake in ad libitum and time-restricted feeding, and exacerbates daily body weight variations. Mice lacking Nav1.8+ neurons show impaired prandial regulation of gut hormone secretion and gut microbiota composition, and altered intestinal immunity.Our study demonstrates that Nav1.8+ neurons are required to control food intake and daily body weight changes, as well as to maintain physiological enteroendocrine and immune responses and the rhythmicity of the gut microbiota, which highlights the potential of Nav1.8+ neurons to restore energy balance in metabolic disorders.

Pathogenic NLRP3 mutants form constitutively active inflammasomes resulting in immune-metabolic limitation of IL-1ß production.

Cryopyrin-associated periodic syndrome (CAPS) is an autoinflammatory condition resulting from monoallelic NLRP3 variants that facilitate IL-1ß production. Although these are gain-of-function variants characterized by hypersensitivity to cell priming, patients with CAPS and animal models of the disease may present inflammatory flares without identifiable external triggers. Here we find that CAPS-associated NLRP3 variants are forming constitutively active inflammasome, which induce increased basal cleavage of gasdermin D, IL-18 release and pyroptosis, with a concurrent basal pro-inflammatory gene expression signature, including the induction of nuclear receptors 4 A. The constitutively active NLRP3-inflammasome of CAPS is responsive to the selective NLRP3 inhibitor MCC950 and its activation is regulated by deubiquitination. Despite their preactivated state, the CAPS inflammasomes are responsive to activation of the NF-κB pathway. NLRP3-inflammasomes with CAPS-associated variants affect the immunometabolism of the myeloid compartment, leading to disruptions in lipids and amino acid pathways and impaired glycolysis, limiting IL-1ß production. In summary, NLRP3 variants causing CAPS form a constitutively active inflammasome inducing pyroptosis and IL-18 release without cell priming, which enables the host's innate defence against pathogens while also limiting IL-1ß-dependent inflammatory episodes through immunometabolism modulation.

Vocal learning-associated convergent evolution in mammalian proteins and regulatory elements.

Vocal production learning ("vocal learning") is a convergently evolved trait in vertebrates. To identify brain genomic elements associated with mammalian vocal learning, we integrated genomic, anatomical, and neurophysiological data from the Egyptian fruit bat (Rousettus aegyptiacus) with analyses of the genomes of 215 placental mammals. First, we identified a set of proteins evolving more slowly in vocal learners. Then, we discovered a vocal motor cortical region in the Egyptian fruit bat, an emergent vocal learner, and leveraged that knowledge to identify active cis-regulatory elements in the motor cortex of vocal learners. Machine learning methods applied to motor cortex open chromatin revealed 50 enhancers robustly associated with vocal learning whose activity tended to be lower in vocal learners. Our research implicates convergent losses of motor cortex regulatory elements in mammalian vocal learning evolution.

Nitrogen doped 1 T/2H mixed phase MoS2/CuS heterostructure nanosheets for enhanced peroxidase activity.

Heteroatom doping and phase engineering are effective ways to promote the catalytic activity of nanoenzymes. Nitrogen-doped 1 T/2H mixed phase MoS2/CuS heterostructure nanosheets N-1 T/2H-MoS2/CuS are prepared by a simple hydrothermal approach using polyoxometalate (POM)-based metal-organic frameworks (MOFs) (NENU-5) as a precursor and urea as nitrogen doping reagent. The XPS spectroscopy (XPS) and Raman spectrum of N-1 T/2H-MoS2/CuS prove the successful N-doping. NENU-5 was used as the template to prepare 1 T/2H-MoS2/CuS with high content of 1 T phase by optimizing the reaction time. The use of urea as nitrogen dopant added to 1 T/2H-MoS2/CuS, resulted in N-1 T/2H-MoS2/CuS with an increase in the content of the 1 T phase from 80 % to 84 % and higher number of defects. N-1 T/2H-MoS2/CuS shows higher peroxidase activity than 1 T/2H-MoS2/CuS and a catalytic efficiency (Kcat/Km) for H2O2 twice as high as that of 1 T/2H-MoS2/CuS. The enhanced catalytic activity has probably been attributed to several reasons: (i) the insertion of urea during the hydrothermal process in the S-Mo-S layer of MoS2, causing an increase in the interlayer spacing and in 1 T phase content, (ii) the replacement of S atoms in MoS2 by N atoms from the urea decomposition, resulting in more defects and more active sites. As far as we know, N-1 T/2H-MoS2/CuS nanosheets have the lowest detection limit (0.16 µm) for the colorimetric detection of hydroquinone among molybdenum disulfide-based catalysts. This study affords a new approach for the fabrication of high-performance nanoenzyme catalysts.

One-Step Synthesis of Hollow CoS2 Spheres Derived from Polyoxometalate-Based Metal-Organic Frameworks with Peroxidase-like Activity.

In this work, hollow CoS2 particles were prepared by a one-step sulfurization strategy using polyoxometalate-based metal-organic frameworks as the precursor. The morphology and structure of CoS2 have been monitored by scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray powder diffraction. The mechanism for the formation of CoS2 is discussed. The reaction time and sulfur content are found to be important factors that affect the morphology and pure phase formation of CoS2, and a hollow semioctahedral morphology of CoS2 with open voids was obtained when the sulfur source was twice as large as the precursor and the reaction time was 24 h. The CoS2 (24 h) particles show an excellent peroxidase-like activity for the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized (oxTMB) by hydrogen peroxide. The polyoxometalate used as a precursor helps to stabilize oxTMB during catalytic oxidation, forming a stable curve platform for at least 8 min. Additionally, the colorimetric detection of hydroquinone is developed with a low detection limit of 0.42 µM. This research provides a new strategy to design hollow materials with high peroxidase-mimicking activity.

A lipidomic and metabolomic signature of a very low-carbohydrate high-fat diet and high-intensity interval training: an additional analysis of a randomized controlled clinical trial.

INTRODUCTION: Regular physical activity and dietary variety are modifiable and influential factors of health outcomes. However, the cumulative effects of these behaviors are not well understood. Metabolomics may have a promising research potential to extend our knowledge and use it in the attempts to find a long-term and sustainable personalized approach in exercise and diet recommendations. OBJECTIVE: The main aim was to investigate the effect of the 12 week very low carbohydrate high fat (VLCHF) diet and high-intensity interval training (HIIT) on lipidomic and metabolomic profiles in individuals with overweight and obesity. METHODS: The participants (N = 91) were randomly allocated to HIIT (N = 22), VLCHF (N = 25), VLCHF + HIIT (N = 25) or control (N = 19) groups for 12 weeks. Fasting plasma samples were collected before the intervention and after 4, 8 and 12 weeks. The samples were then subjected to untargeted lipidomic and metabolomic analyses using reversed phase ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry. RESULTS: The VLCHF diet affected plasma lipids considerably while the effect of HIIT was unremarkable. Already after 4 weeks of intervention substantial changes of plasma lipids were found in both VLCHF diet groups. The changes persisted throughout the entire 12 weeks of the VLCHF diet. Specifically, acyl carnitines, plasmalogens, fatty acyl esters of hydroxy fatty acid, sphingomyelin, ceramides, cholesterol esters, fatty acids and 4-hydroxybutyric were identified as lipid families that increased in the VLCHF diet groups whereas lipid families of triglycerides and glycerophospholipids decreased. Additionally, metabolomic analysis showed a decrease of theobromine. CONCLUSIONS: This study deciphers the specific responses to a VLCHF diet, HIIT and their combination by analysing untargeted lipidomic and metabolomic profile. VLCHF diet caused divergent changes of plasma lipids and other metabolites when compared to the exercise and control group which may contribute to a better understanding of metabolic changes and the appraisal of VLCHF diet benefits and harms. CLINICAL TRIAL REGISTRY NUMBER: NCT03934476, registered 1st May 2019 https://clinicaltrials.gov/ct2/show/NCT03934476?term=NCT03934476&draw=2&rank=1 .

Isomerism tunes the diradical character of difluorenopyrroles at constant Hückel-level anti-aromaticity.

A new diradical based on diindenocarbazole or difluorenopyrrole was synthesized and experimentally characterized by optical, electrochemical, and magnetic techniques, as well as quantum chemical calculations. The isomerism of these structures tunes the diradical character and the associated properties, representing a unique case of such important modulation. A full study of the electronic structure was carried out considering the perturbative interactions between different canonical forms as well as the anti-aromatic character of the molecular cores. Such a study reveals how we can tune diradical character simply by reorganizing the bonding patterns at constant chemical costs (composition).

Proliferation, Migration and Invasion of Breast Cancer Cell Lines Are Inhibited by 1,5-Disubstituted Tetrazol-1,2,3-triazole Hybrids through Interaction with p53.

The anticarcinogenic potential of a series of 1,5-disubstituted tetrazole-1,2,3-triazole hybrids (T-THs) was evaluated in the breast cancer (BC)-derived cell lines MCF-7 (ER+, PR+, and HER2-), CAMA-1 (ER+, PR+/-, and HER2-), SKBR-3 (ER+, PR+, and HER2+), and HCC1954 (ER+, PR+, and HER2+). The T-THs 7f, 7l, and 7g inhibited the proliferation of MCF-7 and CAMA-1, HCC1954, and SKBR-3 cells, respectively. The compounds with stronger effect in terms of migration and invasion inhibition were 7o, 7b, 7n, and 7k for the CAMA-1, MCF-7, HCC1954, and SKBR-3 cells respectively. Interestingly, these T-THs were the compounds with a fluorine present in their structures. To discover a possible target protein, a molecular docking analysis was performed for p53, p38, p58, and JNK1. The T-THs presented a higher affinity for p53, followed by JNK1, p58, and lastly p38. The best-predicted affinity for p53 showed interactions between the T-THs and both the DNA fragment and the protein. These results provide an opportunity for these compounds to be studied as potential drug candidates for breast cancer treatment.

Tetrafluorenofulvalene as a sterically frustrated open-shell alkene.

Electronic and steric effects are known to greatly influence the structure, characteristics and reactivity of organic compounds. A typical π bond is weakened by oxidation (corresponding to the removal of electrons from bonding orbitals), by reduction (through addition of electrons to antibonding orbitals) and by unpairing of the bonding electrons, such as in the triplet state. Here we describe tetrafluorenofulvalene (TFF), a twisted, open-shell alkene for which these general rules do not hold. Through the synthesis, experimental characterization and computational analysis of its charged species spanning seven redox states, the central alkene bond in TFF is shown to become substantially stronger in the tri- and tetraanion, generated by chemical reduction. Furthermore, although its triplet state contains a weaker alkene bond than the singlet, in the quintet state its bond order increases substantially, yielding a flatter structure. This behaviour originates from the doubly bifurcated topology of the underlying spin system and can be rationalized by the balancing effects of benzenoid aromaticity and spin pairing.

The Versatility of Ethylene Glycol to Tune the Dimensionality and Magnetic Properties in DyIII-Anilato-Based Single-Ion Magnets.

We exploit the high versatility of the solvent ethylene glycol (eg = CH2OH-CH2OH) acting as a ligand with three different coordination modes: terminal (κO), chelate (κ2O,O'), and bridge (1κO,2κO') to prepare a novel family of six different coordination polymers with DyIII and three different anilato ligands (3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone dianion = C6O4X22-, with X = H, Cl, and Br). With the X = H derivative (dhbq2-), we have prepared [Dy2(dhbq)3(eg)2(µ-eg)]·4eg·2H2O (1), a 3D diamond-like network with a chelate and bridging eg molecules. With the X = Cl derivative (chloranilato), we have prepared [Dy2(C6O4Cl2)3(eg)4]·2eg·H2O (2) and [Dy2(C6O4Cl2)3(µ-eg)(H2O)4]·2eg·7H2O (3). Compound 2 has a 2D (6,3)-gon brick-wall lattice and contains a chelate and a terminal eg molecule. Compound 3 has a 3D diamond-like topology as 1, although now the chelate eg has been replaced by two water molecules. Finally, with the X = Br derivative (bromanilato), we have obtained [Dy2(C6O4Br2)3(eg)2(CH3OH)2]·2eg·4CH3OH (4), [Dy2(C6O4Br2)3(eg)4]·4eg (5), and [Dy2(C6O4Br2)3(eg)3(H2O)]·2eg·H2O (6). Compound 4 has a 2D (6,3)-gon herringbone topology and contains a chelate eg and a MeOH molecule. Compounds 5 and 6 have a 2D (6,3)-gon brick-wall topology with a chelate and a terminal eg molecules (in 5 and in one of the two independent Dy centers of 6). The other Dy center in 6 has a chelate eg and a water molecule. All the compounds show slow relaxation of the magnetization at low temperatures (in compounds 1, 2, and 5 with no applied DC field). The magnetization of compounds 1-6 relaxes through Orbach and direct mechanisms when a DC field is applied and through an Orbach and/or quantum tunneling mechanism when no DC field is applied.

Dinor[7]helicene and Beyond: Divergent Synthesis of Chiral Diradicaloids with Variable Open-Shell Character.

Diradicaloid helicenes constructed formally by non-benzenoid double π-extension of phenanthrene were synthesized by a common strategy involving double electrophilic benzannulation. Steric effects in the second benzannulation step led to considerable structural diversity among the products, yielding a symmetrical dinor[7]helicene 1 and two isomeric unsymmetrical double helicenes 2 and 3, containing a nor[5]helicene and [4]helicene fragment, respectively, in addition to a common nor[6]helicene motif. Geometries, configurational dynamics, and electronic structure of these helicenes were analyzed using solid-state structures, spectroscopic methods, and computational analyses. The open-shell character of the singlet states of these helicenes increases in the order 3<1<2, with strongly varying diradicaloid indexes and singlet-triplet gaps. Compounds 1-3 displayed narrow optical gaps of 0.79-1.25 eV, resulting in significant absorption in the near infrared (NIR) region. They also exhibit reversible redox chemistry, each of them yielding stable radical cations, radical anions, and dianions, in some cases possessing intense NIR absorptions extending beyond 2500 nm.

Chiropterans Are a Hotspot for Horizontal Transfer of DNA Transposons in Mammalia.

Horizontal transfer of transposable elements (TEs) is an important mechanism contributing to genetic diversity and innovation. Bats (order Chiroptera) have repeatedly been shown to experience horizontal transfer of TEs at what appears to be a high rate compared with other mammals. We investigated the occurrence of horizontally transferred (HT) DNA transposons involving bats. We found over 200 putative HT elements within bats; 16 transposons were shared across distantly related mammalian clades, and 2 other elements were shared with a fish and two lizard species. Our results indicate that bats are a hotspot for horizontal transfer of DNA transposons. These events broadly coincide with the diversification of several bat clades, supporting the hypothesis that DNA transposon invasions have contributed to genetic diversification of bats.

Rational Design of Iron Spin-Crossover Complexes Using Heteroscorpionate Chelates.

The optical, structural, and magnetic properties of iron(II,III) sandwich complexes, Fe(Tp')2n+ (Tp' = bis(3,5-dimethylpyrazolyl)benzotriazolylborate), are described. The intensely colored FeII(Tp')2 (orange) and FeIII(Tp')2+ (purple) show strong MLCT bands. Geometric isomerism for M(Tp')2 is established crystallographically in the racemate of chiral cis-Fe(Tp')2. For the first time, paramagnetic 11B NMR describes solution-phase low-spin (LS, S = 0) to high-spin (HS, S = 2) crossover behavior in Fe(Tp')2. Thermochemical parameters for solution-phase SCO of Fe(Tp')2 demonstrate the endothermic LS to HS conversion and entropic preference of the HS state. Entropy changes for both Fe(Tp')2 isomers are significantly larger than for the majority of iron scorpionate SCO systems. Solid-state magnetic and thermochemical measurements show cis-Fe(Tp')2 to be thermally stable up to 520 K, allowing experimental investigation of a solid-state SCO magnetic hysteresis of over 45 K. A large solution vs solid-state SCO difference was observed: cis-Fe(Tp')2 shows Tc ≈ 270 K (solution) and Tc ≈ 385 K (solid), with the remarkably wide ΔTc ≈ 115 K; trans-Fe(Tp')2 shows Tc ≈ 278 K (solution) and Tc ≈ 372 K (solid). Solid-state Tc values are among the highest seen for iron(II) molecular systems. The large solution/solid ΔTc difference is explained by "anchoring" intermolecular interactions in the solid state that prevent thermal expansion of the LS iron(II) coordination sphere in its transition to the HS state. DFT calculations, validated against LS cis-Fe(Tp')2 crystallography and LS to HS SCO thermochemical parameters, demonstrate the role the benzotriazole rings play in its structural and optical properties. The Lewis basicity of M(Tp')2 is shown with the structural characterization of the air-stable tin(II) adduct [cis-Fe(Tp')2-SnCl2]; tin(II) coordination does not alter the iron(II) spin state. The Tp' chelate adds functionality (asymmetry, chirality, chemical reactivity) to the array of iron SCO materials for potential incorporation into nanoscale magnetic switches and spintronic devices.

Untargeted Metabolomics Reveals New Markers of Food Processing for Strawberry and Apple Purees.

In general, food processing and its conditions affect nutrients, bioactive compounds, and sensory characteristics of food products. This research aims to use a non-targeted metabolomics approach based on UPLC-ESI-QTOF-MS to determine how fruit processing can affect the metabolic profile of fruits and, through a comprehensive metabolic analysis, identify possible markers to assess their degree of processing. The present study uses a real case from the food industry to evaluate markers of the processing of strawberry and apple purees industrially elaborated with different processing techniques and conditions. The results from the multivariate analysis revealed that samples were grouped according to the type of processing, evidencing changes in their metabolic profiles and an apparent temperature-dependent effect. These metabolic profiles showed changes according to the relevance of thermal conditions but also according to the exclusively cold treatment, in the case of strawberry puree, and the pressure treatment, in the case of apple puree. After data analysis, seven metabolites were identified and proposed as processing markers: pyroglutamic acid, pteroyl-D-glutamic acid, 2-hydroxy-5-methoxy benzoic acid, and 2-hydroxybenzoic acid ß-d-glucoside in strawberry and di-hydroxycinnamic acid glucuronide, caffeic acid and lysoPE(18:3(9Z,12Z,15Z)/0:0) in apple purees. The use of these markers may potentially help to objectively measure the degree of food processing and help to clarify the controversial narrative on ultra-processed foods.

Synthesis of a Polyoxometalate-Encapsulated Metal-Organic Framework via In Situ Ligand Transformation Showing Highly Catalytic Activity in Both Hydrogen Evolution and Dye Degradation.

In situ molecular transformation under hydrothermal conditions is a feasible method to introduce distinct organic ligands and suppress competitive reactions between different synthons. However, this strategy has not yet been explored for the preparation of polyoxometalate (POM)-encapsulated metal-organic frameworks (MOFs). In this work, we designed and prepared a new compound, [Co2(3,3'-bpy)(3,5'-bpp)(4,3'-bpy)](H2O)3[SiW12O40] (1) (4,3'-bpy = 4,3'-dipyridine, 3,5'-bpp = 3,5'-bis(pyrid-4-yl)pyridine, and 3,3'-bpy = 3,3'-bis(pyrid-4-yl) dipyridine), via an in situ ligand synthesis route. The compound shows a novel POM-encapsulated MOF structure with two pairs of left- and right-handed double helixes. These left- and right-handed helical chains further lead to triangular and rhombus-like channels, respectively. Moreover, the as-synthesized title compound shows superior electrocatalytic activity toward the hydrogen evolution reaction (HER) in 1 M KOH aqueous solution with a low overpotential and Tafel slope of 92 mV and 92.1 mV dec-1, respectively, under a current density of 10 cm-2. Also, the compound exhibits a high activity for the photocatalytic degradation of the dye rhodamine B. The excellent performance of the compound may be attributed to the synergistic effect between W and Co elements and the presence of encapsulated POMs. The title compound proves that it is possible to prepare multifunctional MOFs with POMs and transition metals showing HER activity and dye degradation activity.