Immunomodulation of cuproptosis and ferroptosis in liver cancer.

According to statistics, the incidence of liver cancer is increasing yearly, and effective treatment of liver cancer is imminent. For early liver cancer, resection surgery is currently the most effective treatment. However, resection does not treat the disease in advanced patients, so finding a method with a better prognosis is necessary. In recent years, ferroptosis and cuproptosis have been gradually defined, and related studies have proved that they show excellent results in the therapy of liver cancer. Cuproptosis is a new form of cell death, and the use of cuproptosis combined with ferroptosis to inhibit the production of hepatocellular carcinoma cells has good development prospects and is worthy of in-depth discussion by researchers. In this review, we summarize the research progress on cuproptosis combined with ferroptosis in treating liver cancer, analyze the value of cuproptosis and ferroptosis in the immune of liver cancer, and propose potential pathways in oncotherapy with the combination of cuproptosis and ferroptosis, which can provide background knowledge for subsequent related research.

Assembly of highly efficient overall CO2 + H2O electrolysis cell with the matchup of CO2 reduction and water oxidation catalyst.

The exploitation of highly active and stable catalysts for reduction of CO2 and water oxidation is one of the approaches to facilitate scalable and sustainable CO2 reduction potentially at the industrial scale. Herein, a feasible strategy to rationally build an overall CO2 + H2O electrocatalytic reaction device is the preparation and matchup of a high-performance CO2 reduction catalyst and low-cost and highly active oxygen anode catalyst. A heterostructured nanosheet, γ-NiOOH/NiCO3/Ni(HCOO)2, exhibited superior catalytic activity in the oxygen evolution reaction, and was integrated with CoPc/Fe-N-C to build an overall CO2 + H2O cell with a current density of 10 mA cm-2 at a very low cell voltage of 1.97 V, and the faradaic deficiency of CO2 to CO was maintained at greater than 90% at 1.9 V.

A Novel Manner of Anchoring Cobalt Phthalocyanine on Edge-Defected Carbon for Highly Electrocatalytic CO2 Reduction.

Cobalt phthalocyanine anchored on carbon material has attracted an enormous amount of attention due to its superior performance in electrocatalytic CO2 reduction. However, the interaction between cobalt phthalocyanine and the carbon substrate remains problematic, and the role of intrinsic carbon defects is unfortunately ignored in the anchoring of cobalt phthalocyanine on carbon. Herein, new interactions between the bridging N atoms of cobalt phthalocyanine and the edge defects of carbon have been discovered, which result in a novel model of anchoring of cobalt phthalocyanine on ketjen black carbon. Such anchored cobalt phthalocyanine has been found to be responsible for superior catalysis for electrochemical reduction of CO2 to CO with high selectivity and low overpotential.

Construction of a C@MoS2@C sandwiched heterostructure for accelerating the pH-universal hydrogen evolution reaction.

Herein a facile and versatile hydrothermal method has been developed to construct a polypyrrole-derived carbon nanotube (PCN), MoS2 nanosheets and a carbon shell integrated sandwich-like heterostructure (PCN@MoS2@C). This heterostructure shows excellent performance in the hydrogen evolution reaction (HER) over a wide pH range. The results indicate that the porous carbon shell coated heterostructure provides MoS2 nanosheets with sufficient conductivity, increased number of active sites, and strong structural stability, and thus boosts its HER performance.

Highly Selective and Active Electrochemical Reduction of CO2 to CO on a Polymeric Co(II) Phthalocyanine@Graphitic Carbon Nitride Nanosheet-Carbon Nanotube Composite.

The electrochemical reduction of CO2 using intermittent renewable electricity is an attractive strategy for producing value-added fuels and chemicals, but until now, it has been greatly hindered by the shortage of high-performance electrocatalysts. In this study, we have demonstrated a type of molecular-catalyst-based hybrid material by the polymerization of cobalt phthalocyanine (CoPc) on a three-dimensional (3D) g-C3N4 nanosheet-carbon nanotube support for the aqueous electrochemical reduction of CO2. The electrocatalytic results show that the obtained composite can selectively transform CO2 to CO with considerable Faradaic efficiency (FE) of 95 ± 1.8%, a turnover frequency of 4.9 ± 0.2 s-1, and excellent long-term stability over 24 h at -0.8 V vs the reversible hydrogen electrode (RHE). In comparison to the analogous hybrid electrocatalysts prepared by the drop-drying or dip-coating method, the polymeric form of the molecular catalyst immobilized on 3D carbonaceous materials with an interconnected network enlarges the electrochemically active surface area and enhances the structural and operational robustness.

A Water-Stable Uranyl Organic Framework as a Highly Selective and Sensitive Bifunctional Luminescent Probe for Fe3+ and Tetracycline Hydrochloride.

A new coordination polymer (H2 bpy)0.5 ⋅[(UO2 )1.5 (ipa)2 (H2 O)] (1) (H2 ipa=isophthalic acid, bpy=4,4'-bipyridine) was synthesized by hydrothermal condition. It was characterized by IR spectroscopy, elemental analysis, TG-DTA analysis, and powder X-ray diffraction. Analysis of single-crystal X-ray diffraction results showed that the title compound exhibited a double chain bridged by the different uranyl ions and ipa2- ligands. Through the hydrogen bond interactions and π⋅⋅⋅π stacking interactions, the double chains were assembled into the three-dimensional supramolecular framework. Furthermore, the compound can be used as a promising bifunctional luminescence sensor for detecting and identifying Fe3+ and tetracycline hydrochloride antibiotic molecules with high selectivity and sensitivity in aqueous solutions. Moreover, the luminescent sensing mechanisms for different analytes were proposed. Moreover, the electronic properties of title compound were explored by density functional theory (DFT) calculations. The sensor system has been successfully applied for the detection of Fe3+ and tetracycline hydrochloride with high recovery percentages and low relative standard deviation in real river water samples.

Nitro-functionalized metal-organic frameworks with catalase mimic properties for glutathione detection.

In the present study, four copper-based metal-organic frameworks were facilely prepared to study the effects of the substituent groups of the ligand on the enzyme-like properties of these frameworks. It was found that all of them were capable of catalyzing the reaction between 3,3',5,5'-tetramethylbenzidine (TMB) and H2O2; this demonstrated their enzyme-like properties. Moreover, the enzyme-like catalytic properties of all the Cu-MOFs obtained herein were studied in detail. Interestingly, the results indicate that the four Cu-MOFs should be addressed as different enzyme mimics although the chemical structures of their ligands are quite similar. Among these four MOFs, the Cu-MOF with the -NO2 group (Cu-MOF (ii)) exhibits highest catalytic activity at neutral pH, which would be beneficial for its application in real biological samples. Moreover, its catalytic activity should be ascribed to the generation of oxygen induced by Cu-MOF (ii)-catalyzed H2O2 decomposition; this accordingly indicates that this MOF should be called a catalase mimic. Under optimized conditions, the Cu-MOF (ii) was applied to develop a (GSH) colorimetric assay for glutathione (GSH). In addition, GSH detection in serum was performed, and satisfactory results were obtained. Therefore, a simple, sensitive and selective colorimetric assay based on the MOF catalase mimic for the detection of GSH was developed.

Ratiometric system based on graphene quantum dots and Eu3+ for selective detection of tetracyclines.

In this study, a system was established for the detection of tetracyclines (TCs) by simply mixing graphene quantum dots (GQDs) and Eu3+. The GQDs-Eu3+ system exhibits both strong emission of GQDs and weak characteristic emission of Eu3+ upon 360 nm excitation. In the presence of TCs, the luminescence of GQDs was quenched, while the luminescence of Eu3+ was significantly enhanced. It is worth to mention that the GQDs we prepared possess a lot of carboxyl groups on the surface and edge. This carboxyl groups play an important role in fluorescent enhancement of Eu3+. On the basis of this effect, a novel label free ratiometric sensor was developed for the detection of TCs. Under the optimized conditions, linear concentration ranges from 0 to 20 µM for tetracycline was found, and the detection limits was 8.2 nM. This system also exhibited excellent selectivity toward TCs over other antibiotics. In addition, it was successfully applied to the determination of tetracycline in river water and milk samples. The proposed system was simple in design, fast in operation, rapid in response and cost-effective. In view of the advantages, the developed system demonstrates great potential for the detection of TCs in environmental and biological samples.

Six uranyl-organic frameworks with naphthalene-dicarboxylic acid and bipyridyl-based spacers: syntheses, structures, and properties.

A new series of uranium coordination polymers have been hydrothermally synthesized by using 1,4-naphthalene dicarboxylic acid (H2NDC), namely, (H3O)2[(UO2)2(NDC)3]·H2O (1), (H2-bpp)[(UO2)2(NDC)3]·EtOH·5H2O (2), (H2-bpe)2/2[(UO2)2(NDC)3]·EtOH (3), (H2-bpp)[(UO2)2(NDC)3]·5H2O (4), (H2-bpp)[(UO2)(HNDC)(NDC)]2·2H2O (5), and (H2-bpy)[(UO2)(NDC)2] (6) [bpp = 1,3-di(4-pyridyl) propane, bpe = 4,4'-vinylenedipyridine, bpy = 4,4'-bipyridine]. Single-crystal X-ray diffraction demonstrates that complex 1 represents the uranyl-organic polycatenated framework derived from a simple two-dimensional honeycomb grid network structure via a H2NDC linker. Complexes 2-4 contain the dinuclear motifs of the two UO7 pentagonal and one UO8 hexagonal bipyramids which are linked by NDC2- anions creating a (UO2)4(NDC)2 unit, and further extend to a 2D layer through NDC2- anions. Complex 5 displays a 1D zigzag double chain structure, in which the carboxylate groups of the NDC2- anions adopt a chelate mode and further extends to a 2D framework via hydrogen bonds. The 1D structure of complex 6 is similar to the zigzag chain of complex 5. In addition, powder X-ray diffraction, elemental analysis, IR, thermal stability and luminescence properties of all complexes have also been investigated in this paper. The photocatalytic properties of the six complexes for the degradation of tetracycline hydrochloride (TC) under UV irradiation have been examined. Moreover, density functional theory (DFT) calculations were carried out to explore the electronic structural and bonding properties of the uranyl complexes 1-6.

Theoretical investigations on the unsymmetrical effect of ß-link Zn-porphyrin sensitizers on the performance for dye-sensitized solar cells.

Dye sensitizers play an important role in dye-sensitized solar cells (DSSCs). As a promising strategy for the design of novel porphyrin sensitizers, the asymmetric modification of the porphyrin ring to meso-link porphyrin sensitizer has emerged in recent years, which can improve the light-harvesting properties and enhance the electron distribution. In this work, in order to reveal the essence of the effect of unsymmetrical substitution on the performance of ß-link porphyrin dyes in DSSCs, four kinds of common ß-link porphyrin dyes with different structures are calculated by using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The electronic structures and optical properties of these studied dyes in dimethylformamide (DMF) are also investigated. The key parameters of the short-circuit current density (Jsc), including light harvesting efficiency (LHE), electron injection driving force (ΔGinject), and intra-molecular charge transfer (ICT) are discussed in detail. In addition, the periodic DFT calculations in the dye-TiO2 systems are also employed to investigate the geometrical and electronic injection process of the different connection types of these studied dyes adsorbed on the periodic TiO2 model with an exposed anatase (101) surface. We expect the present study would deepen the understanding of the alternative function of unsymmetrical substitution and may contribute to future DSSC design.

Co3O4 nanocrystals as an efficient catalase mimic for the colorimetric detection of glutathione.

Nanomaterial-based artificial enzymes (nanozymes), as an emerging generation of artificial enzymes, have received extensive attention in recent years owing to their striking merits. In this study, the obtained Co3O4 nanocrystals exhibited catalase-like activity and could catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2, and a clear absorption peak at 652 nm can be observed. It was verified that the catalytic activity for the oxidation of TMB originated from the oxygen, which is generated by Co3O4 catalyzed H2O2 decomposition. Upon addition of glutathione (GSH), the catalytic ability of the Co3O4 nanocrystals was inhibited. And, the changes of absorbance at 652 nm could be utilized to quantify the concentration of GSH. Under the optimized conditions, the proposed assay showed good linear relationships and a low detection limit towards GSH. Moreover, the Co3O4 nanocrystals had excellent stability and can maintain the catalytic activity for a long time. Thus, a simple, sensitive and selective nanozyme-based biosensor was developed for the colorimetric detection of GSH.

A pyrene-modified cobalt salophen complex immobilized on multiwalled carbon nanotubes acting as a precursor for efficient electrocatalytic water oxidation.

Immobilization of earth-abundant water oxidation catalysts (WOCs) on carbon supports to produce functional electrodes for electrochemical water splitting is a crucial approach for future clean energy production. Herein we report the non-covalent immobilization of a pyrene-bearing cobalt(ii) Schiff base complex (2) on the surface of multiwalled carbon nanotubes (MWCNTs) to form a hybrid anode for electrocatalytic water oxidation. The 2/MWCNT anode displayed excellent catalytic activity and durability in neutral aqueous solution, and a catalytic current density of 1.0 mA cm-2 was achieved at 1.15 V vs. the normal hydrogen electrode (NHE), corresponding to a low overpotential of 330 mV. A Tafel slope of 96 mV per decade was obtained. The Faradaic efficiency of oxygen evolution was more than 90% by bulk electrolysis measurement. After bulk electrolysis, the hybrid anode characterization using X-ray photoelectron spectroscopy (XPS) confirmed that complex 2 decomposed to form heterogeneous cobalt hydroxides and the cobalt hydroxides should be true catalytic active species, which are responsible for electrocatalytic oxygen evolution.

Electrocatalytic water oxidation using a chair-like tetranuclear copper(ii) complex in a neutral aqueous solution.

The development of viable molecular water oxidation catalysts is an important issue in the conversion of electricity or solar fuel into chemical fuels via water splitting, and copper complexes have become promising candidates for catalyzing water oxidation because of their low cost, well-defined redox properties and relatively high reactivity. Herein, we describe the first tetranuclear Cu(ii)-based water oxidation catalyst: [Cu4(bpy)4(µ2-OH)2(µ3-OH)2(H2O)2](2+). The complex comprises a chair-like Cu4O4 core with aqua and bridging µ-hydroxo ligands, and the multinuclear core is expected to be advantageous for promoting multi-electron transfer. In pH 7.0 phosphate buffer, the complex shows as being hydrolytically stable and a relatively low overpotential of ca. 730 mV is obtained according to a cyclic voltammetry experiment. Bulk electrolysis measurements at 1.80 V vs. a normal hydrogen electrode provided a stable current density of 0.78 mA cm(-2) and the current persists for at least 10 h. A Faradaic efficiency of nearly 98% is achieved. Importantly, the electrochemical data support that this tetranuclear complex works as a robust homogeneous water oxidation catalyst.

New Cu(II) complexes based on the hydroxo-bridged dinuclear [Cu(OH)2Cu] units: step-like di- and trimerizations of [Cu(OH)2Cu] units.

Four new Cu(II) complexes {[Cu(4)(bpy)(4)(OH)(4)(H(2)O)(2)]}(NO(3))(2)(C(7)H(5)O(2))(2)·6H(2)O 1, {[Cu(4)(bpy)(4)(OH)(4)(H(2)O)(2)]}(NO(3))(2)(C(5)H(6)O(4))·8H(2)O 2, {[Cu(4)(bpy)(4)(OH)(4)(H(2)O)(2)]}(C(5)H(6)O(4))(2)·16H(2)O 3 and {[Cu(6)(bpy)(6)(OH)(6)(H(2)O)(2)]}(C(8)H(7)O(2))(6)·12H(2)O 4 were synthesized (bpy = 2,2'-bipyridine, H(2)(C(5)H(6)O(4)) = glutaric acid, H(C(7)H(5)O(2)) = benzoic acid, H(C(8)H(7)O(2)) = phenyl acetic acid). The building units in 1-3 are the tetranuclear [Cu(4)(bpy)(4)(H(2)O)(2)(µ(2)-OH)(2)(µ(3)-OH)(2)](4+) complex cations, and in 4 the hexanuclear [Cu(6)(bpy)(6)(H(2)O)(2)(µ(2)-OH)(2)(µ(3)-OH)(4)](6+) complex cations, respectively. The tetra- and hexanuclear cluster cores [Cu(4)(µ(2)-OH)(2)(µ(3)-OH)(2)] and [Cu(6)(µ(2)-OH)(2)(µ(3)-OH)(4)] in the complex cations could be viewed as from step-like di- and trimerization of the well-known hydroxo-bridged dinuclear [Cu(2)(µ(2)-OH)(2)] entities via the out-of-plane Cu-O(H) bonds. The complex cations are supramolecularly assembled into (4,4) topological networks via intercationic ππ stacking interactions. The counteranions and lattice H(2)O molecules are sandwiched between the 2D cationic networks to form hydrogen-bonded networks in 1-3, while the phenyl acetate anions and the lattice H(2)O molecules generate 3D hydrogen-bonded anionic framework to interpenetrate with the (4,4) topological cationic networks with the hexanuclear complex cations in the channels. The ferromagnetic coupling between Cu(II) ions in the [Cu(4)(µ(2)-OH)(2)(µ(3)-OH)(2)] cores of 1-3 is significantly stronger via equatorial-equatorial OH(-) bridges than via equatorial-apical ones. The outer and the central [Cu(2)(OH)(2)] unit within the [Cu(6)(µ(2)-OH)(2)(µ(3)-OH)(4)] cluster cores in 4 exhibit weak ferromagnetic and antiferromagnetic interactions, respectively. Results about i.r. spectra, thermal and elemental analyses are presented.

A family of new glutarate compounds: synthesis, crystal structures of: Co(H2O)5L(1), Na2[CoL2] (2), Na2[L(H2L)4/2] (3), {[Co3(H2O)6L2](HL)2}.4H2O (4), {[Co3(H2O)6L2](HL)2}.10H2O (5), {[Co3(H2O)6L2]L2/2}.4H2O (6), and Na2{[Co3(H2O)2]L8/2].6H2O (7), and magnetic properties of 1 and 2 with H2L = HOOC-(CH2)3-COOH.

Seven new glutaric acid complexes, Co(H 2O) 5L 1, Na 2[CoL 2] 2, Na 2[L(H 2L) 4/2] 3, {[Co 3(H 2O) 6L 2](HL) 2}.4H 2O 4, {[Co 3(H 2O) 6L 2](HL) 2}.10H 2O 5, {[Co 3(H 2O) 6L 2]L 2/2}.4H 2O 6, and Na 2{[Co 3(H 2O) 2]L 8/2].6H 2O 7 were obtained and characterized by single-crystal X-ray diffraction methods along with elemental analyses, IR spectroscopic and magnetic measurements (for 1 and 2). The [Co(H 2O) 5L] complex molecules in 1 are assembled into a three-dimensional supramolecular architecture based on intermolecular hydrogen bonds. Compound 2 consists of the Na (+) cations and the necklace-like glutarato doubly bridged [ C o L 4 / 2 ] 2 - infinity 1 anionic chains, and 3 is composed of the Na (+) cations and the anionic hydrogen bonded ladder-like [ L ( H 2 L ) 4 / 2 ] 2 - infinity 1 anionic chains. The trinuclear {[Co 3(H 2O) 6L 2](HL) 2} complex molecules with edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 4 and 5 are hydrogen bonded into two-dimensional (2D) networks. The edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 6 are bridged by glutarato ligands to generate one-dimensional (1D) chains, which are then assembled via interchain hydrogen bonds into 2D supramolecular networks. The corner-shared linear [Co 3O 16] trioctahedra in 7 are quaternate bridged by glutarato ligands to form 1D band-like anionic {[Co 3(H 2O) 2]L 8/2} (2+) chains, which are assembled via interchain hydrogen bonds into 2D layers, and between them are sandwiched the Na (+) cations. The magnetic behaviors of 1 and 2 obey the Curie-Weiss law with chi m = C/( T - Theta) with the Curie constant C = 3.012(8) cm (3) x mol (-1) x K and the Weiss constant Theta = -9.4(7) K for 1, as well as C = 2.40(1) cm (3) x mol (-1) x K and Theta = -2.10(5) K for 2, indicating weak antiferromagnetic interactions between the Co(II) ions.

A novel mixed-valence copper complex, poly[[mu2-4,4'-bipyridine-mu3-pyridine-2,4,6-tricarboxylato-dicopper(I,II)] monohydrate].

In the title novel mixed-valence copper complex, {[Cu2(C8H2NO6)(C10H8N2)].H2O}n, the Cu(I) and Cu(II) ions are linked by 4,4'-bipyridine (bpy) and pyridine-2,4,6-tricarboxylate (ptc) ligands into corrugated layers, which are assembled via interlayer C-H...O hydrogen bonds to give a three-dimensional supramolecular architecture.

A new trinuclear cobalt(II) complex: decaaqua-1kappa3O,2kappa4O,3kappa3O-bis(benzene-1,3,5-tricarboxylato)-1kappaO,3kappaO-di-mu-4,4'-bipyridine-1:2kappa2N:N';2:3kappa2N:N'-di-4,4'-bipyridine-1kappaN,3kappaN-tricobalt(II) 4,4'-bipyridine solvate octahydrate.

The principal building units in the title compound, [Co3(C9H3O6)2(C10H8N2)4(H2O)10].C10H8N2.8H2O, are the linear centrosymmetric tricobalt(II) complex molecules resulting from two square-pyramidal [Co(btc)(bpy)(H2O)3]- entities (bpy is 4,4'-bipyridine and btc is the benzene-1,3,5-tricarboxylate trianion) bridged by one trans-[Co(bpy)2(H2O)4]2+ unit. The trinuclear complex molecules are assembled into infinite chains through intermolecular O-H...N hydrogen bonds and pi-pi stacking interactions between adjacent monodentate bpy ligands. The chains and uncoordinated bpy molecules are further assembled into two-dimensional open layers, which are stacked in a staggered manner to give a three-dimensional supramolecular architecture with the solvent water molecules in the cavities.

catena-Poly[bis[(1,10-phenanthroline)nickel(II)]-mu-3,6-dicarboxycyclohexane-1,2,4,5-tetracarboxylato].

In the title compound, [Ni2(C12H8O12)(C12H8N2)2]n, the 3,6-dicarboxycyclohexane-1,2,4,5-tetracarboxylate (H2chhc4-) anion has crystallographically imposed C(2) symmetry and bridges the six-coordinate Ni atoms to generate polymeric infinity1[Ni2(H2chhc)2/2(C12H8N2)2] chains extending in the [010] direction. The coordination polymer chains are linked into a three-dimensional framework by O-H...O and C-H...O hydrogen bonds.

catena-Poly[[mu-hexanedioato-1kappaO1:2kappaO6-bis[aqua(5-carboxypentanoato-kappaO)copper(II)]]-di-mu-4,4'-bipyridine-1kappaN:1'kappaN';2kappaN:2'kappaN'].

In the title compound, [Cu2(C6H8O4)(C6H9O4)2(C10H8N2)2(H2O)2]n, the square-pyramidally coordinated Cu atoms are bridged by both 4,4-bipyridine and adipate ligands into ladder-like chains, with exo-orientated 5-carboxypentanoate ligands pendant from both side rails. Half of the adipate ligand is related to the other half by inversion symmetry. Interchain O-H...O hydrogen bonds from the aqua ligands to the carbonyl O atoms of the 5-carboxypentanoate ligands are responsible for the formation of two-dimensional grid-like (4,4)-networks, which complete a twofold interpenetration.

catena-Poly[[diaquabis(5-carboxypentanoato-kappaO)cobalt(II)]-mu-1,2-di-4-pyridylethane-kappa2N:N'].

The title compound, [Co(C6H9O4)2(C12H12N2)(H2O)2]n, crystallizes in the space group P-1. The Co atom is on a center of symmetry and the 1,2-di-4-pyridylethane (bpe) ligand also sits across a crystallographic inversion center. The Co atom is octahedrally coordinated by two aqua ligands, two carboxylate O atoms and two pyridyl N atoms, and is bridged by the anti-bpe ligands to generate one-dimensional 1infinity{[Co(Hadip)2(H2O)2](bpe)2/2} chains (Hadip is 5-carboxypentanoate), which are further interlinked by O-H...O and C-H...O hydrogen bonds into two-dimensional layers.