Tumor microenvironment‐activatable oridonin‐loaded iron‐based metal–organic frameworks for targeting cancer therapy

Tumor microenvironment-activatable oridonin-loaded iron-based metal–organic frameworks for targeting cancer therapy

A water-dispersible Ori-loaded Fe-MOF NPs with suitable particle size and good biocompatibility were successfully synthesized and modified with tumor-targeting FA on its surface. The obtained Fe-MOF-FA@Ori NPs possess low cytotoxicity, good drug loading capacity, and pH-responsive drug release property. Meanwhile, the Fe-MOF-FA@Ori NPs exhibit better cancer therapeutic efficiency and could signally induce apoptosis, interfere with the cell cycle progression, and inhibit the migration ability of SMMC-7721 cells.


Oridonin (Ori) is a natural active component with superior anticancer properties; however, its clinical application is severely limited by the inherent properties of short half-life, limited bioavailability, and low water solubility. Some metal–organic frameworks (MOFs) materials have unique porous structure and appropriate nanometer particle size that are attractive in drug delivery. Herein, a folic acid (FA)-functionalized Fe-MOF was designed to efficiently incorporate Ori for targeting delivery to cancer cells and improve anticancer effects. The synthesized Fe-MOF-FA@Ori showed an average particle size of 200 nm with a loading capacity of 12.57%. The cytotoxicity assay confirmed that Fe-MOF-FA@Ori was effective in inhibiting the proliferation of SMMC-7721 cells. Mechanistically, the synthesized nanoparticle induced apoptosis and blocked the progression of the G0/G1 phase cell cycle on SMMC-7721 cells. Cell metastasis and invasion assays demonstrated that Fe-MOF-FA@Ori had good anti-metastatic ability against SMMC-7721 cells. Overall, Fe-MOF-FA is a potent drug carrier for targeting cancer therapy.

From tetramerization to oligomerization/polymerization of ethylene by dinuclear pyridyl‐imine Co‐ and Ni‐based catalysts

From tetramerization to oligomerization/polymerization of ethylene by dinuclear pyridyl-imine Co- and Ni-based catalysts

We developed the one-pot synthesis route to prepare dinuclear Co- and Ni-based catalysts. The Co-based catalysts tetramerize ethylene with high selectivity, while oily to branched solid polyethylene were produced by Ni-based catalysts. Empirical conforming evidences for cooperative effect between the centers by changing the monomer length confirmed.


A series of dinuclear pyridyl-imine Co- and Ni-based complexes (Co: C 1 and C 2 and Ni: C 3 and C 4 ) were prepared in reasonable yields through one-pot synthesis method. Toward ethylene oligomerization/polymerization, C 1 and C 2 , activated by MMAO, were capable to produce oligomers with moderate activity (up to 5.1 × 105 g mol−1 Co h−1 for C 2 ) which α-C8 was the major product. In contrast, C 3 and C 4 polymerized ethylene that the activity of C 4 was twofold greater than C 2 . The high impact of o-substituent in C 2 and C 4 was along with dinuclearity effect leading to high productivity and selectivity for ethylene oligomerization and polymerization, respectively. Moreover, polymerization parameters had strong influence on catalytic behavior of C 4 and polyethylene samples made. For instance, high sensitivity of the structures led to formation of an oily branched oligoethylene to highly branched, high M w polyethylene by changing the polymerization conditions. Polymerization of higher α-olefins such as 1-hexene and 1-octene, moreover, emphasized the effect of effective distance between the centers where an oily low M w oligo-1-hexene and a solid poly(1-octene) having higher M w were yielded. On the other side, quantum chemistry calculations were performed to investigate the structural properties and reactivity of the Ni- and Co-based species. The obtained results indicated that the Ni atoms have strong molecular orbital interactions with the CC bond which may increase the reactivity of the catalyst in comparison with the Co metals.

Photocatalytic activity of co‐doped NPs based on ZnO as a new class of anti‐microbial agents: Synthesis, characterization, kinetics, isotherm, and in silico molecular docking simulation

Photocatalytic activity of co-doped NPs based on ZnO as a new class of anti-microbial agents: Synthesis, characterization, kinetics, isotherm, and in silico molecular docking simulation

Pure ZnO and the co-doped ZnO synthetize using a hydrothermal technique. After characterizing, XPS and EDX showed that Sm3+, La3+, and Sr2+ ions integrated into the ZnO lattice. The Zeta potential proved the positivity surface charge of nanomaterials. Consequently, they utilized it to investigate the breakdown of reactive red 43. The Sm-Sr CDZ NPs exhibit high photocatalytic activity. Surprisingly, most of these nanomaterials expressed bactericidal and fungicidal potential. Finally, investigated the molecular docking simulation.


This work effectively synthesized pure ZnO (PZ) and the co-doped ZnO as Sm-La CDZ NPs, La-Sr CDZ NPs, and Sm-Sr CDZ NPs using a hydrothermal technique. To characterize synthetic nanomaterials used, several techniques, including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectra, ultraviolet and visible (UV/Vis), photoluminescence (PL), scanning electron microscopy (SEM), and graphs by energy dispersive X-ray spectroscopy (XPS), Zeta potential, point of (pHpzc), and specific surface areas. Furthermore, the XRD, SEM, and TEM confirmed the hexagonal crystalline structure. However, XPS and EDX showed that Sm3+, La3+, and Sr2+ ions integrated into the ZnO lattice. The UV-estimated band gaps increased in the co-doped ZnO; BET surface areas declined. The Zeta potential proved the positivity surface charge of nanomaterials. Consequently, they utilized it to investigate the breakdown of reactive red 43 (RR43). The degradation percentages for PZ, Sm-La CDZ NPs, La-Sr CDZ NPs, and Sm-Sr CDZ NPs were 72.88%, 82.63%, 87.08%, and 91.31%, respectively. According to the results, the Sm-Sr CDZ NPs exhibit high photocatalytic activity. In addition, the pseudo-first-order kinetic model and Langmuir model were a better fit. The photocatalytic nanomaterials were also recyclable, which added to their stability. The prepared nanoparticles were evaluated against four bacterial strains and two fungal pathogenic, and the result exhibited a broad spectrum against tested strains. The co-doped NPs revealed MIC values ranging between1.95 and 62.5 μg/mL and MBC values of (31.3–250 μg/mL) compared with PZ (MIC = 7.81–62.5 μg/mL and MBC = 31.3–250 μg/mL) against bacterial strains. Surprisingly, most of these NPs expressed bacteriocidal and fungicidal potential. In silico molecular docking simulation suggested that the antibacterial activity may be related to the inhibition of DNA gyrase, cell wall synthesis (Upps and Fos A), and biofilm activity (PqsR).

Recent advances in catalytic and electrocatalytic applications of half‐sandwich nickel(0/II) N–heterocyclic carbene complexes

Recent advances in catalytic and electrocatalytic applications of half-sandwich nickel(0/II) N–heterocyclic carbene complexes

Nickle-based half-sandwich complexes derived from N-heterocyclic carbene ligands are summarized. Their design, synthesis, characterization, and catalytic and electrocatalytic potentials have been reviewed. This study provides a new avenue for the potent design of active and stable nickel-based catalysts.


Diverse structural and catalytic features of half-sandwich nickel N–heterocyclic carbene (NHC) complexes provide an encouraging platform not only to address the drawbacks of other group X (palladium and platinum) metal NHC catalysts but also to bring about their superior performance. The chemistry of nickel NHC complexes has gained substantial interest from the organometallic community owing to their remarkable stability to air and moisture, easier preparation protocols, and availability of wide scope for structural fine tuning in order to achieve targeted applications. The recent progress in the field of half-sandwich nickel(0/II) NHC complexes is covered in this review article with a special emphasis on the different synthetic strategies employed, structural characterization including spectral and X-ray diffraction techniques, and surface morphology of the films of complexes. Both, homogeneous and electrocatalytic applications of half-sandwich nickel NHC complexes are discussed with respect to their potential in various C–C and C–S bond constructions, targeted C–H bond activations, reductions using silylating agents, electrocatalytic glucose sensing, and electrocatalytic hydrogen evolution reactions. Donor functionalized complexes displayed improved catalytic potential in several C–C and C–S coupling reactions over non–functionalized counterparts. Overall, this assessment, from a comprehensive standpoint, affords evidence that is advantageous in the design of novel NHC ligands to access targeted half-sandwich nickel(0/II) NHC complexes encompassing potential homogeneous catalytic and electrocatalytic applications.

Silver(I) complexes with nitrile ligands: New materials with versatile applications

Silver(I) complexes with nitrile ligands: New materials with versatile applications

The complexes of silver nitrate and nitrite with organic nitriles show very good antimicrobial and antifungal properties, connected with the facile release of silver ions. Along with the antimicrobial activity, interesting electrical phenomena related to the electronic structure of organic ligands have been observed.


In the present study, the structure, thermal stability, conductive properties, and antimicrobial activity of silver(I) complexes with nitrile ligands were investigated. For the construction of the materials, 2-cyanopyridine (2-cpy), 4-cyanopyridine (4-cpy), 1,2-dicyanobenzene (1,2-dcb), and 1,3-dicyanobenzene (1,3-dcb) were used in addition to the silver nitrite and nitrate. Four new compounds were isolated and structurally characterized: one molecular complex [Ag4(1,2-dcb)4(NO3)4], two 1-D coordination polymers [Ag(2-cpy)2(NO2)], [Ag2(1,3-dcb)2(NO3)2], and one 3-D coordination polymer [Ag(4-cpy)(NO2)]. The results indicate that the nitrile complexes display good antimicrobial properties against the tested bacterial and fungal strains. The presence of weakly coordinating CN groups increases the release of silver ions into the bacterial and yeast cell environments. Moreover, these materials exhibit unusual electrical properties in thin-layer devices. On the other hand, the nitrite and nitrate counterions give rise to the low thermal stability of the complexes.

Experimental and computational studies of two binuclear Co(II) and Ni(II) bis(salamo)‐like complexes

Experimental and computational studies of two binuclear Co(II) and Ni(II) bis(salamo)-like complexes

Acetate-bridged Co(II) and Ni(II) complexes, [Co(L)(μ-OAc)(EtOH)] (1) and [Co(L)(μ-OAc)(EtOH)] (2) were synthesized by reacting the bis(salamo)-like ligand with two different metal(II) acetates. The ratio of the ligand and metal(II) ions in the solid and liquid phases of the complexes was determined by X-ray single crystal diffraction and UV–vis spectral titration, and the uniqueness of the solid–liquid two-phase substance was determined.


Acetate-bridged binuclear Co(II) and Ni(II) complexes, [Co2(L)(μ-OAc)(EtOH)] (1) and [Ni2(L)(μ-OAc)(EtOH)] (2) were synthesized via the reaction of a new bis(salamo)-like ligand with two different metal(II) acetates. X-ray single crystal diffraction analyses showed that two metal(II) ions (Co or Ni) occupy two sets of N2O2 cavities, respectively. The acetate group bridges the two metals, and the ethanol oxygen atom participates in the coordination. Furthermore, UV–vis titration experiments clearly indicated that the complexation between H3L and M(II) ions leads to the 1:2 complexes [(L)M2]+ through a highly synergistic process. Bond valence sum (BVS) calculations exhibited that the Co(II) and Ni(II) ions are divalent. Secondly, the ligand H3L highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO-LUMO) gap analysis and surface electrostatic potential were theoretically analyzed by theoretical calculation (density functional theory), and the reactivity of M(II) ions and the ligand in the complex formation process was demonstrated. Finally, the microscopic properties of the complexes were deeply understood through the calculation of the weak intramolecular interactions and the unstressed regions outside the complexes.

Synthesis, structural characterization, and in vitro biological activity studies of ternary metal complexes of 1,10‐phenanthroline and the anti‐inflammatory bromhexine drug

Synthesis, structural characterization, and in vitro biological activity studies of ternary metal complexes of 1,10-phenanthroline and the anti-inflammatory bromhexine drug

The current research describes the synthesis of a unique series of mixed ligand complexes of Cr(III), Fe(III), Ni(II), Mn(II), Cu(II), Co(II), Zn(II), and Cd(II) produced from BHX (1ry ligand) and 1,10-phenanthroline (Phen; 2ry ligand) and distinguished by spectral. The two ligands' potential for coordination with metal ions has been suggested by chemical analysis and spectral (1H-nuclear magnetic resonance, ultraviolet-visible, and mass spectrometry) and thermal studies. BHX and Phen are neutrally bidentately coupled to the metal ions.


The medication bromhexine (BHX) is well-known for its unique properties and therapeutic advantages, with prospective uses in the prevention and treatment of cancer growth and bacterial infections. The current research describes the synthesis of a unique series of mixed ligand complexes of Cr(III), Fe(III), Ni(II), Mn(II), Cu(II), Co(II), Zn(II), and Cd(II) produced from BHX (1ry ligand) and 1,10-phenanthroline (Phen; 2ry ligand) and distinguished by spectral. The two ligands' potential for coordination with metal ions has been suggested in view of chemical analysis and spectral (1H-nuclear magnetic resonance, ultraviolet–visible, and mass spectrometry) and thermal studies. BHX and Phen are neutrally bidentately coupled to the metal ions, according to infrared spectral study. The general formula of [M(BHX)(Phen)(H2O)n.Clm] was suggested using the molar conductivity, elemental analyses, and thermal information of the complexes that were produced. Where M = Fe(III) (n = y = 2, m = 0, and x = 3), Co(II) (n = x = 2, m = 0, and y = 3), Ni(II) (n = x = 2, m = 0, and y = 6), and Cd(II) (n = x = y = 2 and m = 0) with an octahedral geometry was proposed. Thermal analyses revealed that the complexes lost anionic part and organic ligands in continual changes after first losing water molecules of hydration. Compared with their parent BHX ligand, the mixed ligand complexes demonstrated promising microbiological activities against a variety of bacterial species, including Gram-positive bacteria (Bacillus subtilis and Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). According to the results, mixed ligand complexes are more efficient than the parent BHX and Phen ligands. The complexes moderately inhibit the development of the MCF-7 antibreast cancer cell line. The chemistry of the linking energy, H-bond, and hydrophobic interactions of the BHX ligand and its mixed Cu(II) complex with Phen are revealed by molecular docking investigations with the crystal structure of S. aureus nucleoside (PDB: 3Q8U) and human prostate-specific antigen (PDB: 3QUM).

Molybdenum (VI) complex of resorcinol‐based ligand immobilized on silica‐coated magnetic nanoparticles for biodiesel production

Molybdenum (VI) complex of resorcinol-based ligand immobilized on silica-coated magnetic nanoparticles for biodiesel production

Molybdenum (VI) complex of resorcinol-based ligand immobilized on silica-coated magnetic nanoparticles was prepared. The catalyst was characterized with analytical techniques such as FT-IR, SEM, TEM, XRD, XPS, VSM, ICP, EDX, NH3-TPD, and TGA. This novel catalyst with acidic and basic sites was used in (trans)esterification reaction for biodiesel production of rapeseed, soybean, and sunflower and used frying oils under mild reaction conditions with easy reusability, high activity, and selectivity with acidic and basic sites.


Reusability and durability of catalysts are main factors in biodiesel production. Fe3O4@SiO2-APTES-MoO2L2 DHAPh catalyst was prepared in five steps. At first, Fe3O4 was synthesized and coated with silica (Fe3O4@SiO2). After that, the nanoparticles were functionalized by APTES (Fe3O4@SiO2-APTES). In following, DHAPh ligand was anchored covalently onto the surface of aminated magnetic nanoparticles (Fe3O4@SiO2-APTES-LDHAPh), and at the end, DHAPh ligand was metalled by MoO2(acac)2 salt (Fe3O4@SiO2-APTES-MoO2L2 DHAPh). The catalyst was characterized with analytical techniques such as FT-IR, SEM, TEM, XRD, XPS, VSM, ICP, EDX, NH3-TPD, and TGA. This novel catalyst with acidic and basic sites was used in (trans)esterification reaction for biodiesel production of rapeseed and other oils. The biodiesel yield of rapeseed, soybean, sunflower, and used frying oils was attained 97%, 98%, 96%, and 87%, respectively, under optimized reaction conditions, such as 0.1 mol% amount of catalyst, 0.05 mmol KOH as methanol activator, a short reaction time of 2 h, and methanol to oil ratio of 3:1 at room temperature. The conversion of oil to methyl ester biodiesel was confirmed by FT-IR, 1H NMR, and GC-MS analysis. The leaching and reusability tests of the prepared catalyst were checked, which displayed the biodiesel production proceeded via a heterogeneous pathway. Also, this catalyst can be reused for 11 cycles without tangible loss in its catalytic activity. The mentioned heterogeneously homogenized nanocatalyst has the main benefits such as easy reusability, high activity, and selectivity with acidic and basic sites that makes it a potential candidate for both esterification and (trans)esterification of low quality feedstock for low cost biodiesel production.

Iron integrated carbon nitride: A recoverable heterogeneous catalyst for the construction of bis (hetero/homoarylidene)cycloalkanones

Iron integrated carbon nitride: A recoverable heterogeneous catalyst for the construction of bis (hetero/homoarylidene)cycloalkanones

Iron tethered carbon nitride has been developed and utilized as a recoverable heterogeneous catalyst for the construction of bis (hetero/homoarylidene)cycloalkanones in water, an environmentally nonthreatening medium at ambient temperature.


Iron integrated graphitic carbon nitride (GCN) was synthesized by adopting co-precipitation method. No appreciable change in XRD main peak of both GCN and Fe(III)-GCN indicates the lattice structure remains the same and there is no bulk doping of Fe(III). More sharp IR bands of Fe(III)-GCN between 1000 and 1750 cm−1 compared with GCN reflect ordered packing of tri-s-triazine units in the nanosheets. Scanning electron microscopy (SEM) analysis reveals less thin and large two dimensional sheets have formed from bulk GCN during catalyst preparation. The absence of bright spots in transmission electron microscopy (TEM) indicates that there is no crystalline metal oxide phase confirming that iron(III) is present as ions. Fe(III)-GCN was then exploited as an efficient heterogeneous catalyst for the synthesis of bis (hetero/homoarylidene)cycloalkanones from heteroaromatic/homoaromatic carbaldehydes and cycloalkanone through carbon–carbon double bond construction. The reaction effected well in water, a green solvent as a reaction medium at ambient temperature. The catalytic competency exposed good performance towards reusability. Added advantages include easy preparation and inexpensiveness.

Catalytic combustion of a dendrimer containing ferrocene units with anti‐migration performance on composite propellant

Catalytic combustion of a dendrimer containing ferrocene units with anti-migration performance on composite propellant

A new dendrimer containing ferrocene units is used as an efficient combustion catalyst for ammonium perchlorate-based propellant.


Ferrocene-based compounds are promising burning rate catalysts due to their attractive catalytic activity, flammability, and non-toxic performance. Unfortunately, the high-migration issue of the ferrocene-based catalysts makes it challenging to store composite solid propellants for a long time. Therefore, a dendrimer containing ferrocene units with anti-migration ability was designed herein. The introduction of polar groups provides a large number of interaction sites for anti-migration, and no migration of the dendrimer in the propellant was observed after 4 weeks of the aging test. For catalytic performance, the results showed that the thermal decomposition temperature of ammonium perchlorate could be reduced from 404°C to 369°C by adding 3 wt% ferrocene-based dendrimer. Moreover, compared with the propellant mixed with Catocene, the propellant containing ferrocene-based dendrimer showed a lower pressure exponent (0.47) and a higher burning rate (2.03 mm·s−1, at 0.1 MPa).