Expanding Mn loading capacity of BSA via mild non-thermal denaturing and cross-linking as a tool to maximize the relaxivity of water protons.

Development of nanoparticles (NPs) serving as contrast enhancing agents in MRI requires a combination of high contrasting effect with the biosafety and hemocompatibility. This work demonstrates that bovine serum albumin (BSA) molecules bound to paramagnetic Mn ions are promising building blocks of such NPs. The desolvation-induced denaturation of BSA bound with Mn ions followed by the glutaraldehyde-facilitated cross-linking provides the uniform in size 102.

Specificity of hexarhenium cluster anions for synthesis of Mn-based nanoparticles with lamellar shape and pH-induced leaching for specific organ selectivity in MRI contrasting.

The present work demonstrates the structure variation of hexarhenium anionic cluster units [{ReS}(CN)(OH)] (n = 0, 2, 4) as the strategy to develop Mn-containing nanoparticles (NPs) exhibiting pH-dependent leaching. The dicyanotetrahydroxo complex [{ReS}(CN)(OH)] is the optimal for the synthesis of the Mn-based NPs with a lamellar shape exhibiting the pH-dependent aggregation and magnetic relaxation behavior. The pH-dependent behavior of the NPs derives from the easy protonation of the apical hydroxo ligands of [{ReS}(CN)(OH)] cluster, which triggers partial leaching of Mn ions and aggregation of the NPs driven by the surface neutralization.

ROS-producing nanomaterial engineered from Cu(I) complexes with PN-ligands for cancer cells treating.

The work presents core-shell nanoparticles (NPs) built from the novel Cu(I) complexes with cyclic PN-ligands (1,5-diaza-3,7-diphosphacyclooctanes) that can visualize their entry into cancer and normal cells using a luminescent signal and treat cells by self-enhancing generation of reactive oxygen species (ROS). Variation of P- and N-substituents in the series of PN-ligands allows structure optimization of the Cu(I) complexes for the formation of the luminescent NPs with high chemical stability. The non-covalent modification of the NPs with triblock copolymer F-127 provides their high colloidal stability, followed by efficient cell internalization of the NPs visualized by their blue (⁓450 nm) luminescence.

Carbonized Nickel Complex of Sodium Pectate as Catalyst for Proton-Exchange Membrane Fuel Cells.

Sodium pectate derivatives with 25% replacement of sodium ions with nickel ions were obtained by carbonization to temperatures of 280, 550, and 800 °C, under special protocols in an inert atmosphere by carbonization to temperatures of 280, 550, and 800 °C. The 25% substitution is the upper limit of substitution of sodium for nickel ions, above which the complexes are no longer soluble in water. It was established that the sample carburized to 550 °C is the most effective active element in the hydrogen-oxidation reaction, while the sample carbonized up to 800 °C was the most effective in the oxygen-reduction reaction.

Synthesis, Structure, and Electrochemical Properties of 2,3,4,5-Tetraphenyl-1-Monophosphaferrocene Derivatives.

Heteroleptic 2,3,4,5-tetraphenyl-1-monophosphaferrocene [FeCp(η-PCPh)] was obtained at a 62% yield through the reaction of lithium 2,3,4,5-tetraphenyl-1-monophosphacyclopentadienide Li(PCPh) () with [FeCp(η-CHCH)][PF]. The structure of 1-monophosphaferrocene and its W(CO)-complex were confirmed by multinuclear NMR and single-crystal X-ray diffraction study and further supported by DFT calculations. Cyclic voltammetry demonstrated that [FeCp(η-PCPh)] has a quasi-reversible oxidation wave.

Specific nanoarchitecture of silica nanoparticles codoped with the oppositely charged Mn and Ru complexes for dual paramagnetic-luminescent contrasting effects.

The silica nanoparticles (SNs) co-doped with paramagnetic ([Mn(HL)],) and luminescent ([Ru(dipy)]) complexes are represented. The specific distribution of [Mn(HL)] within the SNs allows to achieve about ten-fold enhancing in magnetic relaxivities in comparison with those of [Mn(HL)] in solutions. The leaching of [Mn(HL)] from the shell can be minimized through the co-doping of [Ru(dipy)] into the core of the SNs.

The Phosphinate Group in the Formation of 2D Coordination Polymer with Sm(III) Nodes: X-ray Structural, Electrochemical and Mössbauer Study.

A coordination polymer has been synthesized using ferrocene-based ligand-bearing phosphinic groups of 1,1'-ferrocene-diyl-bis(-phosphinic acid)), and samarium (III). The coordination polymer's structure was studied by both single-crystal and powder XRD, TG, IR, and Raman analyses. For the first time, the Mössbauer effect studies were performed on ferrocenyl phosphinate and the polymer based on it.

Complexes of Sodium Pectate with Nickel for Hydrogen Oxidation and Oxygen Reduction in Proton-Exchange Membrane Fuel Cells.

A number of nickel complexes of sodium pectate with varied Ni content have been synthesized and characterized. The presence of the proton conductivity, the possibility of the formation of a dense spatial network of transition metals in these coordination biopolymers, and the immobilization of transition ions in the catalytic sites of this class of compounds make them promising for proton-exchange membrane fuel cells. It has been established that the catalytic system composed of a coordination biopolymer with 20% substitution of sodium ions for divalent nickel ions, Ni (20%)-NaPG, is the leading catalyst in the series of 5, 15, 20, 25, 35% substituted pectates.

pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [AuL]{ReQ} Colloids (L = PNNP Ligand; Q = S or Se).

The present work introduces a simple, electrostatically driven approach to engineered nanomaterial built from the highly cytotoxic [AuL] complex (Au, L = 1,5-bis(p-tolyl)-3,7-bis(pyridine-2-yl)-1,5-diaza-3,7-diphosphacyclooctane (PNNP) ligand) and the pH-sensitive red-emitting [{ReQ}(OH)] (Re-Q, Q = S or Se) cluster units. The protonation/deprotonation of the Re-Q unit is a prerequisite for the pH-triggered assembly of Au and Re-Q into AuRe-Q colloids, exhibiting disassembly in acidic (pH = 4.5) conditions modeling a lysosomal environment.

Molecular and Nano-Structural Optimization of Nanoparticulate Mn-Hexarhenium Cluster Complexes for Optimal Balance of High T- and T-Weighted Contrast Ability with Low Hemoagglutination and Cytotoxicity.

The present work introduces rational design of nanoparticulate Mn(II)-based contrast agents through both variation of the μ (inner) ligands within a series of hexarhenium cluster complexes [{Re(μ-Q)}(CN)] (ReQ, Q = S, Se or Te) and interfacial decoration of the nanoparticles (NPs) KMnReQ ( = 1.3 - 1.8) by a series of pluronics (F-68, P-123, F-127).

Data of characterization of sodium pectate complexes with iron and manganese.

Data for iron and manganese-containing sodium pectate complexes are reported. Such complexes are potentially capable of exhibiting catalytic properties to the electroreduction of small molecules. Also, the complexes are water-soluble due to their ligands.

A Water-Soluble Sodium Pectate Complex with Copper as an Electrochemical Catalyst for Carbon Dioxide Reduction.

A selective noble-metal-free molecular catalyst has emerged as a fruitful approach in the quest for designing efficient and stable catalytic materials for CO reduction. In this work, we report that a sodium pectate complex of copper (PG-NaCu) proved to be highly active in the electrocatalytic conversion of CO to CH in water. Stability and selectivity of conversion of CO to CH as a product at a glassy carbon electrode were discovered.

Structure impact on photodynamic therapy and cellular contrasting functions of colloids constructed from dimeric Au(I) complex and hexamolybdenum clusters.

Electrostatically driven self-assembly of [AuL] (L is cyclic PNNP ligand) with [{MoI}(L')] (L' = I, CHCOO) in aqueous solutions is introduced as facile route for combination of therapeutic and cellular contrasting functions within heterometallic colloids (Mo-Au). The nature of L' affects the size and aggregation behavior of crystalline Mo-Au aggregates, which in turn affect the luminescence of the cluster units incorporated into Mo-Au colloids. The spin trap facilitated electron spin resonance spectroscopy technique indicates that the level of ROS generated by Mo-Au colloids is also affected by their size.

Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine.

The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeI] (). Molecular structure of was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex at room temperature and the magnetic behavior of in the temperature range of 2-300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively.

Surface modification of silica nanoparticles by hexarhenium anionic cluster complexes for pH-sensing and staining of cell nuclei.

The surface deposition of luminescent anionic cluster complex [{ReS}(OH)] advantages to the design and synthesis of composite luminescent silica nanoparticles (SNs) for intracellular imaging and sensing, while the encapsulation of the cluster units into SNs lacks for efficient luminescence. The deposition of the Re clusters resulted from their assembly at the silica surface functionalized by amino-groups provides the synthetic route for the composite SNs with bright cluster-centered luminescence invariable in pH range from 4.0 to 12.

Synthesis, structure, and electrochemical properties of 4,5-diaryl-1,2,3-triphosphaferrocenes and the first example of multi(phosphaferrocene).

The reaction between aryl substituted sodium 1,2,3-triphospholides or disodium bis(1,2,3-triphospholide) and [Fe(η6-(C6H5CH3)Cp]+[PF6]- in boiling diglyme results in pure 1,2,3-triphosphaferrocenes 1-3 or bis(1,2,3-triphosphaferrocene) 4, respectively, in good yields. The structure of all obtained 1,2,3-triphosphaferrocenes 1-4 has been extensively studied experimentally (NMR, UV-Vis spectroscopy, and X-ray analysis for 1 and 4) and quantum chemically. The electrochemical properties of 1,2,3-triphosphaferrocenes 1-4 in the solid state were studied for the first time and a reversible one-electron oxidation (E1/2 = 0.

ROS-generation and cellular uptake behavior of amino-silica nanoparticles arisen from their uploading by both iron-oxides and hexamolybdenum clusters.

The present work introduces combination of superparamagnetic iron oxides (SPIONs) and hexamolybdenum cluster ([{MoI}I]) units within amino-decorated silica nanoparticles (SNs) as promising design of the hybrid SNs as efficient cellular contrast and therapeutic agents. The heating generated by SNs doped with SPIONs (FeO@SNs) under alternating magnetic field is characterized by high specific absorption rate (SAR = 446 W/g). The cluster units deposition onto both FeO@SNs and "empty" silica nanoparticles (SNs) results in FeO@SNs[{MoI}I] and SNs[{MoI}I] with red cluster-centered luminescence and ability to generate reactive oxygen species (ROS) under the irradiation.

Synthetic Tuning of Co-Doped Silica Nanoarchitecture Towards Electrochemical Sensing Ability.

The present work introduces both synthesis of silica nanoparticles doped with Co ions by means of differently modified microemulsion water-in-oil (w/o) and Stöber techniques and characterization of the hybrid nanoparticles (Co@SiO) by TEM, DLS, XRD, ICP-EOS, SAXS, UV-Vis, and UV-Vis/DR spectroscopy and electrochemical methods. The results reveal the lack of nanocrystalline dopants inside the hybrid nanoparticles, as well as no ligands, when Co ions are added to the synthetic mixtures as Co(bpy) complexes, thus pointing to coordination of Co ions with Si-O groups as main driving force of the doping. The UV-Vis/DR spectra of Co@SiO in the range of d-d transitions indicate that Stöber synthesis in greater extent than the w/o one stabilizes tetrahedral Co ions versus the octahedral ions.

[{ReQ}(SO)] (Q = S or Se): Facile Synthesis and Properties of the Most Highly Charged Octahedral Cluster Complexes and High Magnetic Relaxivity of Their Colloids with Gd Ions.

New octahedral rhenium cluster complexes [{ReQ}(SO)] (Q = S or Se) were synthesized starting from [{ReQ}(HO)(OH)]·12HO. The complexes were crystallized as sodium salts and characterized by X-ray single-crystal diffraction and elemental analyses, IR, UV/vis and luminescence spectroscopies. Magnetic relaxation data demonstrate the complex formation of the cluster units with gadolinium ions.

Fluorescent magnetic nanoparticles for modulating the level of intracellular Ca in motoneurons.

This report introduces both synthesis and in vitro biological behaviour of dual magnetic-fluorescent silica nanoparticles. The amino group-decoration of 78 nm sized silica nanoparticles enables their efficient internalization into motoneurons, which is visualized by the red fluorescence arising from [Ru(dipy)3]2+ complexes encapsulated into a silica matrix. The internalized nanoparticles are predominantly located in the cell cytoplasm as revealed by confocal microscopy imaging.

Nano-architecture of silica nanoparticles as a tool to tune both electrochemical and catalytic behavior of Ni@SiO.

The present work introduces a facile synthetic route for efficient doping of [Ni(bpy) ] into silica nanoparticles with various sizes and architectures. Variation of the latter results in different concentrations of the Ni complexes at the interface of the composite nanoparticles. The UV-Vis analysis of the nanoparticles reveals changes in the inner-sphere environment of the Ni complexes when embedded into the nanoparticles, while the inner-sphere of Ni is invariant for the nanoparticles with different architecture.

Interfacial uploading of luminescent hexamolybdenum cluster units onto amino-decorated silica nanoparticles as new design of nanomaterial for cellular imaging and photodynamic therapy.

The present work introduces a facile synthetic route to embed phosphorescent K[{MoI}I] and (nBuN)[{MoI}(CHCOO)] clusters (C) onto silica-water interface of amino-decorated silica nanoparticles (SNs, 60 ± 6 nm). The assembled C-SNs gain in the luminescence intensity, which remains stable within three months after their assembly. High uptake capacity of the clusters (8700 of K[{MoI}I] and 6500 of (nBuN)[{MoI}(CHCOO)] per the each nanoparticle) derives from ionic self-assembly and coordination bonds between the cluster complexes and ionic (amino- and siloxy-) groups at the silica surface.

Silica-supported silver nanoparticles as an efficient catalyst for aromatic C-H alkylation and fluoroalkylation.

The efficient catalysis of oxidative alkylation and fluoroalkylation of aromatic C-H bonds is of paramount importance in the pharmaceutical and agrochemical industries, and requires the development of convenient Ag0-based nano-architectures with high catalytic activity and recyclability. We prepared Ag-doped silica nanoparticles (Ag0/+@SiO2) with a specific nano-architecture, where ultra-small sized silver cores are immersed in silica spheres, 40 nm in size. The nano-architecture provides an efficient electrochemical oxidation of Ag+@SiO2 without any external oxidant.

Silica nanoparticles with Tb(III)-centered luminescence decorated by Ag as efficient cellular contrast agent with anticancer effect.

The present work introduces composite luminescent nanoparticles (Ag-Tb-SNs), where ultra-small nanosilver (4 ± 2 nm) is deposited onto amino-modified silica nanoparticles (35±6 nm) doped by green luminescent Tb(III) complexes. Ag-Tb-SNs are able to image cancer (Hep-2) cells in confocal microscopy measurements due to efficient cell internalization, which is confirmed by TEM images of the Hep-2 cells exposed by Ag-Tb-SNs. Comparative analysis of the cytotoxicity of normal fibroblasts (DK-4) and cancer cells (Hep-2) incubated with various concentrations of Ag-Tb-SNs revealed the concentration range where the toxic effect on the cancer cells is significant, while it is insignificant towards the nonmalignant fibroblasts cells.