The present work reports the synthesis of the silica nanoparticles (SNs) incorporated by two photoactive components , which are the representatives of RuII nitrosyl complexes and [{Mo6I8}(CH3COO)6]2 � cluster units. The RuII nitrosyl complexes are incorporated through the doping procedure into the SNs. The embedding of amino-groups onto the RuII-doped SNs facilitates the deposition of the cluster units, thus, resulting in the heterometallic core-shel l SNs. Combination of the two photoactive components in the SNs results in the anti-synergistic effect on the photochemical and photodynamic activities of the RuI I and {Mo6I8}-based complexes correspondingly. The enhanced leaching of the cluster units from the heterometallic SNs correlates with the nitrosyl & RARR; nitro transformation of the encapsulated RuI I nitrosyl complexes. The formation of the so-called protein corona onto the heterometallic SNs is revealed as the reason for high colloid stability and efficientce l l internalization, which is visualized through the red emission of the {Mo6I8}-clusters. The cytotoxicity measurements reveal both synergistic effect of both components on the cytotoxicity evaluated in the so-called dark conditions and anti-synergistic effect on the photo-induced cytotoxicity. The significant dark cytotoxicity of the heterometallic SNs correlates with their high internalization and the enhanced leaching of the cluster units.

Magnetic nanoparticles (MNPs) have recently begun to be actively used in biomedicine applications, for example, for targeted drug delivery, in tissue engineering, and in magnetic resonance imaging. The study of the magnetic field effect on MNPs internalized into living cells is of particular importance since it allows a non-invasive influence on cellular activity. There is data stating the possibility to manipulate and control individual MNPs utilizing the local magnetic field gradient created by electromagnetic needles (EN). The present work aimed to demonstrate the methodological and technical approach for manipulating the local magnetic field gradient, generated by EN, novel luminescent MNPs internalized in HeLa cancer cells. The controlling of the magnetic field intensity and estimation of the attractive force of EN was demonstrated. Both designs of EN and their main characteristics are also described. Depending on the distance and applied voltage, the attractive force ENs ranged from 0.056 ± 0.002 to 37.85 ± 3.40 pN. As a practical application of the presented, the evaluation of viscous properties of the HeLa cell's cytoplasm, based on the measurement of the movement rate of MNPs inside cells under impact of a known magnetic force, was carried out; the viscosity was 1.45 ± 0.04 Pa·s.

Methods using fluorescence polarization analysis and an amperometric immunosensor for the immunochemical determination of the non-steroidal anti-inflammatory drug diclofenac in drugs, artificial urine, and surface water are proposed. High analytical sensitivity was achieved by using promising nanomaterials, in particular, silicon nanoparticles doped with highly luminescent ruthenium complexes and electrochemically active hexarhenium cluster complexes. The relative standard deviation was (0.070. It was shown that the developed procedures for immunochemical determination of diclofenac had a wider range of determined concentrations than other methods.

Results are presented from testing the temperature of a two-phosphor composite ([Ru(dipy)3]2+@SiO2 and NaYF4:Eu, Gd) in order to determine the prospects for its application as a luminescent thermal sensor in the range of 200–310 K. By calibrating the temperature dependences of individual spectral components of emissions produced upon irradiation with a cw laser at 405 nm, the possibilities of temperature sensing by means of ratiometric method are analyzed in four different spectral ranges of the composite’s visible luminescence.

This study introduces multifunctional silica nanoparticles that exhibit both high photothermal and chemodynamic therapeutic activities, in addition to luminescence. The activity of the silica nanoparticles is derived from their plasmonic properties, which are a result of infusing the silica nanoparticles with multiple Cu2-xS cores. This infusion process is facilitated by a recoating of the silica nanoparticles with a cationic surfactant. The key factors that enable the internal incorporation of the Cu2-xS cores and the external deposition of red-emitting carbon dots are identified. The Cu2-xS cores within the silica nanoparticles exhibit both self-boosting generation of reactive oxygen species and high photothermal conversion efficacy, which are essential for photothermal and chemodynamic activities. The silica nanoparticles' small size (no more than 70 nm) and high colloidal stability are prerequisites for their cell internalization. The internalization of the red-emitting silica nanoparticles within cells is visualized using fluorescence microscopy techniques. The chemodynamic activity of the silica nanoparticles is associated with their dark cytotoxicity, and the mechanisms of cell death are evaluated using an apoptotic assay. The photothermal activity of the silica nanoparticles is demonstrated by significant cell death under near-infrared (1064 nm) irradiation.

•Recent achievements are thoroughly collected in this review article.•Manganese-based nanoparticulate MRI contrasting is discussed.•Special attention is paid to biocompatibility and surface modification.•Potential pathways are recommended to guide researchers in the field of MRI.

The silica nanoparticles (SNs) co-doped with paramagnetic ([Mn(HL)]n-,) and luminescent ([Ru(dipy)3]2+) complexes are represented. The specific distribution of [Mn(HL)]n- within the SNs allows to achieve about ten-fold enhancing in magnetic relaxivities in comparison with those of [Mn(HL)]n- in solutions. The leaching of [Mn(HL)]n- from the shell can be minimized through the co-doping of [Ru(dipy)3]2+ into the core of the SNs. The co-doped SNs exhibit colloid stability in aqueous solutions, including those modeling a blood serum. The surface of the co-doped SNs was also decorated by amino- and carboxy-groups. The cytotoxicity, hemoagglutination and hemolytic activities of the co-doped SNs are on the levels convenient for "in vivo" studies, although the amino-decorated SNs cause more noticeable agglutination and suppression of cell viability. The co-doped SNs being intravenously injected into mice allows to reveal their biodistribution in both ex vivo and in vivo conditions through confocal microscopy and magnetic resonance imaging correspondingly.

This review is devoted to the analysis of various supramolecular interactions that facilitate the incorporation of water-soluble complexes of d- and f-metals and inorganic nanoparticles into silica-based nanomaterials formed within the framework of two main methods (the water-in-oil microemulsion and Stöber methods). The interest in such nanomaterials is due to the possibility of their use in different fields of chemistry and medicine. The driving forces and regularities of the incorporation of transition metal ions and complexes and nanoparticles of metal oxides and sulfides (dopants) into silica nanoparticles are discussed. The presented regularities, correlations, and possible mechanisms of incorporating diverse dopants into polymer matrices have shown the multifactor character of this process and provided the prerequisites for the control over it via the selection of an incorporation method or a preliminary treatment of the used ions, complexes, and nanoparticles.

The present work introduces the factors controlling the encapsulation of oleate-oleylamine-stabilized Cu((2-x))S nanoparticles (NPs) into silica nanocomposites (SNs) through the water-in-oil microemulsion method. The tendency of the Cu((2-x))S NPs to form negatively charged aggregates is highlighted as the factor restricting their loading into the SNs. The different preliminary treating of Cu((2-x))S NPs reveals that the recharging is rather than the de-aggregation facilitates their loading into the SNs. The treating of Cu((2-x))S NPs by [Ru(dipy)(3)](2+) complexes both facilitates their loading into the SNs and gain in their luminescence. The interfacial post-treating of the SNs by pluronic F-127 (F-127) is represented as the factor affecting both aggregation behavior and therapeutic function of the SNs. The electron spin resonance (ESR) spectroscopy results reveal the factors (heating, treating by F-127, addition of glutathione) that suppress and enhance the generation of reactive oxygen species (ROS) by the SNs. The luminescence of the SNs reveals the specificity in the intracellular trafficking of their treated and untreated counterparts. The cytotoxicity enhancement under the low power NIR-irradiation of the cancer cells incubated by the SNs is explained by the heating-induced increase in the level of ROS generation. The greater cytotoxicity of the treated by F-127 vs the untreated SNs both in "dark" and NIR-irradiated conditions is correlated with the difference in their ability to stand against the suppressive effect of glutathione.

The present work introduces coordinative binding of CuII ions with both amino-functionalized silica nanoparticles (SNs) and green-emitting carbon dots (CDs) as the pregrequisite for the CuII-assisted self-assembly of the CDs at the surface of the SNs. The produced composite SNs exhibit stable in time stimuli-responsive green fluorescence derived from the CuII-assisted assemblage of CDs. The fluorescence response of the composite SNs is sensitive to the complex formation with glutathione (GSH), enabling them to detect it with the lower limit of detection of 0.15 μM. The spin-trap-facilitated electron spin resonance technique indicated that the composite SNs are capable of self-boosting generation of ROS due to CuII→CuI reduction by carbon in low oxidation states as a part of the CDs. The intensity of the ESR signals is enhanced under the heating to 38 °C. The intensity is suppressed at the GSH concentration of 0.35 mM but is enhanced at 1.0 mM of glutathione, while it is suppressed once more at the highest intracellular concentration level of GSH (10 mM). These tendencies reveal the concentrations optimal for the scavenger or reductive potential of GSH. Flow cytometry and fluorescence and confocal microscopy methods revealed efficient cell internalization of SNs-NH2-CuII-CDs comparable with that of “free” CDs.

We developed a procedure for determining tricyclic antidepressant amitriptyline using fluorescence polarization immunoassay against the background of a buffer solution, urine, and breast milk with a relative standard deviation of no more than 5%. Tracers were synthesized by the noncovalent adsorption of amitriptyline on the surface of silicate nanoparticles doped with ruthenium(II) complexes. For the practical application of the proposed method, we selected the optimal concentrations of the tracer and antibodies by dilution. The amounts of reagents were selected based on fluorescence intensity and fluorescence polarization. According to the sensitivity requirements of the tracer, a dilution of 1 : 2 was selected, the fluorescence intensity of which was ten times higher than the background value, while the optimal fluorescence polarization value was fixed at 32. The optimal dilution of antibodies, corresponding to 70% of the fluorescence polarization value from the maximum signal, was 1 : 200. The range of working concentrations of amitriptyline was 1 × 10 –10 –1 × 10 –5 M; the lower limits of determination were at a level of (7–8) × 10 –11 M. The results are promising for monitoring the concentration of amitriptyline both in the pharmaceutical preparation and biological fluids to determine the effectiveness of ongoing therapeutic treatments and for medical and forensic purposes.

The interest in functional supramolecular systems for the design of innovative materials and technologies, able to fundamentally change the world, is growing at a high pace. The huge array of publications that appeared in recent years in the global literature calls for systematization of the structural trends inherent in the formation of these systems revealed at different molecular platforms and practically useful properties they exhibit. The attention is concentrated on the topics related to functional supramolecular systems that are actively explored in institutes and universities of Russia in the last 10–15 years, such as the chemistry of host–guest complexes, crystal engineering, self-assembly and self-organization in solutions and at interfaces, biomimetics and molecular machines and devices. The bibliography includes 1714 references.

The present paper reports the synthesis of iron-oxide nanoparticles (diameter 12.8±2.2 nm) coated with silica shell doped with paramagnetic Gd(III)-based complexes. The resulting nanoparticles with a silica shell thickness of about 45 nm have an average diameter of 113.1±14.3 nm and feature high transverse and longitudinal relaxivities (356 and 25 mM−1 s−1, respectively) at 1.5 T and 25 °C on a medical whole body NMR scanner. It has been also revealed using magnetic heating measurements that the prepared core-shell nanoparticles possess a high specific adsorption rate of around 236 W/g in aqueous media. The surface of the composite nanoparticles was decorated by amino-groups for a greater cellular uptake behaviour. The cell viability measurements reveal the concentration-dependent cytotoxicity of the nanoparticles, which agrees well with the high content of Gd(III) complexes in the nanomaterial. The obtained results show that the core-shell design of nanoparticles with superparamagnetic and paramagnetic parts can be promising for high transverse (and longitudinal) relaxivity as well as magnetic hyperthermia.

The present work introduces various synthetic and post-synthetic modes of co-doping of oleate-oleylamine-stabilized Cu(2−x)S cores with red emitting [Ru(dipy)3]2+ into amino-modified silica nanoparticles (SNs) with the aim to combine chemodynamic therapy (CDT) with cellular uptake and imaging functions. Thereto, the ROS generation by the Cu(2−x)S embedded into the SNs was manifested by the spin trap facilitated ESR technique and correlated with such parameters as size of the embedded cores, content and oxidation extent of copper ions. The parameters were varied through the different extent of an oxidative degradation of the embedded Cu(2−x)S cores by their post-treating with histidine, polyethylenimine and citrate-stabilized carbon dots (CDs). The treating by CDs was chosen as the optimal post-synthetic modification of the composite SNs due to combination of CDT with high stability to aggregation. The green or dual green-red emission of the CD-treated composite SNs visualizes their cell internalization and intracellular localization by means of fluorescence and confocal microscopy methods. Correlation of cytotoxicity data of the differently treated composite SNs with their ability to ROS generation and the intracellular localization highlight the enhanced cell internalization and nuclear confinement of the CD-treated composite SNs as the factor enhancing their cytotoxicity in greater extent than the CDT function.

The interaction of the NPEL-128 epoxy oligomer with silica nanoparticles doped with terbium(III) complex withp-sulfonatothiacalix[4]arene was studied for two types of nanoparticles: possessing silanol hydroxyl groups on the non-modified surface of the nanoparticles (SNs) or amino and hydroxyl groups on the amino-modified silica surface (ASNs). The possible reaction schemes of amino and hydroxyl groups on the surface of ASNs with epoxy molecules were revealed using IR spectroscopy and DSC. Based on the obtained data, a method for producing epoxy nanocomposites was developed, and their thermophysical, physicomechanical, and luminescent properties were investigated. The chemical bonding of epoxy with ASNs compared with that of SNs allows one to obtain a higher dispersion and uniform distribution of the nanoparticles in the polymer matrix, as well as to increase the glass transition temperature of the polymer. Due to the presence of terbium(III) complex in silica nanoparticles, the cured epoxyamine polymer filled by ASNs exhibits luminescent properties.

DNA aptamers have many benefits for cell imaging, such as high affinity and specificity, easiness of chemical functionalization, and low cost of production. Among known aptamers, Sgc8-aptamer was selected against acute lymphoblastic leukemia cells with a dissociation constant in a nanomolar range. The aptamer was previously used for the covalent coupling with fluorescent and magnetic nanoparticles, as well as for the fabrication of aptamer-based biosensors. Among commonly used fluorescent tags, lanthanide nanoparticles offer stable luminescence with narrow, well-resolved emission peaks and the absence of photoblinking. In other words, lanthanide nanoparticles could serve as luminescence reporters and be used in biosensing. In our study, we conjugated amino- and carboxyl-modified silica-coated terbium (III) thiacalix[4]arenesulfonate luminescent nanoparticles with Sgc8-aptamer and showed the ability of the aptamer-conjugated nanoparticles to detect leukemia cells using fluorescence microscopy. In addition, we conducted a cell viability assay and confirmed that the nanoparticles do not induce spontaneous cell apoptosis or necrosis and could be potentially used for bioimaging applications.

The present work introduces combination of superparamagnetic iron oxides (SPIONs) and hexamolybdenum cluster ([{Mo6I8}I6]2-) 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 (Fe3O4@SNs) under alternating magnetic field is characterized by high specific absorption rate (SAR = 446 W/g). The cluster units deposition onto both Fe3O4@SNs and "empty" silica nanoparticles (SNs) results in Fe3O4@SNs[{Mo6I8}I6] and SNs[{Mo6I8}I6] with red cluster-centered luminescence and ability to generate reactive oxygen species (ROS) under the irradiation. The monitoring of spin-trapped ROS by ESR spectroscopy technique indicates that the ROS-generation decreases in time for SNs[{Mo6I8}I6] and [{Mo6I8}I6]2- in aqueous solutions, while it remains constant for Fe3O4@SNs[{Mo6I8}I6]. The cytotoxicity is low for both Fe3O4@SNs[{Mo6I8}I6] and SNs[{Mo6I8}I6], while the flow cytometry indicates preferable cellular uptake of the former versus the latter type of the nanoparticles. Moreover, entering into nucleus along with cytoplasm differentiates the intracellular distribution of Fe3O4@SNs[{Mo6I8}I6] from that of SNs[{Mo6I8}I6], which remain in the cell cytoplasm only. The exceptional behavior of Fe3O4@SNs[{Mo6I8}I6] is explained by residual amounts of iron ions at the silica surface.

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. The magnetic function of the nanoparticles resulted from the incorporation of 17 nm sized superparamagnetic iron oxide cores into the silica matrix, enabling their responsivity to magnetic fields. Fluorescence analysis revealed the "on-off" switching of Ca2+ influx under the application and further removal of the permanent magnetic field. This result for the first time highlights the movement of the nanoparticles within the cell cytoplasm in the permanent magnetic field as a promising tool to enhance the neuronal activity of motoneurons.

High-valent cobalt(IV)-bpy complex stabilized in silica matrix was detected as catalytically active form and intermediate in cobalt-mediated oxidative C-H/NH cross-coupling reaction. These Co-IV species prepared by electrooxidation of Co-III(bpy)(3)-doped silica nanoparticles (SNs) at relatively low anodic potentials have demonstrated high catalytic activity. Both size and architecture of the SNs are highlighted as the factors beyond the complex structure affecting its oxidation potential and catalytic efficiency. The factors have been optimized for the catalyst with high efficiency, easy separation and reusability for 7 times at least. The optimal nanocatalyst (1 mol%) provides 100 % conversion of reactants in a single step of ligand-directed coupling of H2NTs with arenes under electrochemical regeneration conditions. The results emphasize both synthetic route for efficient embedding of Co-III(bpy)(3) into silica support and the electrochemical generation of Co-IV complexes as a facile route for developing the efficient nanocatalyst of oxidative functionalization. The observed reactivity has the potential in development of Co-catalyzed coupling reactions.

The present work introduces a facile synthetic route for efficient doping of [Ni-II(bpy)(x)] into silica nanoparticles with various sizes and architectures. Variation of the latter results in different concentrations of the Ni-II 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-II complexes when embedded into the nanoparticles, while the inner-sphere of Ni-II is invariant for the nanoparticles with different architecture. Comparative analysis of the electrochemically generated redox transformations of the Ni-II complexes embedded in the nanoparticles of various architectures reveals the latter as the main factor controlling the accessibility of Ni-II complexes to the redox transitions which, in turn, controls the electrochemical behavior of the nanoparticles. The work also highlights an impact of the nanoparticulate architecture in catalytic activity of the Ni-II complexes within the different nanoparticles in oxidative C-H fluoroalkylation of caffeine. Both low leakage and high concentration of the Ni-II complexes at the interface of the composite nanoparticles enables fluoroalkylated caffeine to be obtained in high yields under recycling of the nanocatalyst five times at least.