Silicate-based bioactive glass nano/microspheres hold significant promise for bone substitution by facilitating osteointegration through the release of biologically active ions and the formation of a biomimetic apatite layer. Cu-doping enhances properties such as pro-angiogenic and antibacterial behavior. While sol-gel methods usually yield homogeneous spherical particles for pure silica or binary glasses, synthesizing poorly aggregated Cu-doped ternary glass nano/microparticles without a secondary CuO crystalline phase remains challenging. This article introduces an alternative method for fabricating Cu-doped ternary microparticles using sol-gel chemistry combined with spray-drying. The resulting microspheres exhibit well-defined, poorly aggregated particles with spherical shapes and diameters of a few microns. Copper primarily integrates into the microspheres as Cu0 nanoparticles and as Cu2+ within the amorphous network. This doping affects silica network connectivity, as calcium and phosphorus are preferentially distributed in the glass network (respectively as network modifiers and formers) or involved in amorphous calcium phosphate nano-domains depending on the doping rate. These differences affect the interaction with simulated body fluid. Network depolymerization, ion release (SiO44-, Ca2+, PO43-, Cu2+), and apatite nanocrystal layer formation are impacted, as well as copper release. The latter is mainly provided by the copper involved in the silica network and not from metal nanoparticles, most of which remain in the microspheres after interaction. This understanding holds promising implications for potential therapeutic applications, offering possibilities for both short-term and long-term delivery of a tunable copper dose. STATEMENT OF SIGNIFICANCE: A novel methodology, scalable to industrial levels, enables the synthesis of copper-doped ternary bioactive glass microparticles by combining spray-drying and sol-gel chemistry. It provides precise control over the copper percentage in microspheres. This study explores the influence of synthesis conditions on the copper environment, notably Cu0 and Cu2+ ratios, characterized by EPR spectroscopy, an aspect poorly described for copper-doped bioactive glass. Additionally, copper indirectly affects silica network connectivity and calcium/phosphorus distribution, as revealed by SSNMR. Multiscale characterization illustrates how these features impact acellular degradation in simulated body fluid, highlighting the therapeutic potential for customizable copper dosing to address short- and long-term needs.
A series of mixed-anion Fe(NH2trz)3(BF4)2-x(SiF6)x/2 spin crossover complexes is obtained modifying the reaction time but also using an increase amount of tetraethyl orthosilicate as the source for the production and the incorporation of SiF62- competing with the BF42- anions present in the mother solution. The increase of the SiF62- anion inclusion to the detriment of the BF4- counterpart induces a shift of the temperature transition toward high temperatures leading to interesting bistability properties around room temperature with T1/2 spanning from 300 K to 325 K. Moreover, the implementation of a solid-liquid post synthetic modification approach from the Fe(NH2trz)3(BF4)2 parent complex with identical TEOS proportions and under certain experimental conditions lead systematically to the same Fe(NH2trz)3(BF4)1.2(SiF6)0.4 composition. This compound presents an abrupt spin crossover behaviour with a narrow hysteresis loop just above room temperature (320 K), which is stable under thermal cycling and along time with no specific storage conditions. Such crystalline powder sample incorporates homogeneous rod-shaped particles whose formation and physical properties can be followed simultaneously using infra-red spectroscopy, dynamic light scattering (DLS), transmission electronic microscopy (TEM) and optical reflectance. The observation of a stabilized single ca. 800 nm population of mixed-anion particles starting from insoluble various sizes (from nano- to microscale) Fe(NH2trz)3(BF4)2 particles supports the key role of the solvent (water molecules) on the separation, the reactivity and the reorganization of the 1D iron-triazole chains forming the packing of the structure.
A large amount of research in orthopedic and maxillofacial domains is dedicated to the development of bioactive 3D scaffolds. This includes the search for highly resorbable compounds, capable of triggering cell activity and favoring bone regeneration. Considering the phosphocalcic nature of bone mineral, these aims can be achieved by the choice of amorphous calcium phosphates (ACPs). Because of their metastable property, these compounds are however to-date seldom used in bulk form. In this work, we used a non-conventional "cold sintering" approach based on ultrafast low-pressure RT compaction to successfully consolidate ACP pellets while preserving their amorphous nature (XRD). Complementary spectroscopic analyses (FTIR, Raman, solid-state NMR) and thermal analyses showed that the starting powder underwent slight physicochemical modifications, with a partial loss of water and local change in the HPO42- ion environment. The creation of an open porous structure, which is especially adapted for non-load bearing bone defects, was also observed. Moreover, the pellets obtained exhibited sufficient mechanical resistance allowing for manipulation, surgical placement and eventual cutting/reshaping in the operation room. Three-dimensional porous scaffolds of cold-sintered reactive ACP, fabricated through this low-energy, ultrafast consolidation process, show promise toward the development of highly bioactive and tailorable biomaterials for bone regeneration, also permitting combinations with various thermosensitive drugs.
Two families of phosphorhydrazone dendrons having either an azide or an alkyne linked to the core and diverse types of pyridine derivatives as terminal functions have been synthesized and characterized. These dendrons were grafted via click reaction to graphene oxide (GO) functionalized with either alkyne or azide functions, respectively. The resulting modified-GO and GO-dendrons materials have been characterized by Fourier Transform Infrared (FTIR), Raman spectroscopy (RS), and Magic Angle Spinning Nuclear Magnetic Resonance (MASâ NMR) analyses. In addition, the free dendrons and the dendrons grafted to GO were tested toward cancerous (HCT116) and non-cancerous (RPE1) cell lines.
A pure mixed-anion Fe(NH2trz)3(BF4)(SiF6)0.5 spin crossover complex is obtained implementing a solid-liquid post synthetic modification approach from the Fe(NH2trz)3(BF4)2 parent complex. This method allows obtaining highly crystalline powder samples incorporating homogeneous micrometric (1 µm long) rod-shaped particles. This compound presents an abrupt spin crossover behaviour with a narrow (10 K) hysteresis loop centred just above room temperature (320 K) which makes it very interesting for future integration into devices for various applications.
Shaping of nanomaterials is a necessary step for their inclusion in electronic devices and batteries. For this purpose, the formulation of a moldable material including these nanomaterials is desirable. Organomineral gels are a very interesting option, since the components of the nanomaterial itself form a gel without the help of a binder. As a consequence, the properties of the nanomaterial are not diluted by the binder. In this article we studied organometallic gels based on a [ZnCy2 ] organometallic precursor and a primary alkyl amine which together forms spontaneously gels after few hours. We identified the main parameters controlling the gel properties monitored by rheology and NMR measurements The experiments demonstrate that the gelation time depends on the length of the alkyl chain of the amine and that the gelation mechanism derived firstly from the rigidification of the aliphatic chains of the amine, which takes precedence over the oligomerization of the inorganic backbone. This result highlights that the control of the rheological properties of organometallic gels remains mainly governed by the choice of the amine.
WO3 is a known photocatalytic metal oxide frequently studied for its depollution properties. However, it suffers from a high recombination rate of the photogenerated electron/holes pair that is detrimental to its performance. In this paper, we present a new chemical method to decorate WO3 nanoleaves (NLs) with a complementary metal oxide (ZnWO4) in order to improve the photocatalytic performance of the composite material for the abatement of 400 ppb NO2 under mild UV exposure. Our strategy was to synthesize WO3·2H2O nanoleaves, then, to expose them, in water-free organic solution, to an organometallic precursor of Zn(Cy)2. A structural water molecule from WO3·2H2O spontaneously decomposes Zn(Cy)2 and induces the formation of the ZnO@WO3·H2O nanocomposite. The material was characterized by electronic microscopy (SEM, TEM), TGA, XRD, Raman and solid NMR spectroscopies. A simple thermal treatment under air at 500 °C affords the ZnWO4@WO3 nanocomposite. The resulting material, additionally decorated with 1% wt. Au, presents a remarkable increase (+166%) in the photocatalytic abatement of NO2 under UV compared to the pristine WO3 NLs. This synthesis method paves the way to the versatile preparation of a wide range of MOx@WO3 nanocomposites (MOx = metal oxide).
OBJECTIVE: This study investigated the chemical and structural changes in the mineral phase and collagen of dentin during application of a mild universal adhesive. Particular attention was paid to the role of isopropanol and changes in water molecules. METHODS: In vitro application of the mild universal adhesive on dentin with two established etching modes (self-etch and etch-and-rinse) was studied using solid state nuclear magnetic resonance spectroscopy. RESULTS: It was evidenced that the etch-and-rinse mode leads to a decrease of the inorganic apatite and a reorganization of the residual mineral phase with a low amount of adhesive phosphate monoesters calcium salt formed, compared to the self-etch mode. In contrast, the adhesive interacts very similarly to the level of dentin collagen in both protocols, with a strong decrease in the amount of the free water molecules induced by the presence of isopropanol as the adhesive solvent, but without significant changes in the initial collagen structure. For both modes, the adhesive acrylates monomers remain mobile and can infiltrate the collagen. SIGNIFICANCE: Understanding the molecular interactions between dentin and adhesive solutions is a major challenge for designing products that lead to the formation of ideal dentin resin hybrid layer. Notably, one point considered essential is the presence of unbound water which, over time, is associated with a hydrolytic degradation of the organic matrix. Isopropanol, as an adhesive solvent, leads to a decrease in the amount of the less stable water molecules while the water molecules strongly attached to the collagen are retained, thus preserving the collagen structure.
Dental Bonding , Dentin-Bonding Agents , 2-Propanol , Dental Cements , Dentin , Dentin-Bonding Agents/chemistry , Magnetic Resonance Spectroscopy , Materials Testing , Resin Cements , Solvents , Tensile Strength
The addition of gallium ions to a solution of a double-hydrophilic block copolymer, i.e. poly(ethylene oxide)-block-poly(acrylic acid), leads to the spontaneous formation of highly monodisperse micelles with a Hybrid PolyIon Complexes (HPICs) core. By combining several techniques, a precise description of the HPIC architecture was achieved. In particular and for the first time, NMR and anomalous small angle X-ray scattering (ASAXS) enable tracking of the inorganic ions in solution and highlighting the co-localization of the gallium and the poly(acrylic acid) blocks in a rigid structure at the core of the micelle. Such a core has a radius of ca 4.3 nm while the complete nano-object with its poly(ethylene oxide) shell has a total radius of ca 11 nm. The aggregation number was also estimated using the ASAXS results. This comprehensive structural characterization of the Ga HPICs corroborates the assumptions made for HPICs based on other inorganic ions and demonstrates the universality of the HPIC structure leading, for example, to new families of contrast agents in medical imaging.
Gallium , Micelles , Ions , Polyethylene Glycols , Polymers
Ultrasmall gold nanoparticles (NPs) stabilized in networks by polymantane ligands (diamondoids) were successfully used as precatalysts for highly selective heterogeneous gold-catalyzed dimethyl allyl(propargyl)malonate cyclization to 5-membered conjugated diene. Such reaction usually suffers from selectivity issues with homogeneous catalysts. This control over selectivity further opened the way to one-pot cascade reaction, as illustrated by the 1,6-enyne cycloisomerization-Diels-Alder reaction of dimethyl allyl propargyl malonate with maleic anhydride. The ability to assemble nanoparticles with controllable sizes and shapes within networks concerns research in sensors, medical diagnostics, information storage, and catalysis applications. Herein, the control of the synthesis of sub-2-nm gold NPs is achieved by the formation of dense networks, which are assembled in a single step reaction by employing ditopic polymantanethiols. By using 1,1'-bisadamantane-3,3'-dithiol (BAd-SH) and diamantane-4,9-dithiol (DAd-SH), serving both as bulky surface stabilizers and short-sized linkers, we provide a simple method to form uniformly small gold NPs (1.3 ± 0.2 nm to 1.6 ± 0.3 nm) embedded in rigid frameworks. These NP arrays are organized alongside short interparticular distances ranging from 1.9 to 2.7 nm. The analysis of gold NP surfaces and their modification were achieved in joint experimental and theoretical studies, using notably XPS, NMR, and DFT modeling. Our experimental studies and DFT analyses highlighted the necessary oxidative surface reorganization of individual nanoparticles for an effective enyne cycloisomerization. The modifications at bulky stabilizing ligands allow surface steric decongestion for the alkyne moiety activation but also result in network alteration by overoxidation of sulfurs. Thus, sub-2-nm nanoparticles originating from networks building create convenient conditions for generating reactive Au(I) surface single-sites-in the absence of silver additives-useful for heterogeneous gold-catalyzed enyne cyclization. These nanocatalysts, which as such ease organic products separation, also provide a convenient access for building further polycyclic complexity, owing to their high reactivity and selectivity.
Formation of stable carbides during CO bond dissociation on small ruthenium nanoparticles (RuNPs) is demonstrated, both by means of DFT calculations and by solid state 13C NMR techniques. Theoretical calculations of chemical shifts in several model clusters are employed in order to secure experimental spectroscopic assignations for surface ruthenium carbides. Mechanistic DFT investigations, carried out on a realistic Ru55 nanoparticle model (â¼1 nm) in terms of size, structure and surface composition, reveal that ruthenium carbides are obtained during CO hydrogenation. Calculations also indicate that carbide formation via hydrogen-assisted hydroxymethylidyne (COH) pathways is exothermic and occurs at reasonable kinetic cost on standard sites of the RuNPs, such as 4-fold ones on flat terraces, and not only in steps as previously suggested. Another novel outcome of the DFT mechanistic study consists of the possible formation of µ6 ruthenium carbides in the tip-B5 site, similar examples being known only for molecular ruthenium clusters. Moreover, based on DFT energies, the possible rearrangement of the surface metal atoms around the same tip-site results in a µ-Ru atom coordinated to the remaining RuNP moiety, reminiscent of a pseudo-octahedral metal center on the NP surface.
Herein, we elucidate the key role of amine surfactants in the controlled anisotropic growth of ZnO nanoparticles that is achieved under mild conditions by organometallic hydrolysis. The structuring influence of alkyl substituents on the nitrogen atom of amines is jointly analyzed theoretically by DFT modeling, and experimentally by multinuclear NMR (1H, 13C and 17O) spectroscopy. We demonstrate that in initial steps leading to the growth of colloidal ZnO particles, the nature of molecular species that are involved in the solution strongly depends on the structure of the amine surfactant. By using tertiary, secondary or primary amines, no or weak adducts between the amine and zinc, or stable adducts, or adduct oligomers were identified, respectively. Afterwards, following the course of the reaction, the dynamic behavior of the amines on the grown ZnO nanocrystal surfaces is also strongly correlated with their structure. We identified that in the presence of tertiary, secondary or primary amines, no significant [Znâ¯N] adsorption, or surface adsorption with notable surface mobility, or a very strong adsorption is achieved, respectively. The last case, primary amines, significantly involves the structuring of a hydrogen bonding network. Therefore, such surface dynamic behavior has a predominant role in driving the nanocrystal growth, and orienting the ZnO material final morphology. By forming hydrogen bonds at the nanoparticle surface during the growth process, primary amines specifically lead to the formation of nanorods. Conversely, isotropic nanoparticles and aggregates are obtained when secondary and tertiary amines are used, respectively. These findings shed light on the role of weak surface interactions, herein H-bonding, that rule the growth of nano-objects and are as such crucial to identify, study, and control for achieving progress in nanoscience.
Collecting information about molecular organisation on biological materials such as bone and dentin represents a major challenge in attaining a better understanding of their mechanical properties. To that end, solid state Nuclear Magnetic Resonance (ssNMR) spectroscopic study is an appropriate strategy to provide atomic structural details on these amorphous composite materials. However, species like water molecules and hydroxyl groups are usually observed through 1H magic angle spinning (MAS) ssNMR that suffers from poor resolution due to strong signal overlapping, making their identification difficult. This paper proposes a set of ssNMR experiments for 1H characterization of the main components of human dentin, based on homo- and hetero-nuclear dipolar couplings and composed mostly of fast 1D experiments. The 1H assignment is assisted by straightforward sample modifications: vacuum drying, deuterium exchange and demineralization. These experiments allow the hydrogen signal edition of dentin species like water molecules, HPO42- and OH- groups, depending on their localization (bound to the organic phase, linked to apatite or at the interface) and their dynamic behaviour. This ssNMR toolbox has the potential to provide important structural and dynamic information on chemical and physical modifications of biomaterials. STATEMENT OF SIGNIFICANCE: Molecular characterisation of apatitic biomaterials by biophysical techniques is extremely difficult due to their complex and amorphous nature. It is, however, crucial to obtain such information if we want to understand their mechanical properties in relation to their physical state, for example their hydration levels. In this article we used a set of solid state NMR experiments and sample modifications to distinguish 1H signal of human dentin components with a particular attention to water molecules, known for their major role in biomaterial structuring.
Magnetic Resonance Imaging , Water , Bone and Bones , Dentin , Humans , Magnetic Resonance Spectroscopy
Four lithium phosphine borohydride compounds featuring phenyl and naphthyl linkers have been synthesized. In-depth NMR analysis affords evidence for non-bonded through space P-B coupling. Reactivity towards CO2 leads to LiH transfer and to the quantitative formation of the corresponding ambiphilic phosphine-borane products.
Shaping ability of hybrid nanomaterials is a key point for their further use in devices. It is therefore crucial to control it. To this end, it is necessary that the macroscopic properties of the material remain constant over time. Here, we evidence by multinuclear Magic-Angle Spinning Nuclear Magnetic Resonance spectroscopic study including 17 O isotope exchange that for a ZnO-alkylamine hybrid material, the partial carbonation of amine into ammonium carbamate molecules is behind the conversion from highly viscous liquid to a powdery solid when exposed to air. This carbonation induces modification and reorganization of the organic shell around the nanocrystals and affects significantly the macroscopic properties of the material such as it physical state, its solubility and colloidal stability. This study, straightforwardly extendable, highlights that the nature of the functional chemical group allowing connecting the stabilizing agent (SA) to the surface of the nanoparticles is of tremendous importance especially if the SA is reactive with molecules present in the environment.
Saccharothrix algeriensis NRRL B-24137 is an actinobacterium isolated from Algerian Saharan soil. This strain has the ability to produce several dithiolopyrrolone antibiotic derivatives depending on the precursors added to the culture medium. This group of antibiotics is known for their potent antimicrobial and anticancer activities. Holomycin is a member of the dithiolopyrrolone group of antibiotics, and has already been isolated from several species of actinobacteria belonging to the genus Streptomyces and also from some Gram-negative bacteria. In this study, holomycin was produced for the first time in the culture broth of a non-Streptomyces actinobacteria. This antibiotic was induced by adding 5 mM of L-cystine as precursor to the semi-synthetic fermentation broth of Sa. algeriensis NRRL B-24137 and then fully identified after HPLC purification. The minimum inhibitory concentrations (MIC) of holomycin were determined against several pathogenic microorganisms, including Escherichia coli ATCC 10536 Klebsiella pneumoniae CIP 82.91, Listeria monocytogenes CIP 82110, Staphylococcus aureus CIP 7625, Aspergillus carbonarius M333, Fusarium culmorum FC1, Candida albicans IPA 200. This antibiotic showed a broad-spectrum antimicrobial activity, inhibiting a variety of Gram-positive and Gram-negative bacteria, and micro-fungi.
Actinobacteria/metabolism , Cystine/metabolism , Lactams/metabolism , Anti-Infective Agents/pharmacology , Bacteria/drug effects , Culture Media/chemistry , Fermentation , Fungi/drug effects , Lactams/pharmacology , Microbial Sensitivity Tests
We report the dramatic impact of the addition of N-heterocyclic carbenes (NHCs) on the reactivity and selectivity of heterogeneous Ru catalysts in the context of C-H activation reactions. Using a simple and robust method, we prepared a series of new air-stable catalysts starting from commercially available Ru on carbon (Ru/C) and differently substituted NHCs. Associated with C-H deuteration processes, depending on Ru/C-NHC ratios, the chemical outcome can be controlled to a large extent. Indeed, tuning the reactivity of the Ru catalyst with NHC enabled: 1)â increased chemoselectivity and the regioselectivity for the deuteration of alcohols in organic media; 2)â the synthesis of fragile pharmaceutically relevant deuterated heterocycles (azine, purine) that are otherwise completely reduced using unmodified commercial catalysts; 3)â the discovery of a novel reactivity for such heterogeneous Ru catalysts, namely the selective C-1 deuteration of aldehydes.
Living systems carry out the reduction of N2 to ammonia (NH3) through a series of protonation and electron transfer steps under ambient conditions using the enzyme nitrogenase. In the chemical industry, the Haber-Bosch process hydrogenates N2 but requires high temperatures and pressures. Both processes rely on iron-based catalysts, but molecular iron complexes that promote the formation of NH3 on addition of H2 to N2 have remained difficult to devise. Here, we isolate the tri(iron)bis(nitrido) complex [(Cp'Fe)3(µ3-N)2] (in which Cp' = η5-1,2,4-(Me3C)3C5H2), which is prepared by reduction of [Cp'Fe(µ-I)]2 under an N2 atmosphere and comprises three iron centres bridged by two µ3-nitrido ligands. In solution, this complex reacts with H2 at ambient temperature (22 °C) and low pressure (1 or 4 bar) to form NH3. In the solid state, it is converted into the tri(iron)bis(imido) species, [(Cp'Fe)3(µ3-NH)2], by addition of H2 (10 bar) through an unusual solid-gas, single-crystal-to-single-crystal transformation. In solution, [(Cp'Fe)3(µ3-NH)2] further reacts with H2 or H+ to form NH3.
A key challenge for designing hybrid materials is the development of chemical tools to control the organization of inorganic nanoobjects at low scales, from mesoscopic (~µm) to nanometric (~nm). So far, the most efficient strategy to align assemblies of nanoparticles consists in a bottom-up approach by decorating block copolymer lamellae with nanoobjects. This well accomplished procedure is nonetheless limited by the thermodynamic constraints that govern copolymer assembly, the entropy of mixing as described by the Flory-Huggins solution theory supplemented by the critical influence of the volume fraction of the block components. Here we show that a completely different approach can lead to tunable 2D lamellar organization of nanoparticles with homopolymers only, on condition that few elementary rules are respected: 1) the polymer spontaneously allows a structural preorganization, 2) the polymer owns functional groups that interact with the nanoparticle surface, 3) the nanoparticles show a surface accessible for coordination.
Metal Nanoparticles/chemistry , Peptides/chemistry , Platinum/chemistry , Polymers/chemistry , Metal Nanoparticles/ultrastructure , Photoelectron Spectroscopy , Polymerization
A hybrid material made of mononuclear organophosphorus polypyridyl ruthenium complexes covalently bonded to ruthenium nanoparticles has been synthesized via a one-pot organometallic procedure and finely characterized. These results open new avenues to access unique hybrid transition metal nanomaterials.
