Solid CaCO3 Formation in Glioblastoma Multiforme and its Treatment with Ultra-Nanoparticulated NPt-Bionanocatalysts.

BACKGROUND: Glioblastoma multiforme (GBM), the most prevalent form of central nervous system (CNS) cancer, stands as a highly aggressive glioma deemed virtually incurable according to the World Health Organization (WHO) standards, with survival rates typically falling between 6 to 18 months. Despite concerted efforts, advancements in survival rates have been elusive. Recent cutting-edge research has unveiled bionanocatalysts with 1% Pt, demonstrating unparalleled selectivity in cleaving C-C, C-N, and C-O bonds within DNA in malignant cells. The application of these nanoparticles has yielded promising outcomes. OBJECTIVE: The objective of this study is to employ bionanocatalysts for the treatment of Glioblastoma Multiforme (GBM) in a patient, followed by the evaluation of obtained tissues through electronic microscopy. METHODS: Bionanocatalysts were synthesized using established protocols. These catalysts were then surgically implanted into the GBM tissue through stereotaxic procedures. Subsequently, tissue samples were extracted from the patient and meticulously examined using Scanning Electron Microscopy (SEM). RESULTS AND DISCUSSION: Detailed examination of biopsies via SEM unveiled a complex network of small capillaries branching from a central vessel, accompanied by a significant presence of solid carbonate formations. Remarkably, the patient subjected to this innovative approach exhibited a three-year extension in survival, highlighting the potential efficacy of bionanocatalysts in combating GBM and its metastases. CONCLUSION: Bionanocatalysts demonstrate promise as a viable treatment option for severe cases of GBM. Additionally, the identification of solid calcium carbonate formations may serve as a diagnostic marker not only for GBM but also for other CNS pathologies.

Pr3+-doped YPO4 nanocrystal embedded into an optical fiber.

Optical fiber with YPO4:Pr3+ nanocrystals (NCs) is presented for the first time using the glass powder-NCs doping method. The method's advantage is separate preparation of NCs and glass to preserve luminescent and optical properties of NCs once they are incorporated into optical fiber. The YPO4:Pr3+ nanocrystals were synthesized by the co-precipitation and hydrothermal methods, optimized for size (< 100 nm), shape, Pr3+ ions concentration (0.2 mol%), and emission lifetime. The core glass was selected from the non-silica P2O5-containing system with refractive index (n = 1.788) close to the NCs (no = 1.657, ne = 1.838). Optical fiber was drawn by modified powder-in-tube method after pre-sintering of glass powder-YPO4:Pr3+ (wt 3%) mixture to form optical fiber preform. Luminescent properties of YPO4:Pr3+ and optical fiber showed their excellent agreement, including sharp Pr3+ emission at 600 nm (1D2-3H4) and 1D2 level lifetime (τ = 156 ± 5 µs) under 488 nm excitation. The distribution of the YPO4:Pr3+ NCs in optical fiber were analyzed by TEM-EDS in the core region (FIB-SEM-prepared). The successful usage of glass powder-NCs doping method was discussed in the aspect of promising properties of the first YPO4:Pr3+ doped optical fiber as a new way to develop active materials for lasing applications, among others.

Shiga Toxin-B Targeted Gold Nanorods for Local Photothermal Treatment in Oral Cancer Clinical Samples.

Introduction: A great challenge in nanomedicine, and more specifically in theranostics, is to improve the specificity, selectivity, and targeting of nanomaterials towards target tissues or cells. The topical use of nanomedicines as adjuvants to systemic chemotherapy can significantly improve the survival of patients affected by localized carcinomas, reducing the side effects of traditional drugs and preventing local recurrences. Methods: Here, we have used the Shiga toxin, to design a safe, high-affinity protein-ligand (ShTxB) to bind the globotriaosylceramide receptor (GB3) that is overexpressed on the surfaces of preneoplastic and malignant cancer cells in the head and neck tumors. Results: We find that ShTxB functionalized gold nanorods are efficiently retrotranslocated to the GB3-positive cell cytoplasms. After 3 minutes of laser radiation with a wavelength resonant with the AuNR longitudinal localized surface plasmon, the death of the targeted cancer cells is activated. Both preclinical murine models and patient biopsy cells show the non-cytotoxic nature of these functionalized nanoparticles before light activation and their treatment selectivity. Discussion: These results show how the use of nanomedicines directed by natural ligands can represent an effective treatment for aggressive localized cancers, such as squamous cell carcinoma of the oral cavity.

Adsorptive Capture of Ionic and Non-Ionic Pollutants Using a Versatile Hybrid Amphiphilic-Nanomica.

A versatile, functional nanomaterial for the removal of ionic and non-ionic pollutants is presented in this work. For that purpose, the high charge mica Na-4-Mica was exchanged with the cationic surfactant (C16H33NH(CH3)2)+. The intercalation of the tertiary amine in the swellable nano-clay provides the optimal hydrophilic/hydrophobic nature in the bidimensional galleries of the nanomaterial responsible for the dual functionality. The organo-mica, made by functionalization with C16H33NH3+, was also synthesized for comparison purposes. Both samples were characterized by X-ray diffraction techniques and transmission electron microscopy. Then, the samples were exposed to a saturated atmosphere of cyclohexylamine for two days, and the adsorption capacity was evaluated by thermogravimetric measurements. Eu3+ cations served as a proof of concept for the adsorption of ionic pollutants in an aqueous solution. Optical measurements were used to identify the adsorption mechanism of Eu3+ cations, since Eu3+ emissions, including the relative intensity of different f-f transitions and the luminescence lifetime, can be used as an ideal spectroscopic probe to characterize the local environment. Finally, the stability of the amphiphilic hybrid nanomaterial after the adsorption was also tested.

Targeting Nanomaterials to Head and Neck Cancer Cells Using a Fragment of the Shiga Toxin as a Potent Natural Ligand.

Head and Neck Cancer (HNC) is the seventh most common cancer worldwide with a 5-year survival from diagnosis of 50%. Currently, HNC is diagnosed by a physical examination followed by an histological biopsy, with surgery being the primary treatment. Here, we propose the use of targeted nanotechnology in support of existing diagnostic and therapeutic tools to prevent recurrences of tumors with poorly defined or surgically inaccessible margins. We have designed an innocuous ligand-protein, based on the receptor-binding domain of the Shiga toxin (ShTxB), that specifically drives nanoparticles to HNC cells bearing the globotriaosylceramide receptor on their surfaces. Microscopy images show how, upon binding to the receptor, the ShTxB-coated nanoparticles cause the clustering of the globotriaosylceramide receptors, the protrusion of filopodia, and rippling of the membrane, ultimately allowing the penetration of the ShTxB nanoparticles directly into the cell cytoplasm, thus triggering a biomimetic cellular response indistinguishable from that triggered by the full-length Shiga toxin. This functionalization strategy is a clear example of how some toxin fragments can be used as natural biosensors for the detection of some localized cancers and to target nanomedicines to HNC lesions.

Nd3+-Doped Lanthanum Oxychloride Nanocrystals as Nanothermometers.

The development of optical nanothermometers operating in the near-infrared (NIR) is of high relevance toward temperature measurements in biological systems. We propose herein the use of Nd3+-doped lanthanum oxychloride nanocrystals as an efficient system with intense photoluminescence under NIR irradiation in the first biological transparency window and emission in the second biological window with excellent emission stability over time under 808 nm excitation, regardless of Nd3+ concentration, which can be considered as a particular strength of our system. Additionally, surface passivation through overgrowth of an inert LaOCl shell around optically active LaOCl/Nd3+ cores was found to further enhance the photoluminescence intensity and also the lifetime of the 1066 nm, 4F3/2 to 4I11/2 transition, without affecting its (ratiometric) sensitivity toward temperature changes. As required for biological applications, we show that the obtained (initially hydrophobic) nanocrystals can be readily transferred into aqueous solvents with high, long-term stability, through either ligand exchange or encapsulation with an amphiphilic polymer.

Acacia gums new fractions and sparkling base wines: How their biochemical and structural properties impact foamability?

Foam is the first attribute observed when sparkling wine is served. Bentonite is essentially used to flocculate particles in sparkling base wines but can impair their foamability. Gums from Acacia senegal and Acacia seyal improved the foamability of different bentonite-treated base wines. Our main goal was to see how the supplementation with new fractions separated from Acacia gums by Ion Exchange Chromatography affected foamability of sparkling base wines, deepening the relation between foam behavior and characteristics of wine and gums. High molar mass fractions increased the maximal foam height and the foam height during the stability period in, respectively, 11 out and 8 out of 16 cases (69% and 50%, respectively). The properties of the supplementing gums fractions obtained by IEC and, although to a minor extent, the wine characteristics, affected positively and/or negatively the foam behavior. Wine foamability also depended on the relationship between wine and gums fractions properties.

Solid Lipid Particles for Lung Metastasis Treatment.

Solid lipid particles (SLPs) can sustainably encapsulate and release therapeutic agents over long periods, modifying their biodistribution, toxicity, and side effects. To date, no studies have been reported using SLPs loaded with doxorubicin chemotherapy for the treatment of metastatic cancer. This study characterizes the effect of doxorubicin-loaded carnauba wax particles in the treatment of lung metastatic malignant melanoma in vivo. Compared with the free drug, intravenously administrated doxorubicin-loaded SLPs significantly reduce the number of pulmonary metastatic foci in mice. In vitro kinetic studies show two distinctive drug release profiles. A first chemotherapy burst-release wave occurs during the first 5 h, which accounts for approximately 30% of the entrapped drug rapidly providing therapeutic concentrations. The second wave occurs after the arrival of the particles to the final destination in the lung. This release is sustained for long periods (>40 days), providing constant levels of chemotherapy in situ that trigger the inhibition of metastatic growth. Our findings suggest that the use of chemotherapy with loaded SLPs could substantially improve the effectiveness of the drug locally, reducing side effects while improving overall survival.

Recent advances in the knowledge of wine oligosaccharides.

Oligosaccharides are carbohydrates with a low polymerization degree containing between three and fifteen monosaccharide residues covalently linked through glycosidic bonds. Oligosaccharides are related to plant defense responses and possess beneficial attributes for human health. Research has focused in wine oligosaccharides only in the last decade. In this paper, a summary of these works is provided. They include: (i) wine oligosaccharides origins, (ii) techniques for isolating oligosaccharide fraction and determining their content, composition and structure, (iii) their dependence on the grape origin and cultivar and winemaking process, and (iv) the connection between oligosaccharides and wine sensorial attributes. Further research is required regarding the impact of agricultural aspects and winemaking techniques on wine oligosaccharides. The knowledge concerning their influence on sensorial and physicochemical properties of wines and on human health should also be improved. The implementation of laboratory methods will provide better understanding of these compounds and their performance within wine's matrix.

Development of an accurate method for dispersion and quantification of carbon nanotubes in biological media.

Understanding the biological effects triggered by nanomaterials is crucial, not only in nanomedicine but also in toxicology. The dose-response relation is relevant in biological tests due to its use for determining appropriate dosages for drugs and toxicity limits. Carbon nanotubes can trigger numerous unusual biological effects, many of which could have unique applications in biotechnology and medicine. However, their resuspension in saline solutions and the accurate determination of their concentration after dispersion in biological media are major handicaps to identify the magnitude of the response of organisms as a function of this exposure. This difficulty has led to inconsistent results and misinterpretations of their in vivo behavior, limiting their potential use in nanomedicine. The lack of a suitable protocol that allows comparing different studies of the content of carbon nanotubes and their adequate resuspension in culture cell media gives rise to this study. Here, we describe a methodology to functionalize, resuspend and determine the carbon nanotube concentration in biocompatible media based on UV-Vis spectroscopy. This method allows us to accurately estimate the concentration of these resuspended carbon nanotubes, after removing bundles and micrometric aggregates, which can be used as a calibration standard, for dosage-dependent studies in biological systems. This method can also be extended to any other nanomaterial to properly quantify the actual concentration.

Comment on "Copper-Substituted Lead Perovskite Materials Constructed with Different Halides for Working (CH3NH3)2CuX4-Based Perovskite Solar Cells from Experimental and Theoretical View".

In recent years, two-dimensional perovskites have received considerable attention for their potential applications for optoelectronics. Contrary to previous publications, we demonstrate that (CH3NH3)2CuCl4 hybrid organic-inorganic layered perovskite does not show any room-temperature photoluminescence (PL) under UV excitation. This statement can be extended to other perovskites with general formula AMX3 or A2MX4, based on M: Cu2+ and X: Cl- or Br-. These materials, the object of increasing interest because of their efficient light absorption in a wide UV-vis-NIR range ideal for solar cells and optoelectronics, lack PL at room temperature, in contrast to recent findings reporting PL properties in this and other similar Cu2+-related materials.

A Comparative Study on Luminescence Properties of Y2O3: Pr3+ Nanocrystals Prepared by Different Synthesis Methods.

Pr3+-doped Y2O3 nanocrystals (NCs) have been obtained via five wet-chemistry synthesis methods which were optimized in order to achieve superior optical properties. To this end, a systematic study on the influence of different reaction parameters was performed for each procedure. Specifically, precursor concentration, reaction temperature, calcination temperature, and time, among others, were analyzed. The synthesized Y2O3: Pr3+ NCs were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and reflectance and Raman spectroscopy. In addition, the optical properties of such NCs were investigated by excitation, emission, and luminescence decay measurements. Concretely, emission from the 1D2 level was detected in all samples, while emission from 3PJ was absent. Finally, the effect of the synthesis methods and the reaction conditions on the luminescence decay has been discussed, and a comparative study of the different methods using the fluorescence lifetime of so-obtained Y2O3: Pr3+ NCs as a figure of merit has been carried out.

A custom-made functionalization method to control the biological identity of nanomaterials.

Here we propose a one-step strategy to endow nanomaterials with a custom-designed bio-identity. This study designs a universal 'nanomaterial binding domain' that can be genetically attached to any protein ensuring precise and spontaneous protein orientation. We demonstrate how, despite the simplicity of the method, the bioconjugation achieved: (i) is highly efficient, even in the presence of competing proteins, (ii) is stable at extreme physiological conditions (pH ranges 5.2-9.0; NaCl concentrations 0-1 M); (iii) prevents unwanted protein biofouling days after incubation in biologically-relevant conditions; and finally, (iv) avoids nanoparticle interaction with promiscuous unspecific receptors. In summary, this protein biocoating technique, applicable to a wide array of nano-designs, integrates material science and molecular biology procedures to create hybrid nanodevices with well-defined surfaces and predictable biological behaviors, opening a chapter in precision nanodiagnostics, nanosensing or nanotherapeutic applications.

Engineering Sub-Cellular Targeting Strategies to Enhance Safe Cytosolic Silica Particle Dissolution in Cells.

Mesoporous silica particles (MSP) are major candidates for drug delivery systems due to their versatile, safe, and controllable nature. Understanding their intracellular route and biodegradation process is a challenge, especially when considering their use in neuronal repair. Here, we characterize the spatiotemporal intracellular destination and degradation pathways of MSP upon endocytosis by HeLa cells and NSC-34 motor neurons using confocal and electron microscopy imaging together with inductively-coupled plasma optical emission spectroscopy analysis. We demonstrate how MSP are captured by receptor-mediated endocytosis and are temporarily stored in endo-lysosomes before being finally exocytosed. We also illustrate how particles are often re-endocytosed after undergoing surface erosion extracellularly. On the other hand, silica particles engineered to target the cytosol with a carbon nanotube coating, are safely dissolved intracellularly in a time scale of hours. These studies provide fundamental clues for programming the sub-cellular fate of MSP and reveal critical aspects to improve delivery strategies and to favor MSP safe elimination. We also demonstrate how the cytosol is significantly more corrosive than lysosomes for MSP and show how their biodegradation is fully biocompatible, thus, validating their use as nanocarriers for nervous system cells, including motor neurons.

Effect of TiO2 and ZnO Nanoparticles on the Performance of Dielectric Nanofluids Based on Vegetable Esters During Their Aging.

Over the last few decades the insulating performance of transformer oils has been broadly studied under the point of view of nanotechnology, which tries to improve the insulating and heat dissipation performance of transformer oils by suspending nanoparticles. Many authors have analyzed the thermal and dielectric behavior of vegetable oil based-nanofluids, however, very few works have studied the evolution of these liquids during thermal aging and their stability. In this paper has been evaluated the performance of aged vegetable oil based-nanofluids, which have been subjected to accelerated thermal aging at 150 °C. Nanoparticles of TiO2 and ZnO have been dispersed in a commercial natural ester. Breakdown voltage, resistivity, dissipation factor and acidity of nanofluid samples have been measured according to standard methods, as well as stability. Moreover, it has been analyzed the degradation of Kraft paper through the degree of polymerization (DP). The results have showed that although nanoparticles improve breakdown voltage, they increase the ageing of insulation liquids and dielectric paper.

Dye-doped biodegradable nanoparticle SiO2 coating on zinc- and iron-oxide nanoparticles to improve biocompatibility and for in vivo imaging studies.

In vivo imaging and therapy represent one of the most promising areas in nanomedicine. Particularly, the identification and localization of nanomaterials within cells and tissues are key issues to understand their interaction with biological components, namely their cell internalization route, intracellular destination, therapeutic activity and possible cytotoxicity. Here, we show the development of multifunctional nanoparticles (NPs) by providing luminescent functionality to zinc and iron oxide NPs. We describe simple synthesis methods based on modified Stöber procedures to incorporate fluorescent molecules on the surface of oxide NPs. These procedures involve the successful coating of NPs with size-controlled amorphous silica (SiO2) shells incorporating standard chromophores like fluorescein, rhodamine B or rhodamine B isothiocyanate. Specifically, spherical Fe3O4 NPs with an average size of 10 nm and commercial ZnO NPs (ca. 130 nm), both coated with an amorphous SiO2 shell of ca. 15 and 24 nm thickness, respectively, are presented. The magnetic nanoparticles, with a major presence of magnetite, show negligible coercitivity. Hence, interactions (dipolar) are very weak and the cores are in the superparamagnetic regime. Spectroscopic measurements confirm the presence of fluorescent molecules within the SiO2 shell, making these hybrid NPs suitable for bioimaging. Thus, our coating procedures improve NP dispersibility in physiological media and allow the identification and localization of intracellular ZnO and Fe3O4 NPs using confocal microscopy imaging preserving the fluorescence of the NP. We demonstrate how both Fe3O4 and ZnO NPs coated with luminescent SiO2 are internalized and accumulated in the cell cytoplasm after 24 hours. Besides, the SiO2 shell provides a platform for further functionalization that enables the design of targeted therapeutic strategies. Finally, we studied the degradation of the shell in different physiological environments, pointing out that the SiO2 coating is stable enough to reach the target cells maintaining its original structure. Degradation took place only 24 hours after exposure to different media.

Improvement of the foamability of sparkling base wines by the addition of Acacia gums.

In sparkling wine, foam characteristics are one of the major attributes. The foam quality depends on wine components. Bentonite is added to the base wine to facilitate the riddling process, but causes a loss of foamability. Acacia gum can be used as additive in wine. We have studied if the addition of Acacia senegal gum (AsenG), Acacia seyal gum (AseyG) and different AsenG fractions could improve the foamability of different base wines treated with bentonite. The foamability differs depending on the gum or the gum fraction treatment but also on the wine, being these differences linked to some aspects of their respective compositions and molecular parameters. AsenG and AseyG increase the foamability (by Mosalux - sparging procedure), respectively, in five and seven out of eight base wines treated with bentonite. Therefore, AsenG and AseyG are potential treatments increasing the foamability of these wines.

Pressure-and temperature induced phase transitions, piezochromism, NLC behaviour and pressure controlled Jahn-Teller switching in a Cu-based framework.

In situ single-crystal diffraction and spectroscopic techniques have been used to study a previously unreported Cu-framework bis[1-(4-pyridyl)butane-1,3-dione]copper(ii) (CuPyr-I). CuPyr-I was found to exhibit high-pressure and low-temperature phase transitions, piezochromism, negative linear compressibility, and a pressure induced Jahn-Teller switch, where the switching pressure was hydrostatic media dependent.

Magnetic Properties of a Family of [MnIII4LnIII4] Wheel Complexes: An Experimental and Theoretical Study.

The chelating ligand 1,3-bis(tris(hydroxymethyl)methylamino)propane (H6L) has been used to synthesize a family of octanuclear heterometallic complexes with the formula (NMe4)3[Mn4Ln4(H2L)3(H3L)(NO3)12] (Ln = La (1), Ce (2), Pr (3), Nd (4)). Encapsulation by the ligand causes the Mn(III) centers to lie in an unusually distorted (∼C2v) environment, which is shown by density functional theory and complete active space self-consistent field calculations to impact on the magnetic anisotropy of the Mn(III) ion. The theoretical study also supports the experimental observation of a ferromagnetic superexchange interaction between the Mn(III) ions in 1, despite the ions being separated by the diamagnetic La(III) ion. The optical properties of the compounds show that the distortion of the Mn(III) ions leads to three broad absorption bands originating from the transition metal ion, while the Nd(III) containing complex also displays some weak sharp features arising from the lanthanide f-f transitions.

The Effect of Pressure on Halogen Bonding in 4-Iodobenzonitrile.

The crystal structure of 4-iodobenzonitrile, which is monoclinic (space group I2/a) under ambient conditions, contains chains of molecules linked through C≡N···I halogen-bonds. The chains interact through CH···I, CH···N and π-stacking contacts. The crystal structure remains in the same phase up to 5.0 GPa, the b axis compressing by 3.3%, and the a and c axes by 12.3 and 10.9 %. Since the chains are exactly aligned with the crystallographic b axis these data characterise the compressibility of the I···N interaction relative to the inter-chain interactions, and indicate that the halogen bond is the most robust intermolecular interaction in the structure, shortening from 3.168(4) at ambient pressure to 2.840(1) Å at 5.0 GPa. The π∙∙∙π contacts are most sensitive to pressure, and in one case the perpendicular stacking distance shortens from 3.6420(8) to 3.139(4) Å. Packing energy calculations (PIXEL) indicate that the π∙∙∙π interactions have been distorted into a destabilising region of their potentials at 5.0 GPa. The structure undergoes a transition to a triclinic ( P 1 ¯ ) phase at 5.5 GPa. Over the course of the transition, the initially colourless and transparent crystal darkens on account of formation of microscopic cracks. The resistance drops by 10% and the optical transmittance drops by almost two orders of magnitude. The I···N bond increases in length to 2.928(10) Å and become less linear [