Laboratory Liquid-Jet X-ray Microscopy and X-ray Fluorescence Imaging for Biomedical Applications.

Diffraction-limited resolution and low penetration depth are fundamental constraints in optical microscopy and in vivo imaging. Recently, liquid-jet X-ray technology has enabled the generation of X-rays with high-power intensities in laboratory settings. By allowing the observation of cellular processes in their natural state, liquid-jet soft X-ray microscopy (SXM) can provide morphological information on living cells without staining. Furthermore, X-ray fluorescence imaging (XFI) permits the tracking of contrast agents in vivo with high elemental specificity, going beyond attenuation contrast. In this study, we established a methodology to investigate nanoparticle (NP) interactions in vitro and in vivo, solely based on X-ray imaging. We employed soft (0.5 keV) and hard (24 keV) X-rays for cellular studies and preclinical evaluations, respectively. Our results demonstrated the possibility of localizing NPs in the intracellular environment via SXM and evaluating their biodistribution with in vivo multiplexed XFI. We envisage that laboratory liquid-jet X-ray technology will significantly contribute to advancing our understanding of biological systems in the field of nanomedical research.

Surface modified of polyacrylonitrile nanofibers by TiO2/MWCNT for photodegradation of organic dyes and pharmaceutical drugs under visible light irradiation.

This work describes the fabrication of two composite nanofibers systems containing polyacrylonitrile polymer (PAN), Multiwall carbon nanotubes (MWCNT) and Titania (TiO2) nanoparticles. Photodegradation experiments were performed to study the effect of various parameters including pH, catalyst dose, pollutant concentration and reaction time for three model compounds, methylene blue (MB), indigo carmine (IC), and ibuprofen (IBU) under visible light. Morphology and structure of the modified composite nanofibers were characterized by X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Thermogravimetric analysis (TGA), Photoluminescence (PL) spectroscopy, Raman spectra, and X-ray Photoelectron Spectra (XPS) analyses. The photocatalytic performance was achieved in a rather short time visible light (<30 min) and under low power intensity (125 W) compared to earlier reports. Kinetics data fitted well using pseudo-first order model to describe the mechanism of photocatalytic degradation processes. The stability and flexibility of the fabricated composite nanofibers allow their application in a continuous flow system and their re-use after several cycles.

The frequency of asymptomatic urinary system abnormalities in children detected with cineurography imaging during angiocardiography.

IntroductionDiagnostic and interventional catheter angiography of the heart is frequently used in paediatric cardiology. It is also possible to detect urinary system anomalies with cineurography images that may be obtained during angiocardiography. In this study, the aim was to determine the frequency, distribution, and properties of urinary system anomalies accompanying heart diseases, and to find out the effectiveness of cineurographic images in detecting the urinary system anomalies. METHODS: The cineurographic images of 2022 children who had undergone angiocardiography between 1995 and 2015 were retrospectively examined. RESULTS: Urinary system anomalies were detected in 261 of the 2022 cases (12.9%). Of these 261 cases, 148 were males (56.7%), whereas 113 were females (43.3%). Among the heart diseases, the group most accompanied by urinary system anomalies was the non-cyanotic left-to-right shunted heart diseases, which was detected in 120 (39.1%) patients. Pelvicalyceal ectasia was the most common urinary system anomaly encountered and was detected in 89 patients (34.1%). Of the urinary system anomalies cases, 94 detected by cineurography were determined to be clinically severe. When the effectiveness of the cineurography was evaluated using the ultrasonography records of the patients, it was found to have 63.8% accuracy. CONCLUSION: Many of the patients with CHDs concomitantly have urinary system anomalies. It is possible to determine asymptomatic urinary system anomalies using cineurographic imaging during angiocardiography. This may lead to earlier treatments and improved prognosis for the patients, thus making it possible to prevent potential future problems.

Acetate-Induced Disassembly of Spherical Iron Oxide Nanoparticle Clusters into Monodispersed Core-Shell Structures upon Nanoemulsion Fusion.

It has been long known that the physical encapsulation of oleic acid-capped iron oxide nanoparticles (OA-IONPs) with the cetyltrimethylammonium (CTA+) surfactant induces the formation of spherical iron oxide nanoparticle clusters (IONPCs). However, the behavior and functional properties of IONPCs in chemical reactions have been largely neglected and are still not well-understood. Herein, we report an unconventional ligand-exchange function of IONPCs activated when dispersed in an ethyl acetate/acetate buffer system. The ligand exchange can successfully transform hydrophobic OA-IONP building blocks of IONPCs into highly hydrophilic, acetate-capped iron oxide nanoparticles (Ac-IONPs). More importantly, we demonstrate that the addition of silica precursors (tetraethyl orthosilicate and 3-aminopropyltriethoxysilane) to the acetate/oleate ligand-exchange reaction of the IONPs induces the disassembly of the IONPCs into monodispersed iron oxide-acetate-silica core-shell-shell (IONPs@acetate@SiO2) nanoparticles. Our observations evidence that the formation of IONPs@acetate@SiO2 nanoparticles is initiated by a unique micellar fusion mechanism between the Pickering-type emulsions of IONPCs and nanoemulsions of silica precursors formed under ethyl acetate buffered conditions. A dynamic rearrangement of the CTA+-oleate bilayer on the IONPC surfaces is proposed to be responsible for the templating process of the silica shells around the individual IONPs. In comparison to previously reported methods in the literature, our work provides a much more detailed experimental evidence of the silica-coating mechanism in a nanoemulsion system. Overall, ethyl acetate is proven to be a very efficient agent for an effortless preparation of monodispersed IONPs@acetate@SiO2 and hydrophilic Ac-IONPs from IONPCs.

Chemical Synthesis of Iron Antimonide (FeSb2) and Its Thermoelectric Properties.

Low temperature thermoelectric (TE) materials are in demand for more efficient cooling and power generation applications. Iron antimonide (FeSb2) draws great attention over the past few years because of its enhanced power factor values. Polycrystalline bulk FeSb2 nanopowder was prepared via a low-temperature molten salts approach followed by subsequent thermal treatment in synthetic air and hydrogen gas for calcination and reduction reactions, respectively. Structural analysis confirms the desired final phase with submicrometer grain size and high compaction density after consolidation using spark plasma sintering (SPS). TE transport properties revealed that the material is n-type below 150 K and p-type above this temperature; this suggests antimony vacancies in FeSb2. The electrical conductivity increased significantly, and the highest conductivity achieved was 6000 S/cm at 100 K. The maximum figure-of-merit, ZT, of 0.04 is achieved at 500 K, which is about 6 times higher than the earlier reported state-of-the art ZT value for the same material.

Keeping it real: The importance of material characterization in nanotoxicology.

Nanomaterials are small and the small size and corresponding large surface area of nanomaterials confers specific properties, making these materials desirable for various applications, not least in medicine. However, it is pertinent to ask whether size is the only property that matters for the desirable or detrimental effects of nanomaterials? Indeed, it is important to know not only what the material looks like, but also what it is made of, as well as how the material interacts with its biological surroundings. It has been suggested that guidelines should be implemented on the types of information required in terms of physicochemical characterization of nanomaterials for toxicological studies in order to improve the quality and relevance of the published results. This is certainly a key issue, but it is important to keep in mind that material characterization should be fit-for-purpose, that is, the information gathered should be relevant for the end-points being studied.

Serum endocan concentration in women with pre-eclampsia.

PURPOSE: To investigate serum endocan levels in pregnant subjects with and without pre-eclampsia. METHODS: This cross-sectional study was conducted on 49 pregnant women with pre-eclampsia and 32 healthy pregnant women matched for gestational age. Maternal levels of serum endocan were measured with the use of an enzyme-linked immunosorbent assay kit. RESULTS: Mean endocan levels were not significantly different among groups (10.7 ± 4.5 vs. 10.3 ± 3.2 ng/mL, p 0.763). Mean uterine artery PI and RI were higher in the pre-eclampsia group (p < 0.001, p < 0.001). Mean endocan levels were negatively correlated with BMI at the time of blood sampling (r = -0.247, p = 0.044). There was no correlations between mean endocan levels and all the others parameters. CONCLUSION: These findings suggest that the role of endocan in the pathogenesis of pre-eclampsia was not related to pre-eclampsia; hence, further studies are needed to investigate the role of endocan in the pathogenesis of pre-eclampsia.

Iterative nanoparticle bioengineering enabled by x-ray fluorescence imaging.

Nanoparticles (NPs) are currently developed for drug delivery and molecular imaging. However, they often get intercepted before reaching their target, leading to low targeting efficacy and signal-to-noise ratio. They tend to accumulate in organs like lungs, liver, kidneys, and spleen. The remedy is to iteratively engineer NP surface properties and administration strategies, presently a time-consuming process that includes organ dissection at different time points. To improve this, we propose a rapid iterative approach using whole-animal x-ray fluorescence (XRF) imaging to systematically evaluate NP distribution in vivo. We applied this method to molybdenum-based NPs and clodronate liposomes for tumor targeting with transient macrophage depletion, leading to reduced accumulations in lungs and liver and eventual tumor detection. XRF computed tomography (XFCT) provided 3D insight into NP distribution within the tumor. We validated the results using a multiscale imaging approach with dye-doped NPs and gene expression analysis for nanotoxicological profiling. XRF imaging holds potential for advancing therapeutics and diagnostics in preclinical pharmacokinetic studies.

Angiogenesis in bone tissue engineering via ceramic scaffolds: A review of concepts and recent advancements.

Due to organ donor shortages, long transplant waitlists, and the complications/limitations associated with auto and allotransplantation, biomaterials and tissue-engineered models are gaining attention as feasible alternatives for replacing and reconstructing damaged organs and tissues. Among various tissue engineering applications, bone tissue engineering has become a promising strategy to replace or repair damaged bone. We aimed to provide an overview of bioactive ceramic scaffolds in bone tissue engineering, focusing on angiogenesis and the effect of different biofunctionalization strategies. Different routes to angiogenesis, including chemical induction through signaling molecules immobilized covalently or non-covalently, in situ secretion of angiogenic growth factors, and the degradation of inorganic scaffolds, are described. Physical induction mechanisms are also discussed, followed by a review of methods for fabricating bioactive ceramic scaffolds via microfabrication methods, such as photolithography and 3D printing. Finally, the strengths and weaknesses of the commonly used methodologies and future directions are discussed.

Results of a hybrid approach for high risk term newborn patients with interrupted aortic arch (IAA) with left ventricular outflow tract obstruction.

This study aims to share the results of critically ill newborn cases with interrupted aortic arch (IAA) and Left ventricular outflow tract (LVOT) obstruction (LVOTO) who underwent the hybrid approach, which consists of bilateral pulmonary artery banding and/or patent ductus arteriosus stenting, as first-line treatment. This retrospective study includes the results of high-risk term newborns whom we applied a hybrid approach due to IAA and LVOTO in our clinic between January 1, 2021 and December 31, 2021. The demographic characteristics, hybrid approach methods and results of the cases were evaluated. Nine cases underwent hybrid approach during the study period. The mean age and weight at interventions were 7 days (3-16 days) and 3280 g (2700-4300 g). Six of the patients were diagnosed with type B IAA, 2 with type A, and one with type C. LVOTO was present in 7 patients. The success rate for the procedures was 100%. No patients died during the procedure or within the first 5 days after the procedure or from reasons related to the procedure. The median length of the hospital stay after stent placement was 28 days (22-35 days) for discharged patients. Three patients died in interstage period, and 6 patients underwent total corrective surgery after a median of 7 months (4-10 months). The average LVOT diameter was increased from 3.1 mm to 4.8 mm before total repair surgery. The hybrid approach should be kept in mind for treating high risk newborns with IAA with LVOTO and high-risk newborns who are not suitable for single stage total corrective surgery.

Biodegradation of single-walled carbon nanotubes by eosinophil peroxidase.

Eosinophil peroxidase (EPO) is one of the major oxidant-producing enzymes during inflammatory states in the human lung. The degradation of single-walled carbon nanotubes (SWCNTs) upon incubation with human EPO and H2O2 is reported. Biodegradation of SWCNTs is higher in the presence of NaBr, but neither EPO alone nor H2O2 alone caused the degradation of nanotubes. Molecular modeling reveals two binding sites for SWCNTs on EPO, one located at the proximal side (same side as the catalytic site) and the other on the distal side of EPO. The oxidized groups on SWCNTs in both cases are stabilized by electrostatic interactions with positively charged residues. Biodegradation of SWCNTs can also be executed in an ex vivo culture system using primary murine eosinophils stimulated to undergo degranulation. Biodegradation is proven by a range of methods including transmission electron microscopy, UV-visible-NIR spectroscopy, Raman spectroscopy, and confocal Raman imaging. Thus, human EPO (in vitro) and ex vivo activated eosinophils mediate biodegradation of SWCNTs: an observation that is relevant to pulmonary responses to these materials.

Polymorphism of catechol-o-methyltransferase and uterine leiomyoma.

Uterine leiomyoma (ULM) is the most common gynecological benign tumor that is affecting around 20-50 % of women over the age of 30. Although its molecular pathogenesis is still unknown, ULM has a multifactorial etiology determined by both genetics and environmental factors. The present study was designed to find out whether Val158Met polymorphism in the catechol-o-methyltransferase (COMT) gene is associated with the risk of ULM. We analyzed COMT Val158Met polymorphism in 105 ULMs patients and 105 healthy subjects using a polymerase chain reaction-based restriction fragment length polymorphism assay. We found remarkably similar frequencies in ULM compared with controls for COMT Val158Met genotypes and alleles, and no association was found between ULM and this polymorphism (p = 0.46). The COMT 158 Met allele in patients with large (≥5 cm) fibroids was higher than in patients with small (<5 cm) fibroids, and significant association was found between fibroid size and COMT 158 Met allele (p = 0.011, OR 0.50, 95 %CI 0.28-0.90). Our results reflect that COMT Val158Met polymorphism is not associated with an increased risk of ULMs, but Val158Met polymorphism may be a risk factor for development of large fibroids in Turkish patients with ULM.

Photoluminescence from quasi-type-II spherical CdSe-CdS core-shell quantum dots.

Spherical CdSe-CdS core-shell quantum dots (QDs) are found to be flexible in the transition between the type-I regime and the type-II regime with different core/shell dimensions. The quasi-type-II feature of the colloidal dots is confirmed with time-resolved photoluminescence (PL) measurements. Two recombination paths of the excitons with significantly different decay rates are observed and analyzed. The spherical CdSe-CdS core-shell QDs are numerically simulated to investigate the carrier separation. A relatively long radiative lifetime and high degree of spatial carrier separation provide good potential to achieve lasing under continuous-wave excitation. Amplified spontaneous emission at room temperature is detected from the QDs embedded in the polymer matrix. It is shown that a larger shell thickness results in a lower pumping threshold, while a smaller shell thickness leads to higher PL efficiency.

Magnetoresponsive fluorescent core-shell nanoclusters for biomedical applications.

Nowadays, superparamagnetic iron oxide nanoparticles (SPIONs) have a dominant role in many subfields of biomedicine. Owing to their peculiar properties, they can be employed for magnetic separation, drug delivery, diagnostics, and hyperthermia treatments. However, these magnetic nanoparticles (NPs) suffer from low unit magnetization due to size constraints (up to 20-30 nm) to exhibit superparamagnetic character. In this work, we have designed and synthesized superparamagnetic nanoclusters (SP-NCs) with diameters of up to 400 nm with high unit magnetization for enhanced loading capacity. These were synthesized with conventional or microwave-assisted solvothermal methods, in the presence of either of the two biomolecules (citrate or l-lysine) as the capping agent. Primary particle size, SP-NC size, surface chemistry, and the resultant magnetic properties were observed to be significantly influenced by the choice of synthesis route and capping agent. Selected SP-NCs were then coated with a fluorophore-doped silica shell to provide fluorescence properties, in the near-infrared spectrum region, while silica provided high chemical and colloidal stability. Heating efficiency studies were performed under alternating magnetic field on the synthesized SP-NCs, highlighting their potential in hyperthermia treatment. We envision that their enhanced magnetically-active content, fluorescence, magnetic property, and heating efficiency will pave the way to more effective uses in biomedical applications.

XFCT-MRI hybrid multimodal contrast agents for complementary imaging.

Multimodal contrast agents in biomedical imaging enable the collection of more comprehensive diagnostic information. In the present work, we design hybrid ruthenium-decorated superparamagnetic iron oxide nanoparticles (NPs) as the contrast agents for both magnetic resonance imaging (MRI) and X-ray fluorescence computed tomography (XFCT). The NPs are synthesized via a one-pot polyol hot injection route, in diethylene glycol. In vivo preclinical studies demonstrate the possibility of correlative bioimaging with these contrast agents. The complementarity allows accurate localization, provided by the high contrast of the soft tissues in MRI combined with the elemental selectivity of XFCT, leading to NP detection with high specificity and resolution. We envision that this multimodal imaging could find future applications for early tumor diagnosis, improved long-term treatment monitoring, and enhanced radiotherapy planning.

Two-Photon Polymerization Printing with High Metal Nanoparticle Loading.

Two-photon polymerization (2PP) is an efficient technique to achieve high-resolution, three-dimensional (3D)-printed complex structures. However, it is restricted to photocurable monomer combinations, thus presenting constraints when aiming at attaining functionally active resist formulations and structures. In this context, metal nanoparticle (NP) integration as an additive can enable functionality and pave the way to more dedicated applications. Challenges lay on the maximum NP concentrations that can be incorporated into photocurable resist formulations due to the laser-triggered interactions, which primarily originate from laser scattering and absorption, as well as the limited dispersibility threshold. In this study, we propose an approach to address these two constraints by integrating metallic Rh NPs formed ex situ, purposely designed for this scope. The absence of surface plasmon resonance (SPR) within the visible and near-infrared spectra, coupled with the limited absorption value measured at the laser operating wavelength (780 nm), significantly limits the laser-induced interactions. Moreover, the dispersibility threshold is increased by engineering the NP surface to be compatible with the photocurable resin, permitting us to achieve concentrations of up to 2 wt %, which, to our knowledge, is significantly higher than the previously reported limit (or threshold) for embedded metal NPs. Another distinctive advantage of employing Rh NPs is their role as promising contrast agents for X-ray fluorescence (XRF) bioimaging. We demonstrated the presence of Rh NPs within the whole 2PP-printed structure and emphasized the potential use of NP-loaded 3D-printed nanostructures for medical devices.

Magnetically-assisted viral transduction (magnetofection) medical applications: An update.

Gene therapy involves replacing a faulty gene or adding a new gene inside the body's cells to cure disease or improve the body's ability to fight disease. Its popularity is evident from emerging concepts such as CRISPR-based genome editing and epigenetic studies and has been moved to a clinical setting. The strategy for therapeutic gene design includes; suppressing the expression of pathogenic genes, enhancing necessary protein production, and stimulating the immune system, which can be incorporated into both viral and non-viral gene vectors. Although non-viral gene delivery provides a safer platform, it suffers from an inefficient rate of gene transfection, which means a few genes could be successfully transfected and expressed within the cells. Incorporating nucleic acids into the viruses and using these viral vectors to infect cells increases gene transfection efficiency. Consequently, more cells will respond, more genes will be expressed, and sustained and successful gene therapy can be achieved. Combining nanoparticles (NPs) and nucleic acids protects genetic materials from enzymatic degradation. Furthermore, the vectors can be transferred faster, facilitating cell attachment and cellular uptake. Magnetically assisted viral transduction (magnetofection) enhances gene therapy efficiency by mixing magnetic nanoparticles (MNPs) with gene vectors and exerting a magnetic field to guide a significant number of vectors directly onto the cells. This research critically reviews the MNPs and the physiochemical properties needed to assemble an appropriate magnetic viral vector, discussing cellular hurdles and attitudes toward overcoming these barriers to reach clinical gene therapy perspectives. We focus on the studies conducted on the various applications of magnetic viral vectors in cancer therapies, regenerative medicine, tissue engineering, cell sorting, and virus isolation.

Organ uptake, toxicity and skin clearance of ruthenium contrast agents monitored in vivo by x-ray fluorescence.

Aims: To investigate the distribution and toxicity of ruthenium nanoparticles (Ru NPs) injected intravenously in mice. Methods: We synthesized Ru NPs, followed their biodistribution by x-ray fluorescence (XRF) imaging and evaluated organ toxicity by histopathology and gene expression. Results: Ru NPs accumulated, mainly in liver and spleen, where they were phagocyted by tissue macrophages, giving a transient inflammation and oxidative stress response that declined after 2 weeks. Ru NPs gradually accumulated in the skin, which was confirmed by microscopic examination of skin biopsies. Conclusion: Ru NP toxicity in recipient organs is transient. Particles are at least partially excreted by the skin, supporting a role for the skin as a nanoparticle clearing organ.

Unlocking the Potential of Magnetic Refrigeration: Investigating the Compatibility of the Ga-Based Liquid Metal with a La(Fe,Mn,Si)13Hz Magnetocaloric Material for Enhanced Long-Term Stability.

Magnetic refrigeration (MR) is a cutting-edge technology that promises high energy efficiency and eco-friendliness, making it an exciting alternative to traditional refrigeration systems. However, the main challenge to its widespread adoption is cost competitiveness. In this context, the use of liquid metals as heat transfer liquids in the MR has been proposed as a game-changing solution. Unfortunately, the toxicity and flammability of these liquid metals have raised serious concerns, limiting their practical use. In this study, we investigate the compatibility of a nontoxic and nonflammable GaInSn-based liquid metal with a magnetocaloric material, La(Fe,Mn,Si)13Hz, over a 1.5 year period. Our findings reveal nearly a 14% reduction in specific cooling energy and peak-specific isothermal magnetic entropy change for the considered magnetocaloric material. Our study provides valuable insights into the long-term stability of magnetocaloric materials and their compatibility with liquid metals, facilitating the development of more cost-effective and sustainable MR systems.

Thermoelectric Inks and Power Factor Tunability in Hybrid Films through All Solution Process.

Thermoelectric (TE) materials can have a strong benefit to harvest thermal energy if they can be applied to large areas without losing their performance over time. One way of achieving large-area films is through hybrid materials, where a blend of TE materials with polymers can be applied as coating. Here, we present the development of all solution-processed TE ink and hybrid films with varying contents of TE Sb2Te3 and Bi2Te3 nanomaterials, along with their characterization. Using (1-methoxy-2-propyl) acetate (MPA) as the solvent and poly (methyl methacrylate) as the durable polymer, large-area homogeneous hybrid TE films have been fabricated. The conductivity and TE power factor improve with nanoparticle volume fraction, peaking around 60-70% solid material fill factor. For larger fill factors, the conductivity drops, possibly because of an increase in the interface resistance through interface defects and reduced connectivity between the platelets in the medium. The use of dodecanethiol (DDT) as an additive in the ink formulation enabled an improvement in the electrical conductivity through modification of interfaces and the compactness of the resultant films, leading to a 4-5 times increase in the power factor for both p- and n-type hybrid TE films, respectively. The observed trends were captured by combining percolation theory with analytical resistive theory, with the above assumption of increasing interface resistance and connectivity with polymer volume reduction. The results obtained on these hybrid films open a new low-cost route to produce and implement TE coatings on a large scale, which can be ideal for driving flexible, large-area energy scavenging technologies such as personal medical devices and the IoT.