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The increased production of semiconductor nanomaterials such as heavy metal quantum dots and perovskites for applications such as in energy harvesting, optoelectronic devices, bioanalysis, phototherapy and consumer health products raises concerns regarding nanotoxicity. After disposal, these materials degrade upon interaction with the environment, such as rain and surface waters, soil and oxygen, and solar irradiation, leading to the release of heavy metal ions in the environment with exposure to aquatic and terrestrial animals and plants, and humans. Researchers are in the early stages of understanding the potential toxicity of such nanomaterials by quantifying the amount of heavy metal ions released due to environmental or biological transformation. Here, we evaluate the toxicity of environmentally transformed nanomaterials by considering PbS quantum dots as a model system. Using metal ion sensors and steady-state fluorescence spectroscopy, we quantify the amount of Pb2+ released by the photochemical etching of quantum dots. Furthermore, with the help of cytotoxicity and comet assays, and DNA gel electrophoresis, we evaluate the adverse effects of the released metal ions into the cultured lung epithelial (H1650), and neuronal (PC12) cells. These studies reveal higher levels of cell proliferation and DNA damage to PC12 cells, suggesting the neurotoxicity of lead due to not only the downregulation of glutathione, elevated levels of reactive oxygen and nitrogen species, and a calcium influx but also the proactivation of activator protein 1 that is correlated with protein kinase c. This research shows the significance of molecular biology studies on different cells and animals to critically understand the health and environmental costs of heavy metal-based engineered nanomaterials.Suspensions of neutrally buoyant elliptic particles are modeled in 2D using fully resolved simulations that provide two-way interaction between the particle and the fluid medium. Forces due to particle collisions are represented by a diffuse interface approach that allows the investigation of dense suspensions (up to 47% packing fraction). We focus on the role inertial forces play at low and high particle Reynolds numbers termed low Reynolds number and inertial regimes, respectively. The suspensions are characterized by the orientation distribution function (ODF) that reflects shear induced rotation of the particles at low Reynolds numbers, and nearly stationary (swaying) particles at high Reynolds numbers. In both cases, orientational ordering differs qualitatively from the behavior observed in the Stokesian-regime. The ODF becomes flatter with increasing packing fraction, as opposed to the sharpening previous work predicted in the Stokesian regime. The ODF at low particle concentrations differs significantly for the low Reynolds number and inertial regimes, whereas with increasing packing fraction convergence is observed. For dense suspensions, the particle-particle interactions dominate the particle motion.The triangulenium dyes constitute a family of versatile chromophores whose impressive photo-absorption and emission properties are currently highlighted in numerous novel experimental applications. In this investigation, we provide a comprehensive TDDFT characterization of their spectroscopic properties elucidating the origin of their large and complex absorption and emission vibronic spectra spread over the (whole) visible region. More precisely, by benchmarking the performance of 10 commonly-used exchange-correlation density functionals belonging to different classes of approximation, we develop and validate a computational protocol allowing the accurate modeling of both the position and optical line-shape of their vibrationally-resolved absorption and emission band structures. We find that semilocal approximations provide the best estimate of the structure of the vibronic spectra, however they spuriously and strongly underestimate their position. We finally show that global-hybrid density functionals mixing between 20 and 30% of exact-like exchange are an excellent compromise to get a satisfactory estimate of both of these properties.Electrode integration significantly increases the versatility of droplet microfluidics, enabling label-free sensing and manipulation at a single-droplet (single-cell) resolution. However, common fabrication techniques for integrating electronics into microfluidics are expensive, time-consuming, and can require cleanroom facilities. Here, we present a simple and cost-effective method for integrating electrodes into thermoplastic microfluidic chips using an off-the-shelf conductive ink. The developed conductive ink electrodes cost less than $10 for an entire chip, have been shown here in channel geometries as small as 75 μm by 50 μm, and can go from fabrication to testing within a day without a cleanroom. The geometric fabrication limits of this technique were explored over time, and proof-of-concept microfluidic devices for capacitance sensing, droplet merging, and droplet sorting were developed. This novel method complements existing rapid prototyping systems for microfluidics such as micromilling, laser cutting, and 3D printing, enabling their wider use and application.A surface wetting-driven droplet generation microfluidic chip was developed, and could produce droplets spontaneously once adding a drop of oil and an aqueous sample on the chip without any power source and equipment. The chip is simply composed of three drilled holes connected by a single microchannel. The aqueous sample dropped in the middle hole could be converged and segmented into monodispersed droplets spontaneously by preloading oil in the side hole, and then flow into the other side hole through the microchannel. To address the high throughput and stability in practical applications, a siphon pump was further integrated into the microfluidic chip by simply connecting oil-filled tubing also acting as a collector. In this way, droplets can be generated spontaneously with a high uniformity (CV less then 3.5%) and adjustable size (30-80 μm). Higher throughput (280 Hz) and multi-sample emulsification are achieved by parallel integration of a multi-channel structure. Based on that, the microfluidic chip was used as the droplet generator for the ddPCR to absolutely quantify S. mutans DNA. This is the first time that the feasibility of droplet generation driven only by oil wettability on hydrophobic surfaces is demonstrated. It offers great opportunity for self-sufficient and portable W/O droplet generation in biomedical samples, thus holding the potential for point-of-care testing (POCT).There is currently a lack of efficient reagents to transfect cells with large plasmid DNA, which would be enabling tools for gene editing using CRISPR/Cas9 technology. Herein, we report the discovery of peptide dendrimer Z22 as a non-viral vector for transfecting large CRISPR/Cas9 pDNA into 3D-tumor spheroids with exceptionally high efficiency, low cytotoxicity and low immunogenicity.Permanganate aqueous solutions, MnO4-(aq.), were studied using liquid-micro-jet-based soft X-ray non-resonant and resonant photoelectron spectroscopy to determine valence and core-level binding energies. To identify possible differences in the energetics between the aqueous bulk and the solution-gas interface, non-resonant spectra were recorded at two different probing depths. Similar experiments were performed with different counter ions, Na+ and K+, with the two solutions yielding indistinguishable anion electron binding energies. Our resonant photoelectron spectroscopy measurements, performed near the Mn LII,III- and O K-edges, selectively probed valence charge distributions between the Mn metal center, O ligands, and first solvation shell in the aqueous bulk. Associated resonantly-enhanced solute ionisation signals revealed hybridisation of the solute constituents' atomic orbitals, including the inner valence Mn 3p and O 2s. We identified intermolecular coulombic decay relaxation processes following resonant X-ray excitation of the solute that highlight valence MnO4-(aq.)-H2O(l) electronic couplings. HA130 Furthermore, our results allowed us to infer oxidative reorganisation energies of MnO4˙(aq.) and adiabatic valence ionisation energies of MnO4-(aq.), revealing the Gibbs free energy of oxidation and permitting estimation of the vertical electron affinity of MnO4˙(aq.). Finally, the Gibbs free energy of hydration of isolated MnO4- was determined. Our results and analysis allowed a near-complete binding-energy-scaled MnO4-(aq.) molecular orbital and a valence energy level diagram to be produced for the MnO4-(aq.)/MnO4˙(aq.) system. Cumulatively, our mapping of the aqueous-phase electronic structure of MnO4- is expected to contribute to a deeper understanding of the exceptional redox properties of this widely applied aqueous transition-metal complex ion.
To assess the prevalence and associated factors with early childhood caries (ECC) in a Polish population.
A cross-sectional study was carried out involving 656 three-year-old preschool children of both sexes. Data were collected through oral examination of the children and a questionnaire self-reported by their parents. The questionnaire contained information on sociodemographic aspects, feeding and oral hygiene practices, dental care utilisation and dental health knowledge. Associations between ECC and caries-related factors were analysed with use of bivariate and multivariate logistic regression and Mann-Whitney U test.
ECC was diagnosed in 64.0% children from the rural area and 46.6% from the urban one, more often in boys (57.7%) compared to girls (49.5%) and S-ECC in 37.1%, 24.2%, 31.5% and 27.5%, respectively. The associations between caries experience and living in a rural area, male sex, education level and oral health-related knowledge of a parent, tooth brushing frequency, nocturnal bottle-feedea, consumption of sweetened foods within the first 2 years of age and nocturnal drinking of sweet beverages by the over 12-month-old child.
The impact of smoking habits on periodontal treatment has not been clearly elucidated. This study aimed to specify the effects of cigarette consumption and nicotine addiction on periodontal therapy.
In this retrospective case-control study, 20 moderate smokers and 20 non-smokers with severe periodontitis were examined after initial diagnosis, and non-surgical active and supportive therapies for 1-6 years (mean follow-up = 3.37 years). Fagerström's test of nicotine dependence (FTND) was evaluated at re-examination. Treatment efficacy was assessed by periodontal pocket probing depth (PPD) changes and number of teeth lost per year (TL). Bayesian multilevel and regression analyses were performed at site, tooth, and patient levels.
During the mean follow-up period of > 3 years including active and supportive periodontal therapies, mean PPD, PPD > 3 mm and PPD > 7 mm percentage reductions were 1.03, 1.48 and 2.57 times statistically significantly less pronounced, respectively, in smokers than in non-smokers. Multilevel analysis showed that the variability of PPD > 7 mm reduction was mainly associated with patient-level factors. Smokers presented a higher risk for periodontitis progression. In smokers, periodontal parameter improvement was less pronounced in the maxilla and molars. The mean TL was related to the FTND score, not to cigarette consumption. Regression analysis did not demonstrate other influences of demographic and periodontal treatment characteristics on treatment outcomes, except patient age.
Smoking negatively impacted periodontal treatment outcomes at specific tooth sites (deep pockets, maxillary molars) and periodontitis progression, independent of other risk factors.
Smoking negatively impacted periodontal treatment outcomes at specific tooth sites (deep pockets, maxillary molars) and periodontitis progression, independent of other risk factors.