A high-throughput, straightforward procedure for biomonitoring organomercury species in human hair

Mercury is a pervasive and concerning pollutant due to its toxicity, mobility, and tendency to biomagnify in aquatic and terrestrial ecosystems. Speciation analysis is crucial to assess exposure and risks associated with mercury, as different mercury species exhibit varying properties and toxicities. This study aimed at developing a selective detection method for organic mercury species in a non-invasive biomonitoring matrix like human hair. The method is based on frontal chromatography (FC) in combination with inductively coupled plasma mass spectrometry (ICP-MS), using a low pressure, homemade, anion exchange column inserted in a standard ICP-MS introduction system, without requiring high-performance liquid chromatography (HPLC) hyphenation. In addition to the extreme simplification and cost reduction of the chromatographic equipment, the proposed protocol involves a fast, streamlined and fully integrated sample preparation process (in contrast to existing methods): the optimized procedure features a 15-min ultrasonic assisted extraction procedure and 5 min analysis time. Consequently, up to 100 samples could be analyzed daily, making the method highly productive and suitable for large-scale screening programs in public and environmental health. Moreover, the optimized procedure enables a limit of detection (LOD) of 5.5 μg/kg for a 10 mg hair microsample. All these features undeniably demonstrate a significant advancement in routine biomonitoring practices. To provide additional evidence, the method was applied to forty-nine human hair samples from individuals with varying dietary habits successfully finding a clear correlation between methylmercury levels (ranging from 0.02 to 3.2 mg/kg) in hair and fish consumption, in line with previous literature data

Ultrafast Electrochemical Self-Doping of Anodic Titanium Dioxide Nanotubes for Enhanced Electroanalytical and Photocatalytic Performance

This study explores an ultrarapid electrochemical self-doping procedure applied to anodic titanium dioxide (TiO2) nanotube arrays in an alkaline solution to boost their performance for electroanalytical and photocatalytic applications. The electrochemical self-doping process (i.e., the creation of surface Ti3+ states by applying a negative potential) is recently emerging as a simpler and cleaner way to improve the electronic properties of TiO2 compared to traditional chemical and high-temperature doping strategies. Here, self-doping was carried out through varying voltages and treatment times to identify the most performing materials without compromising their structural stability. Interestingly, cyclic voltammetry characterization revealed that undoped TiO2 shows negligible activity, whereas all self-doped materials demonstrate their suitability as electrode materials: an outstandingly short 10 s self-doping treatment leads to the highest electrochemical activity. The electrochemical detection of hydrogen peroxide was assessed as well, demonstrating a good sensitivity and a linear detection range of 3–200 µM. Additionally, the self-doped TiO2 nanotubes exhibited an enhanced photocatalytic activity compared to the untreated substrate: the degradation potential of methylene blue under UV light exposure increased by 25% in comparison to undoped materials. Overall, this study highlights the potential of ultrafast electrochemical self-doping to unleash and improve TiO2 nanotubes performances for electroanalytical and photocatalytic applications

Site-specific integration of functional transgenes into the human genome by adeno/AAV hybrid vectors

Uncontrolled insertion of gene transfer vectors into the human genome is raising significant safety concerns for their clinical use. The wild-type adeno-associated virus (AAV) can insert its genome at a specific site in human chromosome 19 (AAVS1) through the activity of a specific replicase/integrase protein (Rep) binding both the AAVS1 and the viral inverted terminal repeats (ITRs). AAV-derived vectors, however, do not carry the rep gene and cannot maintain site-specific integration properties. We describe a novel hybrid vector carrying an integration cassette flanked by AAV ITRs and a tightly regulated, drug-inducible Rep expression cassette in the framework of a high-capacity, helper-dependent adenoviral (Ad) vector. Rep-dependent integration of ITR-flanked cassettes of intact size and function was obtained in human primary cells and cell lines in the absence of selection. The majority of integrations were site specific and occurred within a 1000-bp region of the AAVS1. Genome-wide sequencing of integration junctions indicates that nonspecific integrations occurred predominantly in intergenic regions. Site-specific integration was obtained also in vivo, in an AAVS1 transgenic mouse model: upon a single tail vein administration of a nontoxic dose of Ad/AAV vectors, AAVS1-specific integrations were detected and sequenced in DNA obtained from the liver of all animals in which Rep expression was induced by drug treatment. Nonrandom integration of double-stranded DNA can therefore be obtained ex vivo and in vivo by the use of hybrid Ad/AAV vectors, in the absence of toxicity and with efficiency compatible with gene therapy applications

Performance of the Fully Digital FPGA-based Front-End Electronics for the GALILEO Array

In this work we present the architecture and results of a fully digital Front End Electronics (FEE) read out system developed for the GALILEO array. The FEE system, developed in collaboration with the Advanced Gamma Tracking Array (AGATA) collaboration, is composed of three main blocks: preamplifiers, digitizers and preprocessing electronics. The slow control system contains a custom Linux driver, a dynamic library and a server implementing network services. The digital processing of the data from the GALILEO germanium detectors has demonstrated the capability to achieve an energy resolution of 1.53 per mil at an energy of 1.33 MeV.Comment: 5 pages, 6 figures, preprint version of IEEE Transactions on Nuclear Science paper submitted for the 19th IEEE Real Time Conferenc

Spin Echo Decay in a Stochastic Field Environment

We derive a general formalism with which it is possible to obtain the time dependence of the echo size for a spin in a stochastic field environment. Our model is based on ``strong collisions''. We examine in detail three cases where: (I) the local field is Ising-like, (II) the field distribution is continuous and has a finite second moment, and (III) the distribution is Lorentzian. The first two cases show a T2 minimum effect and are exponential in time cubed for short times. The last case can be approximated by a phenomenological stretched exponential.Comment: 11 pages + 3 postscript figure

Octupole strength in the neutron-rich calcium isotopes

Low-lying excited states of the neutron-rich calcium isotopes $^{48-52}$Ca have been studied via $\gamma$-ray spectroscopy following inverse-kinematics proton scattering on a liquid hydrogen target using the GRETINA $\gamma$-ray tracking array. The energies and strengths of the octupole states in these isotopes are remarkably constant, indicating that these states are dominated by proton excitations.Comment: 15 pages, 3 figure

How to clean and safely remove HF from acid digestion solutions for ultra-trace analysis: a microwave-assisted vessel-inside-vessel protocol

The complete dissolution of silicate-containing materials, often necessary for elemental determination, is generally performed by microwave-assisted digestion involving the forced use of hydrofluoric acid (HF). Although highly efficient in dissolving silicates, this acid exhibits many detrimental effects (e.g., formation of precipitates, corrosiveness to glassware) that make its removal after digestion essential. The displacement of HF is normally achieved by evaporation in open-vessel systems: atmospheric contamination or loss of analytes can occur when fuming-off HF owing to the non-ultraclean conditions necessarily adopted for safety reasons. This aspect strongly hinders determination at the ultra-trace level. To overcome this issue, we propose a clean and safe microwaveassisted procedure to induce the evaporative migration of HF inside a sealed \u201cvessel-inside-vessel\u201d system: up to 99.9% of HF can be removed by performing two additional microwave cycles after sample dissolution. HF migrates from the digestion solution to a scavenger (ultrapure H2O) via a simple physical mechanism, and then, it can be safely dismissed/recycled. The procedure was validated by a soil reference material (NIST 2710), and no external or cross-contamination was observed for the 27 trace elements studied. The results demonstrate the suitability of this protocol for ultra-trace analysis when the utilization of HF is mandatory

Spectroscopy of 35^{35}P using the one-proton knockout reaction

The structure of $^{35}$P was studied with a one-proton knockout reaction at88~MeV/u from a $^{36}$S projectile beam at NSCL. The $\gamma$ rays from thedepopulation of excited states in $^{35}$P were detected with GRETINA, whilethe $^{35}$P nuclei were identified event-by-event in the focal plane of theS800 spectrograph. The level scheme of $^{35}$P was deduced up to 7.5 MeV using$\gamma-\gamma$ coincidences. The observed levels were attributed to protonremovals from the $sd$-shell and also from the deeply-bound $p\_{1/2}$ orbital.The orbital angular momentum of each state was derived from the comparisonbetween experimental and calculated shapes of individual ($\gamma$-gated)parallel momentum distributions. Despite the use of different reactions andtheir associate models, spectroscopic factors, $C^2S$, derived from the$^{36}$S $(-1p)$ knockout reaction agree with those obtained earlier from$^{36}$S($d$,\nuc{3}{He}) transfer, if a reduction factor $R\_s$, as deducedfrom inclusive one-nucleon removal cross sections, is applied to the knockout transitions.In addition to the expected proton-hole configurations, other states were observedwith individual cross sections of the order of 0.5~mb. Based on their shiftedparallel momentum distributions, their decay modes to negative parity states,their high excitation energy (around 4.7~MeV) and the fact that they were notobserved in the ($d$,\nuc{3}{He}) reaction, we propose that they may resultfrom a two-step mechanism or a nucleon-exchange reaction with subsequent neutronevaporation. Regardless of the mechanism, that could not yet be clarified, thesestates likely correspond to neutron core excitations in \nuc{35}{P}. Thisnewly-identified pathway, although weak, offers the possibility to selectivelypopulate certain intruder configurations that are otherwise hard to produceand identify.Comment: 5 figures, 1 table, accepted for publication in Physical Review