Ionic Route to Atmospheric Relevant HO2 and Protonated Formaldehyde from Methanol Cation and O2.

Gas-phase ion chemistry influences atmospheric processes, particularly in the formation of cloud condensation nuclei by producing ionic and neutral species in the upper troposphere-stratosphere region impacted by cosmic rays. This work investigates an exothermic ionic route to the formation of hydroperoxyl radical (HO2) and protonated formaldehyde from methanol radical cation and molecular oxygen. Methanol, a key atmospheric component, contributes to global emissions and participates in various chemical reactions affecting atmospheric composition. The two reactant species are of fundamental interest due to their role in atmospheric photochemical reactions, and HO2 is also notable for its production during lightning events. Our experimental investigations using synchrotron radiation reveal a fast hydrogen transfer from the methyl group of methanol to oxygen, leading to the formation of CH2OH+ and HO2. Computational analysis corroborates the experimental findings, elucidating the reaction dynamics and hydrogen transfer pathway. The rate coefficients are obtained from experimental data and shows that this reaction is fast and governed by capture theory. Our study contributes to a deeper understanding of atmospheric processes and highlights the role of ion-driven reactions in atmospheric chemistry.

Formation of H3O+ and OH by CO2 and N2O trace gases in the atmospheric environment.

The impact of cosmic rays' energetic subatomic particles on climate and global warming is still controversial and under debate. Cosmic rays produce ions that can trigger fast reactions affecting chemical networks in the troposphere and stratosphere especially when a large amount of relevant trace gases such as carbon dioxide, methane, sulfur dioxide and water are injected by volcanic eruptions. This work focuses on synchrotron experiments and an ab initio theoretical study of the ion chemistry of carbon dioxide and nitrous oxide radical cations reacting with water. These molecules catalyze a fast exothermic formation of hydronium ions H3O+ and the hydroxyl radical OH, the main oxidant in the atmosphere. Moreover, theoretical calculations demonstrate that at the end of the catalytic cycle, CO2 and N2O are produced vibrationally excited and subsequently they quench in the microsecond time scale by collision with the surrounding atmospheric molecules at the pressure and temperature of the upper-troposphere/stratosphere. The chemistry involved in these reactions has a strong impact on the oxidant capacity of the atmosphere, on the sulfate aerosol production, on the cloud formation and eventually on the chemical networks controlling climate and global warming models.

H2O˙+ and OH+ reactivity versus furan: experimental low energy absolute cross sections for modeling radiation damage.

Radiotherapy is one of the most widespread and efficient strategies to fight malignant tumors. Despite its broad application, the mechanisms of radiation-DNA interaction are still under investigation. Theoretical models to predict the effects of a particular delivered dose are still in their infancy due to the difficulty of simulating a real cell environment, as well as the inclusion of a large variety of secondary processes. This work reports the first experimental study of the ion-molecule reactions of the H2O˙+ and OH+ ions, produced by photoionization with synchrotron radiation, with a furan (c-C4H4O) molecule, a template for deoxyribose sugar in DNA. The present experiments, performed as a function of the collision energy of the ions and the tunable photoionization energy, provide key parameters for the theoretical modelling of the effect of radiation dose, like the absolute cross sections for producing protonated furan (furanH+) and a radical cation (furan˙+), the most abundant products, which can amount up to 200 Å2 at very low collision energies (<1.0 eV). The experimental results show that furanH+ is more fragile, indicating how the protonation of the sugar component of the DNA may favor its dissociation with possible major radiosensitizing effects. Moreover, the ring opening of furanH+ isomers and the potential energy surface of the most important fragmentation channels have been explored by molecular dynamics simulations and quantum chemistry calculations. The results show that, in the most stable isomer of furanH+, the ring opening occurs via a low energy pathway with carbon-oxygen bond cleavage, followed by the loss of neutral carbon monoxide and the formation of the allyl cation CH2CHCH2+, which instead is not observed in the fragmentation of furan˙+. At higher energies the ring opening through the carbon-carbon bond is accompanied by the loss of formaldehyde, producing HCCCH2+, the most intense fragment ion detected in the experiments. This work highlights the importance of the secondary processes, like the ion-molecule reactions at low energies in the radiation damage due to their very large cross sections, and it aims to provide benchmark data for the development of suitable models to approach this low collision energy range.

Ion Chemistry of Carbon Dioxide in Nonthermal Reaction with Molecular Hydrogen.

The exothermic hydrogen transfer from H2 to CO2·+ leading to H and HCO2+ is investigated in a combined experimental and theoretical work. The experimental mass/charge ratios of the ionic product (HCO2+) and the ionic reactant (CO2·+) are recorded as a function of the photoionization energy of the synchrotron radiation. Theoretical density functional calculations and variational transition state theory are employed and adapted to analyze the energetic and the kinetics of the reaction, which turns out to be barrierless and with nonthermal rate coefficients controlled by nonstatistical processes. This study aims to understand the mechanisms and energetics that drive the reactivity of the elementary reaction of CO2·+ with H2 in different processes.

Ionization of 2- and 4(5)-Nitroimidazoles Radiosensitizers: A "Kinetic Competition" Between NO2 and NO Losses.

Nitroimidazoles are a class of chemicals with a remarkable broad spectrum of applications from the production of explosives to the use as radiosensitizers in radiotherapy. The understanding of thedynamics of their fragmentation induced by ionizing sources is of fundamental interest. The goal of this work is to theoretically investigate the kinetic competition between the two most important decomposition channels of 2, 4 and 5-Nitroimidazole cations: the NO and NO2 losses. The calculated rate constants of the two processes are in very good agreement with the experimental Photoelectron-Photoion Coincidence (PEPICO) branching ratio. This study solves the intriguing and theoretically unexplained experimental observation that 2-Nitroimidazole, at variance with the other two regio-isomers is a source for only NO at low energies (<12.76 eV). This is a key point for biomedical application of the nitroimidazoles, because NO is the vasodilator that favors the reoxigenation of hypoxic tumor tissues.

The Reaction of Sulfur Dioxide Radical Cation with Hydrogen and its Relevance in Solar Geoengineering Models.

SO2 has been proposed in solar geoengineering as a precursor of H2 SO4 aerosol, a cooling agent active in the stratosphere to contrast climate change. Atmospheric ionization sources can ionize SO2 into excited states of S O 2 · + , which quickly reacts with trace gases in the stratosphere. In this work we explore the reaction of H 2 D 2 with S O 2 · + excited by tunable synchrotron radiation, leading to H S O 2 + + H ( D S O 2 + + D ), where H contributes to O3 depletion and OH formation. Density Functional Theory and Variational Transition State Theory have been used to investigate the dynamics of the title barrierless and exothermic reaction. The present results suggest that solar geoengineering models should test the reactivity of S O 2 · + with major trace gases in the stratosphere, such as H2 since this is a relevant channel for the OH formation during the nighttime when there is not OH production by sunlight. OH oxides SO2 , triggering the chemical reactions leading to H2 SO4 aerosol.

VUV Photofragmentation of Chloroiodomethane: The Iso-CH2I-Cl and Iso-CH2Cl-I Radical Cation Formation.

Dihalomethanes XCH2Y (X and Y = F, Cl, Br, and I) are a class of compounds involved in several processes leading to the release of halogen atoms, ozone consumption, and aerosol particle formation. Neutral dihalomethanes have been largely studied, but chemical physics properties and processes involving their radical ions, like the pathways of their decomposition, have not been completely investigated. In this work the photodissociation dynamics of the ClCH2I molecule has been explored in the photon energy range 9-21 eV using both VUV rare gas discharge lamps and synchrotron radiation. The experiments show that, among the different fragment ions, CH2I+ and CH2Cl+, which correspond to the Cl- and I-losses, respectively, play a dominant role. The experimental ionization energy of ClCH2I and the appearance energies of the CH2I+ and CH2Cl+ ions are in agreement with the theoretical results obtained at the MP2/CCSD(T) level of theory. Computational investigations have been also performed to study the isomerization of geminal [ClCH2I]•+ into the iso-chloroiodomethane isomers: [CH2I-Cl]•+ and [CH2Cl-I]•+.

HSO2+ Formation from Ion-Molecule Reactions of SO2⋠+ with Water and Methane: Two Fast Reactions with Reverse Temperature-Dependent Kinetic Trend.

In this work an experimental and theoretical study on the formation of HSO2+ ion from the SO2⋅+ +CH4 and SO2⋅+ +H2 O ion-molecule reactions at different temperatures is reported. Tunable synchrotron radiation was used to produce the SO2⋅+ ion in excited ro-vibrational levels of the ionic ground state X2 A1 and mass spectrometry was employed to identify the product ions. Calculations in the frame of the density functional theory and variational transition state theory were combined to explore the dynamics of the reactions. The experimental results show that HSO2+ is the only product in both reactions. Its yield decreases monotonically with photon energy in the SO2⋅+ +H2 O reaction, while it decreases at first and then increases in the SO2⋅+ +CH4 reaction. Theory confirms this trend by calculating the rate constants at different temperatures and explains the results by means of the polar, spin and charge effects as well as structural reorganization occurring in the reaction coordinate. The dynamic behavior observed in these two reactions is of general and fundamental interest. It can also provide some insights on the role of these reactions in astrochemistry as well as in their use as models for bond-activation reactions.

The role of the environment in the ion induced fragmentation of uracil.

The fragmentation of uracil molecules and pure and nano-hydrated uracil clusters by (12)C(4+) ion impact is investigated. This work focuses on the fragmentation behavior of complex systems and the effect of the environment. On the one hand, it is found that the environment in the form of surrounding uracil or water molecules has a significant influence on the fragmentation dynamics, providing an overall 'protective' effect, while on the other hand we observe the opening of specific fragmentation channels. In particular, we report on the first observation of a series of hydrated fragments. This indicates a strong interaction between uracil and water molecules, holding the water clusters bound to the observed molecular fragments.

VUV Photofragmentation of CH2I2: The [CH2I-I](•+) Iso-diiodomethane Intermediate in the I-Loss Channel from [CH2I2](•.).

Diiodomethane is an important halocarbon responsible for several atmospheric processes like ozone depletion and aerosol particle formation. Despite this, the thermochemical data and a detailed analysis of the pathways for the decomposition of this halomethane and its molecular ion [CH2I2](•+) are scarce. In this paper an investigation of the photodissociation dynamics of the CH2I2 molecule focused on the I-loss channel by the photoelectron-photoion coincidence (PEPICO) technique and computational methods is reported. The experimental results show that upon VUV irradiation the dissociation of the lower electronic ionic states of diiodomethane leads only to the CH2I(+) ion and the I atom. The theoretical calculations point out that isomerization of [CH2I2](•+) into iso-diiodomethane [CH2I-I](•+) may play an important role in the emission of iodine atom as compared to direct C-I bond breaking.

A joint theoretical and experimental study on diiodomethane: Ions and neutrals in the gas phase.

The chemical physics of halomethanes is an important and challenging topic in several areas of chemistry in particular in the chemistry of the atmosphere. Among the class of halomethanes, the diiodomethane molecule has attracted some interest in the last years, but despite this, the information on its radical cation [CH2I2](⋅+) is still limited. In this work, we measured and calculated the appearance energy (AE) of the ionic fragments I2(⋅+) and CH2(⋅+) and correlated the different fragmentation channels to the electronic states of the cation via photoelectron-photoion coincidence (PEPICO) experiments. In the case of the CH2/I2(⋅+) channel, the experimentally determined AE is in excellent agreement with the adiabatic theoretical value while a discrepancy is observed for the CH2(⋅+)/I2 channel. This discrepancy can be understood accounting for a fragmentation involving the formation of two I atoms (CH2(⋅+)/2I channel), which, as explained by time dependent density functional theory (TD-DFT) calculations, occurs when [CH2I2](⋅+) excited states are involved.

Photofragmentation spectra of halogenated methanes in the VUV photon energy range.

In this paper an investigation of the photofragmentation of dihalomethanes CH2X2 (X = F, Cl, Br, I) and chlorinated methanes (CH(n)Cl(4-n) with n = 0-3) with VUV helium, neon, and argon discharge lamps is reported and the role played by the different halogen atoms is discussed. Halogenated methanes are a class of molecules used in several fields of chemistry and the study of their physical and chemical proprieties is of fundamental interest. In particular their photodissociation and photoionization are of great importance since the decomposition of these compounds in the atmosphere strongly affects the environment. The results of the present work show that the halogen-loss is the predominant fragmentation channel for these molecules in the VUV photon energy range and confirm their role as reservoir of chlorine, bromine, and iodine atoms in the atmosphere. Moreover, the results highlight the peculiar feature of CH2F2 as a source of both fluorine and hydrogen atoms and the characteristic formation of I2(+) and CH2(+) ions from the photofragmentation of the CH2I2 molecule.

Gold Nanorods as Radiopharmaceutical Carriers: Preparation and Preliminary Radiobiological In Vitro Tests.

Low-energy electrons (Auger electrons) can be produced via the interaction of photons with gold atoms in gold nanorods (AuNRs). These electrons are similar to those emitted during the decay of technetium-99m (99mTc), a radioactive nuclide widely used for diagnostics in nuclear medicine. Auger and internal conversion (IC) electron emitters appropriately targeted to the DNA of tumors cells may, therefore, represent a new radiotherapeutic approach. 99mTc radiopharmaceuticals, which are used for diagnosis, could indeed be used in theragnostic fields when loaded on AuNRs and delivered to a tumor site. This work aims to provide a proof of concept (i) to evaluate AuNRs as carriers of 99mTc-based radiopharmaceuticals, and (ii) to evaluate the efficacy of Auger electrons emitted by photon-irradiated AuNRs in inducing radio-induced damage in T98G cells, thus mimicking the effect of Auger electrons emitted during the decay of 99mTc used in clinical settings. Data are presented on AuNRs' chemical characterization (with an aspect ratio of 3.2 and Surface Plasmon Resonance bands at 520 and 680 nm) and the loading of pharmaceuticals (after 99mTc decay) on their surface. Spectroscopic characterizations, such as UV-Vis and synchrotron radiation-induced X-ray photoelectron (SR-XPS) spectroscopies, were performed to investigate the drug-AuNR interaction. Finally, preliminary radiobiological data on cell killing with AuNRs are presented.

Fabrication of a New, Low-Cost, and Environment-Friendly Laccase-Based Biosensor by Electrospray Immobilization with Unprecedented Reuse and Storage Performances.

The fabrication of enzyme-based biosensors has received much attention for their selectivity and sensitivity. In particular, laccase-based biosensors have attracted a lot of interest for their capacity to detect highly toxic molecules in the environment, becoming essential tools in the fields of white biotechnology and green chemistry. The manufacturing of a new, metal-free, laccase-based biosensor with unprecedented reuse and storage capabilities has been achieved in this work through the application of the electrospray deposition (ESD) methodology as the enzyme immobilization technique. Electrospray ionization (ESI) has been used for ambient soft-landing of laccase enzymes on a carbon substrate, employing sustainable chemistry. This study shows how the ESD technique can be successfully exploited for the fabrication of a new promising environment-friendly electrochemical amperometric laccase-based biosensor, with storage capability up to two months without any particular care and reuse performance up to 63 measurements on the same electrode just prepared and 20 measurements on the one-year-old electrode subjected to redeposition. The laccase-based biosensor has been tested for catechol detection in the linear range 2-100 µM, with a limit of detection of 1.7 µM, without interference from chrome, cadmium, arsenic, and zinc and without any memory effects.

90Y-DOTA-Nimotuzumab: Synthesis of a Promising ß- Radiopharmaceutical.

BACKGROUND: Nimotuzumab is a humanized anti-epidermal growth factor receptor (EGFR) monoclonal antibody, nowadays used for tumour immunochemotherapy. This study aimed to label the conjugate DOTA-nimotuzumab with yttrium-90, in order to provide a ß- emitting radioimmunoconjugate (90Y-DOTA-nimotuzumab) potentially useful to assess the feasibility of a new radio-guided surgery approach. METHODS: The synthesis of 90Y-DOTA-nimotuzumab was performed in two days. Nimotuzumab was conjugated with a 50-fold excess of DOTA and then labelled with 90Y3+. The 90Y-DOTA-nimotuzumab preparation was optimized considering several parameters such as pH, temperature and reaction volume. Moreover, the 90Y-DOTA-nimotuzumab stability was evaluated in human plasma. RESULTS: The radioimmunoconjugate 90Y-DOTA-nimotuzumab was obtained with a radiochemical purity greater than 96%, and showed a good stability at 20°C as well as at 37°C in human plasma. CONCLUSIONS: The optimized conditions for a mild and easy preparation of 90Y-DOTA-nimotuzumab joined to a promising stability under physiological conditions suggest to propose this radioimmunoconjugate as a potential diagnostic radiopharmaceutical for ß- radio-guided surgery.

Double C-H activation of ethane by metal-free SO2*+ radical cations.

The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

Electrospray deposition as a smart technique for laccase immobilisation on carbon black-nanomodified screen-printed electrodes.

Enzymes immobilisation represents a critical issue in the design of biosensors to achieve standardization as well as suitable analytical performances in terms of sensitivity, selectivity, and stability. In this work electrospray deposition (ESD) has been exploited as a novel technique for the immobilisation of laccase enzyme on carbon black modified screen-printed electrodes. The aim is to fabricate an amperometric biosensor for phenolic compound detection. The electrodes produced by ESD have been analysed by scanning electron microscopy and characterised electrochemically to prove that this immobilisation technique is suited to manufacture high performance biosensors. The results show that the laccase enzyme maintains its activity after undergoing the electrospray ionisation process and deposition and the fabricated biosensor has improved performances in terms of storage (up to 3 months at room temperature) and working (up to 25 measurements on the same electrode) stability. The laccase-based biosensor has been tested for phenolic compound detection, with catechol as target analyte, in the linear range 2.5-50 µM, with 2.0 µM limit of detection, without interference from lead, cadmium, atrazine, and paraoxon, and without matrix effect in drinking, surface, and wastewater.

Radioguided surgery with ß- radiation in pancreatic Neuroendocrine Tumors: a feasibility study.

The possibility to use ß- decaying isotopes for radioguided surgery (RGS) has been recently proposed, and first promising tests on ex-vivo samples of Meningioma and intestinal Neuroendocrine Tumor (NET) have been published. This paper reports a study of the uptake of 68Ga-DOTATOC in pancreatic NETs (pNETs) in order to assess the feasibility of a new RGS approach using 90Y-DOTATOC. Tumor and healthy pancreas uptakes were estimated from 68Ga-DOTATOC PET/CT scans of 30 patients with pNETs. From the obtained SUVs (Standardised Uptake Value) and TNRs (Tumor Non tumor Ratio), an analysis algorithm relying on a Monte Carlo simulation of the detector has been applied to evaluate the performances of the proposed technique. Almost all considered patients resulted to be compatible with the application of ß--RGS assuming to administer 1.5 MBq/kg of activity of 90Y-DOTATOC 24 h before surgery, and a sampling time of few seconds. In just 2 cases the technique would have required a mildly increased amount of activity or of sampling time. Despite a high physiological uptake of 68Ga-DOTATOC in the healthy pancreas, the proposed RGS technique promises to be effective. This approach allows RGS to find application also in pancreatic diseases, where traditional techniques are not viable.

Water activation by SO2(*+) ions: an effective source of OH* radicals.

A novel O-H bond activation reaction is reported: thermal SO(2)(*+) radical cations activate water in the gas phase forming OH* radicals with 100% efficiency.

Experimental and theoretical evidence for HS4.

The new radical HS(4) containing three sulfur-sulfur bonds has been detected in the gas phase by mass spectrometric experiments. Structures and energies of HS(4) in the three oxidation states +/0/- have been investigated by ab initio calculations. HS(4) is characterized by the HSSSS open-chain structure, and it is stable toward dissociation into S(2) and HS(2) by 23 kcal mol(-1). The first detection of HS(4)(-), the conjugate base of the strong acid H(2)S(4) is also reported.