Advantages and drawbacks of life cycle assessment application to the pharmaceuticals: a short critical literature review.

Pharmaceuticals are among the most challenging products to assess by life cycle assessment (LCA). The main drawback highlighted by LCA practitioners is the lack of inventory data, both regarding the synthesis of active pharmaceutical ingredient (API) precursors (upstream) and the details concerning the downstream phases (use and end of life). A short critical review of pharma-LCAs found in the literature is here proposed, with discussion of several tools and models used to predict the environmental impacts derived from the life cycle of pharmaceuticals, emphasizing current strengths and weaknesses, and exploring the possibilities for improvements.

Formation of HO and OH by CO and NO 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 theoretical study of the ion chemistry of carbon dioxide and nitrous oxide radical cations reacting with water.

Calculation of electron interaction models in N and O.

Cosmic rays have the potential to significantly affect the atmospheric composition by increasing the rate and changing the types of chemical reactions through ion production. The amount and states of ionization, and the spatial distribution of ions produced are still open questions for atmospheric models. To precisely estimate these quantities, it is necessary to simulate particle-molecule interactions, down to very low energies.

Three-Body Collisions Driving the Ion-Molecule Reaction C + H at Low Temperatures.

We report on the three-body reaction rate of C with H producing CH studied in a cryogenic 16-pole radio frequency ion trap. The reaction was measured in the temperature range from 10 to 28 K, where it was found to only take place via three-body collisions. The experimentally determined termolecular rate coefficient follows the form of with = 20 K, where = 8.

Adsorption and Dissociation of -Methyl -Tolyl Sulfoxide on Au(111).

Sulfur-based molecules producing self-assembled monolayers on gold surfaces have long since become relevant functional molecular materials with many applications in biosensing, electronics, and nanotechnology. Among the various sulfur-containing molecules, the possibility to anchor a chiral sulfoxide to a metal surface has been scarcely investigated, despite this class of molecules being of great importance as ligands and catalysts. In this work, ()-(+)-methyl -tolyl sulfoxide was deposited on Au(111) and investigated by means of photoelectron spectroscopy and density functional theory calculations.

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

The exothermic hydrogen transfer from H to CO leading to H and HCO is investigated in a combined experimental and theoretical work. The experimental mass/charge ratios of the ionic product (HCO) and the ionic reactant (CO) 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.

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

Design of a fluorescent and clickable Ag(SRN) nanocluster platform: synthesis, modeling and self-assembling.

Fluorescent atomically precise Ag(11-azido-2-ol-undecane-thiolate) nanoclusters are easily prepared using sodium ascorbate as a "green" reducer and are extensively characterized by way of elemental analyses, ATR-FTIR, XRD, SAXS, UV-vis, fluorescence spectroscopies, and theoretical modeling. The fluorescence and the atomically determined stoichiometry and structure, the facile and environmentally green synthesis, together with the novel presence of terminal azido groups in the ligands which opens the way to "click"-binding a wide set of molecular species, make Ag(11-azido-2-ol-undecane-thiolate) nanoclusters uniquely appealing systems for biosensing, recognition and functionalization in biomedicine applications and in catalysis.

Exploiting Reaction-Diffusion Conditions to Trigger Pathway Complexity in the Growth of a MOF.

Coordination polymers (CPs), including metal-organic frameworks (MOFs), are crystalline materials with promising applications in electronics, magnetism, catalysis, and gas storage/separation. However, the mechanisms and pathways underlying their formation remain largely undisclosed. Herein, we demonstrate that diffusion-controlled mixing of reagents at the very early stages of the crystallization process (i.

On the Formation of Interstellar CH Anions: Exploring Mechanism and Rates for CH Reacting with H.

We present accurate ab initio calculations on the structural properties of a gas-phase reaction of possible interest for Saturn's outer atmosphere chemistry, in which the CH molecule has been detected. In the present study, that molecule is made to react with the H anion to form the CH species, one considered as a possible intermediate in ionic processes networks. The results indicate that this reaction is markedly exothermic and proceeds with the formation of an intermediate, which occurs via only a shallow barrier below the reagents and progresses directly to the product region.

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

SO has been proposed in solar geoengineering as a precursor of H SO aerosol, a cooling agent active in the stratosphere to contrast climate change. Atmospheric ionization sources can ionize SO into excited states of , which quickly reacts with trace gases in the stratosphere. In this work we explore the reaction of with excited by tunable synchrotron radiation, leading to ( ), where H contributes to O depletion and OH formation.

Modeling Ionic Reactions at Interstellar Temperatures: The Case of NH + H ⇔ NH + H.

Structural features and enthalpy details are presented for the title reactions, both for the exothermic (forward) path to NH formation and for the endothermic (reverse) reaction to NH formation. Both pathways have relevance for the nitrogen chemistry in the interstellar medium (ISM). They are also helpful to document the possible role of H in molecular clouds at temperatures well below room temperature.

A Fast Transient Absorption Study of Co(AcAc).

The study of transition metal coordination complexes has played a key role in establishing quantum chemistry concepts such as that of ligand field theory. Furthermore, the study of the dynamics of their excited states is of primary importance in determining the de-excitation path of electrons to tailor the electronic properties required for important technological applications. This work focuses on femtosecond transient absorption spectroscopy of Cobalt tris(acetylacetonate) (Co(AcAc)) in solution.

Gas Phase Oxidation of Carbon Monoxide by Sulfur Dioxide Radical Cation: Reaction Dynamics and Kinetic Trend With the Temperature.

Gas phase ion chemistry has fundamental and applicative purposes since it allows the study of the chemical processes in a solvent free environment and represents models for reactions occurring in the space at low and high temperatures. In this work the ion-molecule reaction of sulfur dioxide ion with carbon monoxide CO is investigated in a joint experimental and theoretical study. The reaction is a fast and exothermic chemical oxidation of CO into more stable CO by a metal free species, as , excited into ro-vibrational levels of the electronic ground state by synchrotron radiation.

The adsorption of silicon on an iridium surface ruling out silicene growth.

The adsorption of Si atoms on a metal surface might proceed through complex surface processes, whose rate is determined differently by factors such as temperature, Si coverage, and metal cohesive energy. Among other transition metals, iridium is a special case since the Ir(111) surface was reported first, in addition to Ag(111), as being suitable for the epitaxy of silicene monolayers. In this study we followed the adsorption of Si on the Ir(111) surface via high resolution core level photoelectron spectroscopy, starting from the clean metal surface up to a coverage exceeding one monolayer, in a temperature range between 300 and 670 K.

Overexpression of the Cytokine BAFF and Autoimmunity Risk.

Background: Genomewide association studies of autoimmune diseases have mapped hundreds of susceptibility regions in the genome. However, only for a few association signals has the causal gene been identified, and for even fewer have the causal variant and underlying mechanism been defined. Coincident associations of DNA variants affecting both the risk of autoimmune disease and quantitative immune variables provide an informative route to explore disease mechanisms and drug-targetable pathways.

Signature of surface periodicity in the electronic structure of Si(1 1 1)-(7 × 7).

The surface electronic structure of Si(1 1 1)-[Formula: see text] has been studied by angle-resolved photo electron spectroscopy. Replicas of the S surface state are found in correspondence with several [Formula: see text] unit cells in the reciprocal space. This observation resolves in a direct way the long-standing dichotomy between the structural and electronic properties of the system previously discussed on the basis of the [Formula: see text] or [Formula: see text] R30° surface models.

HSO Formation from Ion-Molecule Reactions of SO 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 HSO ion from the SO +CH and SO +H O ion-molecule reactions at different temperatures is reported. Tunable synchrotron radiation was used to produce the SO ion in excited ro-vibrational levels of the ionic ground state X A 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.

A New Anisotropic Charge-Equilibration Method for Self-Assembly of Organics on Metal Surface: d-Alaninol on Cu(100).

The supramolecular chemistry at surfaces has been extensively studied by quantum and classical computational models in order to simulate and reproduce the correct energetics and structures of adsorbed molecules on surfaces at various coverages. We have developed a classical tool able to sample the configuration space overcoming the topological constraints of the standard classical molecular dynamics. Our model is based on the charge equilibration procedure combined with an anisotropic pairwise atomic interaction where an angular dependence, with respect to the metal surface, is explicitly taken into account.

Chlorine Para-Substitution of 1-Phenylethanol: Resonant Photoionization Spectroscopy and Quantum Chemical Calculations of Hydrated and Diastereomeric Complexes.

The conformational landscape of (S)-1-(4-chlorophenyl)ethanol, its monohydrated complex, and its diastereomeric adducts with R- and S-butan-2-ol, have been investigated by resonant two-photon ionization (R2PI) spectroscopy coupled with time-of-flight mass spectrometry. Theoretical calculations at the D-B3LYP/6-31++G** level of theory have been performed to assist in the interpretation of the spectra and in the assignment of the structures. The R2PI spectra and the predicted structures have been compared with those obtained on the analogous non-halogenated and fluorinated systems, i.