Tautomeric Equilibria Studies by Mass Spectrometry

Tautomerism in organic chemistry has been extensively studied in condensed phase by spectrometric methods, mainly by IR and NMR techniques. Mass spectrometry studies start 40 years ago but just recently it has been recognized the importance of the mass spectral data for the study of tautomerism in the gas phase.
Mass spectrometry can provide valuable information in regard to tautomeric equilibria when studying mass spectra among the members of different families of organic compounds.
The relevance of the mass spectral data resides on several facts but there are two that are of key importance:
1-	Mass spectral fragmentation assignments should be tautomer specific since the corresponding abundances ratios are supposed to be correlated to the keto/enol contents.
2-	Ionization in the ion source is supposed to have no effect on the position of the equilibrium so that the results reflect the tautomers content in the gas phase previous to ionization.
Some of the carbonylic compounds do not exhibit noticeable tautomerism so the fragment abundances assigned to the enol form is very low or not measurable. Since enolization is more noticeable in the case of thio-derivatives (which correlates adequately with the oxygenated analogues), the study of their mass spectra is an interesting choice to reach some degree of generalization. 
In addition, experimental findings are supported by semiempirical theoretical calculations, which probed to be adequate not only for supporting tendency correlations among the members of a compound family but also to calculate heats of tautomerization in gas phase.
Reports using mass spectrometry for tautomerism are becoming less common. One of the reasons is that now it would appear that the interpretation of MS results is not as straightforward as it was once believed, even though in a recent review it was written that: “Mass spectrometry is the most informative and practical method for studying and identifying tautomers in the gas phase” [1]. 
In fact, mass spectrometry seems to be very informative for studying and identifying tautomers, because in this case external factors like solvents, intermolecular interactions, etc., can be excluded by transferring the tautomeric system into gas phase, where the process becomes truly unimolecular [1].
This review covers the study of Tautomerism by Mass Spectrometry in the last four decades. 
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The adsorption structure of furan on Pd(1 1 1)

The structure of molecular furan, C4H4O, on Pd(1 1 1) has been investigated by O K-edge near-edge X-ray absorption fine structure (NEXAFS) and C 1s scanned-energy mode photoelectron diffraction (PhD). NEXAFS shows the molecule to be adsorbed with the molecular plane close to parallel to the surface, a conclusion confirmed by the PhD analysis. Chemical-state specific C 1s PhD data were obtained for the two inequivalent C atoms in the furan, the α-C atoms adjacent to the O atom, and the β-C atoms bonded only to C atoms, but only the PhD modulations for the α-C emitters were of sufficiently large amplitude for detailed evaluation using multiple scattering calculations. This analysis shows the α-C atoms to be located approximately 0.6 Å off-atop surface Pd atoms with an associated C–Pd bondlength of 2.13 ± 0.03 Å. Two alternative local geometries consistent with the data place the O atom in off-atop or near-hollow locations, and for each of these local structures there are two equally-possible registries relative to the fcc and hcp hollow sites. The results are in good agreement with earlier density functional theory calculations which indicate that the fcc and hcp registries are equally probable, but the PhD results fail to distinguish the two distinct local bonding geometries

A structural study of a C3H3 species coadsorbed with CO on Pd(1 1 1)

The combination of chemical-state-specific C 1s scanned-energy mode photoelectron diffraction (PhD) and O K-edge near-edge X-ray absorption fine structure (NEXAFS) has been used to determine the local adsorption geometry of the coadsorbed C3H3 and CO species formed on Pd(1 1 1) by dissociation of molecular furan. CO is found to adopt the same geometry as in the Pd(1 1 1)c(4 × 2)-CO phase, occupying the two inequivalent three-fold coordinated hollow sites with the C–O axis perpendicular to the surface. C3H3 is found to lie with its molecular plane almost parallel to the surface, most probably with the two ‘outer’ C atoms in equivalent off-atop sites, although the PhD analysis formally fails to distinguish between two distinct local adsorption sites

A WIRELESS SENSOR NETWORK BOARD FOR ENVIRONMENTAL MONITORING USING GNSS AND ANALOG TRIAXIAL ACCELEROMETER

Wireless Sensor Networks (WSNs) have attracted an increasing attention in recent years because of the large number of potential applications. They are used for collecting, storing and sharing data, for monitoring applications, surveillance purposes and much more. On the other hand GNSSs are used in various systems devoted to monitor different atmospheric parameters and to trace displacements of landslides and glaciers in severe environmental conditions and in all weather situations. A first example of low cost DGPS wireless sensor network was installed in 2009 on a serac located at 4100 m above a populated area in the Aosta Valley, Italy, and it is still operative. This work presents an evolution of the WSN node used in that systems with improved functionalities and flexibility. The electronic board developed as a multipurpose board to be used in different WSNs, has been completely redesigned as an open system in order to reduce its sizes and to be configured by only varying the firmware on the microcontroller. It allows different interfaces and is equipped with a recovery system, guaranteed by a watchdog chip which continuously monitor the onboard microcontroller. The board is equipped with both a GNSS module and an analog triaxial accelerometer in order to merge GNSS raw data and accelerometer data to keep track of both fast events and slow events. A free open source operative system has been ported on the microcontroller in order to perform multiple operations and to manage the communications between the network nodes with improved efficiency. The board firmware can be modified in real time using a custom bootloader to avoid difficult maintenance operations

Local adsorption structure and bonding of porphine on Cu(111) before and after self-metalation

We have experimentally determined the lateral registry and geometric structure of free-base porphine (2H-P) and copper-metalated porphine (Cu-P) adsorbed on Cu(111), by means of energy-scanned photoelectron diffraction (PhD), and compared the experimental results to density functional theory (DFT) calculations that included van der Waals corrections within the Tkatchenko-Scheffler approach. Both 2H-P and Cu-P adsorb with their center above a surface bridge site. Consistency is obtained between the experimental and DFT-predicted structural models, with a characteristic change in the corrugation of the four N atoms of the molecule's macrocycle following metalation. Interestingly, comparison with previously published data for cobalt porphine adsorbed on the same surface evidences a distinct increase in the average height of the N atoms above the surface through the series 2H-P, Cu-P, cobalt porphine. Such an increase strikingly anti-correlates the DFT-predicted adsorption strength, with 2H-P having the smallest adsorption height despite the weakest calculated adsorption energy. In addition, our findings suggest that for these macrocyclic compounds, substrate-to-molecule charge transfer and adsorption strength may not be univocally correlated

Photoelectron diffraction investigation of the structure of the clean TiO2(110)(1×1) surface

The surface relaxations of the rutile TiO2(110)(1×1) clean surface have been determined by O 1 s and Ti 2p3∕2 scanned-energy mode photoelectron diffraction. The results are in excellent agreement with recent low-energy electron diffraction (LEED) and medium energy ion scattering (MEIS) results, but in conflict with the results of some earlier investigations including one by surface x-ray diffraction. In particular, the bridging O atoms at the surface are found to relax outward, rather than inward, relative to the underlying bulk. Combined with the recent LEED and MEIS results, a consistent picture of the structure of this surface is provided. While the results of the most recent theoretical total-energy calculations are qualitatively consistent with this experimental consensus, significant quantitative differences remain

The Effect of Bicarbonate Administration via Continuous Venovenous Hemofiltration on Acid-Base Parameters in Ventilated Patients

Background. Acute kidney injury (AKI) and metabolic acidosis are common in the intensive care unit. The effect of bicarbonate administration on acid-base parameters is unclear in those receiving continuous venovenous hemofiltration (CVVH) and mechanical ventilatory support. Methods. Metabolic and ventilatory parameters were prospectively examined in 19 ventilated subjects for up to 96 hours following CVVH initiation for AKI at an academic tertiary care center. Mixed linear regression modeling was performed to measure changes in pH, partial pressure of carbon dioxide (pCO2), serum bicarbonate, and base excess over time. Results. During the 96-hour study period, pCO2 levels remained stable overall (initial pCO2 42.0 ± 14.6 versus end-study pCO2 43.8 ± 16.1 mmHg; P=0.13 for interaction with time), for those with initial pCO2 ≤40 mmHg (31.3 ± 5.7 versus 35.0 ± 4.8; P=0.06) and for those with initial pCO2 >40 mmHg (52.7 ± 12.8 versus 53.4 ± 19.2; P=0.57). pCO2 decreased during the immediate hours following CVVH initiation (42.0 ± 14.6 versus 37.3 ± 12.6 mmHg), though this change was nonsignificant (P=0.052). Conclusions. We did not detect a significant increase in pCO2 in response to the administration of bicarbonate via CVVH in a ventilated population. Additional studies of larger populations are needed to confirm this finding

Mass spectrometric study of the photooxidation of the ophthalmic drugs timolol and pindolol

A mass spectrometric study of the photooxidation products of the ophthalmic drugs pindolol (1-[1H-indol-4-yloxyl]-3-[isopropylamino]-2-propanol) and timolol (S-[-]-1-[t-butylamino]-3-[(4-morpholino-1,2,5-thiadiazol-3-yl)oxyl]-2-propanol) in water has been performed by LC-MS. Based on these data and the assumption that photooxidation mainly occurs through singlet molecular oxygen attack, a possible reaction mechanism is proposed. The mechanistic pathways involve singlet oxygen attack to the pindolol indole ring and oxidation of the pindolol isopropyl or timolol terbutyl methyl groups.Instituto de Investigaciones Fisicoquímicas Teóricas y AplicadasLaboratorio de Estudio de Compuestos Orgánico

Remoción de plaguicidas MCPA e Imazapic de solución acuosa con materiales carbonosos

El objetivo general de este trabajo se orienta a la búsqueda de alternativas simples y accesibles para la remediación de aguas contaminadas, teniendo en cuenta que la presencia de contaminantes emergentes en nuestros recursos hídricos, tales como fármacos y pesticidas, es motivo de preocupación para la salud y seguridad ambiental. Se realizaron estudios de adsorción de dos pesticidas: MCPA (ácido 4-cloro-2-metil fenoxiacético) e Imazapic (ácido 2-[4,5-dihidro-4-metil-4-(1-metiletil)-5-oxo-1H-imidazol-2-il]-5-metil-3-piridin carboxílico), en dos diferentes tipos de material carbonoso. Fueron utilizados dos tipos de carbón activado, cada uno con diferentes características físicas y químicas, CAT-Ox 4 sulfuro de hidrógeno, adquirido en pellets de 4mm y CARBOPAL MB 4S (Donau). Se realizaron diferentes experimentos en batch de los herbicidas MCPA e Imazapic sobre dos tipos de carbón activado, CAT y CARBOPAL, bajo diferentes condiciones. Ambos materiales parecen ser muy efectivos removiendo estos contaminantes, pero CAT parece tener una mayor capacidad. Ambos pesticidas siguen cinéticas de adsorción de pseudo segundo orden en ambos materiales, lo que indicaría una mayor contribución de quimisorción con formación de monocapa. La capacidad de adsorción (qe) de herbicidas es significativamente influenciada por el valor de pH. En el presente estudio, ambos pesticidas tienen una disminución en la capacidad de adsorción cuando se utilizan condiciones básicas debido a que la superficie de los carbones están cargadas negativamente y en estas condiciones los herbicidas se encuentran en forma aniónica. Además, diferentes modelos fueron analizados para predecir propiedades de cada proceso de adsorción. MCPA se adapta al modelo teórico de Langmuir en ambos materiales. Debido a esto, se predice un proceso de quimisorción con la formación de una monocapa. Por otro lado, Imazapic se adapta al modelo GAB sobre CAT y CARBOPAL, con la formación de multicapas. La capacidad de adsorción es muy alta, por lo que ambos materiales pueden ser usados como método efectivo y de bajo costo para remover MCPA e Imazapic de recursos acuosos.Trabajo presentado por el Centro de Estudio de Compuestos Orgánicos (CEDECOR