Enantioselective HF loss promoted by resonant two photon ionization of supersonically expanded (R)-1-phenyl-2,2,2-trifluoroethanol clusters.

(R)-1-Phenyl-2,2,2-trifluoroethanol and its hydrogen bonded adducts with achiral (water, tetrahydrofuran) and chiral solvent mols. ((R)- and (S)-butan-2-ol, (R)- and (S)-3-hydroxy-tetrahydrofuran) have been ionized by resonant two-photon absorption. The presence of photofragments, attributable to the occurrence of a hydrogen fluoride loss reaction, has been interpreted with the aid of theor. predictions at the DFT level of theory with the inclusion of dispersive terms. The HF elimination process takes place by a mechanism involving the preliminary C.alpha.-H hydrogen transfer to an hydroxyl oxygen assisted by the solvent mol. which is followed by extrusion of the HF mol. The calcd. energy barriers depend on the type of solvent as well as on its configuration and are consistent with the obsd. fragmentation ratios

Molecular and supramolecular chirality: R2PI spectroscopy as a tool for the gas-phase recognition of chiral systems of biological interest.

A review. In life sciences, diastereomeric chiral mol./chiral receptor complexes are held together by a different combination of intermol. forces and are therefore endowed with different stability and reactivity. Detn. of these forces, which are normally affected in the condensed phase by solvent and supramol. interactions, can be accomplished through the generation of diastereomeric complexes in the isolated state and their spectroscopic investigation. This review presents a detailed discussion of the mass resolved Resonant Two Photon Ionization (R2PI-TOF) technique in supersonic beams and introduces an overview of various other technologies currently available for the spectroscopic study of gas phase chiral mols. and supramol. systems. It reports case studies primarily from the authors' recent work using R2PI-TOF methodol. for chiral recognition in clusters contg. mols. of biol. interest. The measurement of absorption spectra, ionization and fragmentation thresholds of diastereomeric clusters by this technique allow the detn. of the nature of the intrinsic interactions, which control their formation and which affect their stability and reactivity

Tools for in vitro propagation/synchronization of the liverwort Marchantia polymorpha and application of a validated HPLC-ESI-MS-MS method for glutathione and phytochelatin analysis

Bryophytes, due to their poikilohydric nature and peculiar traits, are useful and versatile organisms for studies on metal accumulation and detoxification in plants. Among bryophytes, the liverwort Marchantia polymorpha is an excellent candidate as a model organism, having a key role in plant evolutionary history. In particular, M. polymorpha axenic cultivation of gametophytes offers several advantages, such as fast growth, easy propagation and high efficiency of crossing. Thus, the main purpose of this work was to promote and validate experimental procedures useful in the establishment of a standardized set-up of M. polymorpha gametophytes, as well as to study cadmium detoxification processes in terms of thiol-peptide production, detection and characterisation by HPLC-mass spectrometry. The results show how variations in the composition of the Murashige and Skoog medium impact the growth rate or development of this liverwort, and what levels of glutathione and phytochelatins are produced by gametophytes to counteract cadmium stress

Contribution of 3H-thymidine labelling index and flow cytometric S-phase in predicting survival of patients with non-Hodgkin's lymphoma.

The 3H-thymidine labelling index (3H-dT LI) of cell suspensions from fresh material and the flow cytometric S-phase (FCM-S) of nuclei recovered from paraffin blocks were determined on the same pathologic lymph node specimen for 190 non-Hodgkin's lymphomas (NHLs). FCM-S was defined by a planimetric method and by an optimization procedure. Poor correlation coefficients were observed among the three cell kinetic variables. All three cell kinetic variables were significant indicators of 8-year survival and median survival time. The life-regression procedure evidenced a significant relative contribution of 3H-dT LI and FCM-S, thus suggesting a different biologic meaning of the two cell kinetic variables. This finding was further supported by evidence that simultaneous use of 3H-dT LI and FCM-S can identify groups of patients with different survival better than when either modality is used alone. Multivariate analysis indicated that the risk groups as defined by cell kinetic variables are predictors of survival even in the presence of established factors such as histology and stage

Autonomous decision-making against induced seismicity in deep fluid injections

The rise in the frequency of anthropogenic earthquakes due to deep fluid injections is posing serious economic, societal, and legal challenges to geo-energy and waste-disposal projects. We propose an actuarial approach to mitigate this risk, first by defining an autonomous decision-making process based on an adaptive traffic light system (ATLS) to stop risky injections, and second by quantifying a "cost of public safety" based on the probability of an injection-well being abandoned. The ATLS underlying statistical model is first confirmed to be representative of injection-induced seismicity, with examples taken from past reservoir stimulation experiments (mostly from Enhanced Geothermal Systems, EGS). Then the decision strategy is formalized: Being integrable, the model yields a closed-form ATLS solution that maps a risk-based safety standard or norm to an earthquake magnitude not to exceed during stimulation. Finally, the EGS levelized cost of electricity (LCOE) is reformulated in terms of null expectation, with the cost of abandoned injection-well implemented. We find that the price increase to mitigate the increased seismic risk in populated areas can counterbalance the heat credit. However this "public safety cost" disappears if buildings are based on earthquake-resistant designs or if a more relaxed risk safety standard or norm is chosen.Comment: 8 pages, 4 figures, conference (International Symposium on Energy Geotechnics, 26-28 September 2018, Lausanne, Switzerland

Effects of Lactobacillus acidophilus D2/CSL (CECT 4529) supplementation on healthy cat performance

Background The present study aimed to evaluate the effects of the probiotic strain Lactobacillusacidophilus D2/CSL (CECT 4529) on nutritional condition and faecal quality in cats. Methods Ten healthy adult cats from the same cattery were included (aged >9 months; male:female sex ratio=3:7). The animals were randomly assigned to a control group (CTR; n=5; male:female=1:4; room 1: 16 m 2) and to a treated group (LACTO; n=5; male:female=2:3; room 2: 16 m 2) receiving the same commercial dry diet. The LACTO group diet was supplemented with the probiotic (5 x 10 9 cfu/kg feed at least). A five-week experimental period was applied, and nutritional status was monitored by bodyweight (BW) and body condition score (BCS). Faecal quality was evaluated using faecal score (FS) and faecal moisture (FM) parameters. Plate counts of some faecal bacteria species were carried out. The data obtained were analysed using MIXED, GLM and NPAR1WAY procedures (SAS V.9.4; P 640.05). Results The two groups did not show differences in BW and BCS data. A clear effect of the probiotic supplementation on FM was recorded (LACTO 44 per cent v CTR group 46 per cent; P=0.04). FS in the LACTO group (3.35) was close to ideal values (2-3) in comparison with the CTR group (3.75). Positive effects of Lacidophilus D2/CSL have been recorded in terms of increase in faecal lactobacilli counts and reduction in faecal coli counts. Conclusions This study's preliminary results describe how inclusion of Lacidophilus D2/CSL (CECT 4529) probiotic strain in cats' diets could effectively improve faecal quality parameters and consequently gut health in adult healthy cats

egg quality and productive performance of laying hens fed different levels of skimmed milk powder added to a diet containing lactobacillus acidophilus

Abstract The current trial was carried out on a commercial poultry farm to study the effect of skim milk powder (SMP) added to a diet containing Lactobacillus acidophilus on performance and egg quality of laying hens from 20 to 49 wk of age. A total of 2,400 Hy-Line W-36 laying hens were housed in 600 unenriched cages (4 hens each) located over 4 tier levels. Animals were assigned to 1 of 3 experimental treatments (0, 3, and 4). The laying hens assigned to treatments 3 and 4 received a diet enriched respectively with 3 and 4% SMP, whereas the animals in treatment 0 were fed a diet without SMP. All diets, moreover, were supplemented with L. acidophilus D2/CSL. Hen performance was determined throughout the experimental period and egg quality was measured on 30 eggs per treatment every week. Results showed that productive performance in terms of egg production, egg weight, and feed conversion ratio was not influenced by SMP at 3 or 4% of the diet. Egg quality was significantly affected by SMP included at 3 or 4% of the diet. Eggs from treatments 3 and 4, in fact, displayed higher shell thickness than those from treatment 0 (

Chiral recognition between 1-(4-fluorophenyl)ethanol and 2-butanol: higher binding energy of homochiral complexes in the gas phase

Diastereomeric adducts between (S)-1-(4-fluorophenyl)-ethanol and R and S 2-butanol, formed by supersonic expansion, were studied by a combination of mass selected resonant two-photon ionization-spectroscopy and IR depletion spectroscopy. Chiral recognition is evidenced by the specific spectroscopic signatures of the S1 S0 electronic transition as well as different frequencies and intensities of the OH stretch vibrational mode in the ground state. D-DFT calcns. were performed to assist in the anal. of the spectra and the detn. of the structures. The homochiral and heterochiral complexes show slight structural differences, in particular in the interaction of the alkyl groups of 2-butanol with the arom. ring. The homochiral [FESBS] complex is more stable than the heterochiral [FESBR] diastereomer in both the ground and excited states. The binding energy difference was evaluated to be >0.60 kcal mol-1

Relationship between dielectric properties and critical behavior of the electric birefringence in binary liquid mixtures

We present experimental results on the critical exponent ψEKE describing the divergence of the Kerr constant of binary liquid mixtures near the critical consolute point. We show that the measured value of ψEKE agrees with the theoretical prediction only if the measurement is performed with a mixture of two liquids presenting a small mismatch in the dielectric constant, and that the measured ψEKE grows as the dielectric constant mismatch increases. Such findings are consistent with a recent model which assumes that the elongation of critical fluctations along the direction of the electric field can become so strong that fluctuations in the direction perpendicular to the electric field may cross over from Ising to mean-field behavior

Photochemical R2PI study of chirality and intermolecular forces in supersonic beam

One and two-color, mass selected R2PI spectra of theS1←S0transitions in the bare(+)-(R)- 1-phenyl-1-ethanol(ER) and its complexes with different solvent molecules (solv) (-)-(R)-2-butanol(BR) or(+)-(S)-2-butanol(BS), (—)-(R)-2-pentanol (TR) or(+)-(S)-2-pentanol(TS) and(-)-(R)-2-butylamine(AR) or(+)-(S)-2-butylamine(AS), have been recorded after a supersonic molecular beam expansion. The one-color R2PI excitation spectra of the diastereomeric complexes are characterized by significant shifts of their band origin relative to that of bareER. The extent and the direction of these spectral shifts are found to depend upon the structure and the configuration ofsolvand are attributed to different short-range interactions in the ground and excited states of the complexes. In analogy with other diastereomeric complexes, the phenomenological binding energy of the homochiral cluster is found to be greater than that of the heterochiral one. Preliminary measurements of excitation spectrum of(+)-(R)-1-Indanol(IR) is also reported