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Metal–ligand cluster ions are structurally characterized by means of gas-phase infrared multiple photon dissociation spectroscopy. The mass-selected complexes consist of one or two metal cations M3+ (M = Al, Fe, or Ru) and two to five anionic bidentate acetylacetonate ligands. Experimental IR spectra are compared with different density functional theory calculations, namely, PBE/TZVP, B3LYP/6-31G*, and M06/6-31+G**. Frequency analysis was also performed at different levels, namely, scaled static harmonic and unscaled static anharmonic, or with ab initio molecular dynamics simulations at the PBE/TZVP level. All methods lead to simulated spectra that fit rather well with experimental data, and the spectral red shifts of several main bands, in the 1200 cm−1–1800 cm−1 range, are sensitive to the strength of the metal–ligand interaction and to the spin state of the ion. Due to the rigidity of those complexes, first principles molecular dynamics calculations provide spectra similar to that produced by static calculations that are already able to catch the main spectral signatures using harmonic calculations at the B3LYP/6-31G* level. [ABSTRACT FROM AUTHOR]

L'immersion des civelles (Anguilla anguilla L.) dans une solution hyperosmotique (5 % de chlorure de sodium) pendant 3'30 puis dans une solution contenant 1 % de chlorhydrate de tetracycline (CHTC) ou 2 % de fluorescéine (DCAF) pendant encore 3'30, entraîne une accélération de la vitesse d'entrée de ces deux marqueurs vitaux dans l'organisme des poissons et un marquage rapide des organes calcifiés (vertèbres et otolithes). Des résultats similaires sont obtenus en plaçant les civelles dans une solution contenant à la fois 5 % de chlorure de sodium et 1 % de CHTC ou 2 % de DCAF pendant 3'30. Le choc osmotique est proposé comme une avancée technique pour le marquage vital en masse des larves, des alevins et des stades juvéniles car il permet d'abaisser considérablement le temps de contact nécessaire entre les poissons et la solution de fluoromarqueur. Nous présentons une application de cette technique pour le marquage de 500 kg de civelles avec de la tetracycline. La réalisation de cette manipulation a demandé une journée et demie de travail à 5 personnes. Les résultats obtenus sont de très bonne qualité puisque l'on obtient 100 % de spécimens marqués dont 70 % le sont fortement. Il est donc possible de marquer une grande quantité de civelles dans un laps de temps réduit. Le problème de la reconnaissance in situ des animaux ainsi marqués est discuté.

Experimental and theoretical gas-phase studies of several noncovalent complexes of elementary molecules of biological interest are presented. The comparison provides a test of the validity of the employed methods.

Summary: Background: Topical photodynamic therapy (PDT) using methyl aminolaevulinate is a noninvasive treatment option suitable to treat clinical and subclinical actinic keratosis (AK) over a large area (field cancerization). The most widely used, conventional protocol in Europe includes illumination with a red‐light lamp. This illumination commonly causes pain, and patients often cannot complete the treatment. Objectives: The aims of this paper are twofold. The first aim is to introduce a novel protocol, the Phosistos protocol (P‐PDT), which includes illumination with a fabric‐based biophotonic device. The second and major aim is to assess the noninferiority, in terms of efficacy for PDT of AK, of P‐PDT compared with the conventional protocol (C‐PDT). Methods: A randomized, controlled, multicentre, intraindividual clinical study was conducted. Forty‐six patients with grade I–II AK of the forehead and scalp were treated with P‐PDT on one area (280 AK lesions) and with C‐PDT on the contralateral area (280 AK lesions). The primary end point was the lesion complete response (CR) rate at 3 months, with an absolute noninferiority margin of −10%. Secondary end points included pain scores, incidence of adverse effects and cosmetic outcome. Results: Three months following treatment, the lesion CR rate of P‐PDT was noninferior to that of C‐PDT (79·3% vs. 80·7%, respectively; absolute difference −1·6%; one‐sided 95% confidence interval −4·5% to infinity). The noninferiority of P‐PDT to C‐PDT in terms of the lesion CR rate remained at the 6‐month follow‐up (94·2% vs. 94·9%, respectively; absolute difference −0·6%; one‐sided 95% confidence interval −2·7% to infinity). Moreover, the pain score at the end of illumination was significantly lower for P‐PDT than for C‐PDT (mean ± SD 0·3 ± 0·6 vs. 7·4 ± 2·3; P < 0·001). Conclusions: P‐PDT is noninferior to C‐PDT in terms of efficacy for treating AK of the forehead and scalp and resulted in much lower pain scores and fewer adverse effects. What's already known about this topic? Topical photodynamic therapy using methyl aminolaevulinate is effective for treating actinic keratosis.In Europe, the conventional protocol involves illumination with a red‐light lamp. Unfortunately, pain is often experienced by patients undergoing this protocol.An alternative protocol that uses daylight illumination has recently been shown to be as effective as the conventional protocol while being nearly painless. However, this alternative protocol can be conducted only in suitable weather conditions. What does this study add? The Phosistos protocol is demonstrated to be as effective as the conventional protocol, nearly as painless as the daylight protocols and suitable year round for treatment of actinic keratosis. Plain language summary available online Linked Comment: Gilaberte. Br J Dermatol 2020; 182:11–12. [ABSTRACT FROM AUTHOR]

The gas-phase conformation of the intact (parent) unprotected RGD- peptide anion has been investigated using a combination of anion photoelectron spectroscopy and quantum chemistry calculations of its low-energy stable structures. The experimentally observed RGD- species correspond to a conformation in which the guanidinium group is protonated, the C-terminus is neutral, the aspartic acid carboxyl is deprotonated, and the anion’s excess electron orbital is localized on the protonated guanidinium. This structure is reminiscent of the RGD loop, which is the peptide motif recognized by trans-membrane integrins. The parent RGD- radical anion was generated using a unique infrared desorption-photoemission-helium jet ion source, whose ability to produce radical anions of peptides may also have analytical mass spectrometric implications. [ABSTRACT FROM AUTHOR]

Examines the coupling between the dipole bound and valence electronic states of the nitromethane anion. Use of Rydberg electron spectroscopy for the study; Comparison of the solvation behavior of nitromethane anion with acetonitrile anion; Isolation of dipole bound state from the resonance arising from excess electron occupation in the molecular orbital.

Summary: Background: Photodynamic therapy (PDT) is an effective treatment for actinic keratosis (AK), particularly for patients with large areas of field cancerization. Among the approved protocols in Europe, the most widely used requires irradiation with the Aktilite CL 128 lamp. However, pain during irradiation and the suboptimal adaptability of the lamp relative to the treatment area are two limiting factors of this protocol. To overcome these limits, a new protocol (referred to as the Flexitheralight protocol) involving irradiation with a light‐emitting, fabric‐based device was developed. Objectives: This paper aims to assess the noninferiority, in terms of PDT efficacy for treating AK, of the Flexitheralight protocol compared with the conventional protocol, which requires irradiation with the Aktilite CL 128 lamp. Methods: A monocentric, randomized, controlled, phase II clinical study was performed. Twenty‐five patients with grade I–II AKs of the forehead and scalp were treated with methyl aminolaevulinate PDT in two symmetrical areas. One area was treated with the conventional protocol (n = 154 AKs), whereas the other area was treated with the Flexitheralight protocol (n = 156 AKs). The primary end‐point was the lesion complete response (CR) rate at 3 months (an absolute noninferiority margin of –10% was used). The secondary end‐points included patient‐reported pain at the end of the irradiation. Results: At 3 months, the lesion CR rate with the Flexitheralight protocol was noninferior to that obtained with the conventional protocol (66·0% vs. 59·1%, respectively; absolute difference, 6·9%; 95% confidence interval –0·6% to 14·5%). Patient‐reported pain was significantly lower with the Flexitheralight protocol than with the conventional protocol (mean ± SD: 0·4 ± 0·6 vs. 5·0 ± 2·6; P < 0·0001). Conclusions: The Flexitheralight protocol is noninferior in terms of efficacy and superior in terms of tolerability to the conventional protocol for treating AKs of the forehead and scalp. What's already known about this topic? Methyl aminolaevulinate photodynamic therapy (PDT) is an effective and noninvasive treatment for actinic keratosis (AK).Treatment‐associated pain is frequently experienced by patients treated with the conventional protocol, which requires irradiation with the Aktilite CL 128 lamp.PDT using daylight as the activating light source has been confirmed as equally effective and less painful than the conventional protocol, but it cannot be performed in all weather conditions. What does this study add? This study demonstrates that the Flexitheralight protocol, which can be performed in all weather conditions, is equally effective as the conventional PDT protocol for AK and is a less painful technique. Linked Comment:Morton. Br J Dermatol 2019; 180:703–704. Respond to this article Plain language summary available online [ABSTRACT FROM AUTHOR]

A study of electron attachment properties of a series of saturated disulfides: dimethyl disulfide, diethyl disulfide and dipropyl disulfide, by Rydberg electron-transfer spectroscopy (RETS), negative ion photoelectron spectroscopy (NIPES) and quantum chemistry calculation is presented. Both RETS and NIPES show that the valence anions of these disulfides are stable.

Various hydroxypyridine derivatives are endogenous or synthetic photosensitizers which could contribute to solar radiation damage. The study of their excited states could lead to a better understanding of their action mechanisms. We present here the ultraviolet (UV) spectra of the protonated 2-, 3- and 4-hydroxypyridine. These spectra were obtained with an experimental device coupling an electrospray ion source with a cold quadrupole ion trap and a time of flight mass spectrometer. They display well resolved vibrational structures, with a clear influence of the position of the OH group. These results are interpreted with excited states calculations at the coupled cluster CC2 level. [ABSTRACT FROM AUTHOR]

BackgroundNeonatal jaundice is a common condition occurring in 60%-80% of all healthy-term and late-preterm neonates. In the majority of cases, neonatal jaundice resolves spontaneously and causes no harm; however, in some neonates, significant hyperbilirubinemia can develop and lead to kernicterus jaundice, a serious neurological disease. Phototherapy (PT) is the preferred treatment for jaundice; however, to be effective, PT devices need to have a broad light emission surface to generate no or little heat and to provide an optimal wavelength and light intensity (420-490 nm and ≥30 µW/cm²/nm, respectively). ObjectiveThis study aimed to investigate the feasibility, safety, and level of satisfaction of parents and health care teams with the BUBOlight device, an innovative alternative to conventional hospital PT, in which luminous textiles have been incorporated in a sleeping bag. MethodsThis interventional, exploratory, simple group, nonrandomized, single-center trial will be conducted at Lille Hospital. In total, 10-15 neonates and their parents will be included to obtain evaluable data from 10 parent-neonate pairs. Neonates weighing more than 2500 g at birth and born with ≥37 weeks of amenorrhea that required PT in accordance with the guidelines of the National Institute For Health and Clinical Excellence will receive one 4-hour session of illumination. Total serum bilirubin and transcutaneous bilirubin levels were obtained at the start and 2 hours after the end of PT. Cutaneous and rectal temperatures, heart rate, and oxygen saturation will be measured at the beginning and during PT. The number of subjects is therefore not calculated on the basis of statistical assumptions. We aim to obtain a minimum proportion of 90% (ie, 9 of 10) of the neonates included, who have been able to undergo 4-hour PT without unacceptable and unexpected toxicities. We will calculate the mean, median, quartiles, minimum and maximum values of the quantitative parameters, and the frequency of the qualitative parameters. The rate of patients with no unacceptable and unexpected toxicities (ie, the primary endpoint) will be calculated. ResultsThe first patient is expected to be enrolled at the end of 2020, and clinical investigations are intended for up to June 2021. The final results of this study are expected to be available at the end of 2021. ConclusionsOur findings will provide insights into the safety and feasibility of a new PT device based on light-emitting fabrics for the treatment of newborn jaundice. This new system, if proven effective, will improve the humanization of neonatal care and help avoid mother-child separation. Trial RegistrationClinicalTrials.gov NCT04365998; https://clinicaltrials.gov/ct2/show/NCT04365998 International Registered Report Identifier (IRRID)PRR1-10.2196/24808

BackgroundExtramammary Paget disease of the vulva (EMPV) is a rare skin disorder commonly seen in postmenopausal Caucasian females that appears clinically as red, eczematous, pruriginous, and sometimes painful lesions. Although most cases are noninvasive, EMPV may be associated with an underlying or distant adenocarcinoma. EMPV has a chronic and relapsing course. The reference treatment is based on local surgical excision with negative margins. However, disease frequently extends far from the visible lesion, and surgical margins are frequently positive. Topical photodynamic therapy (PDT) is an established treatment modality for various dermatooncologic conditions. For example, red light irradiation with the Aktilite CL 128 and Metvixia (Galderma SA) as a photosensitizing molecule is a conventional protocol approved and widely used in Europe for PDT treatment of actinic keratosis, but this treatment is not yet widely used for EMPV because it has never clearly been demonstrated and is very painful. ObjectiveThe aim of the study is to investigate the efficacy and safety relating to the medical device PAGETEX as a new painless PDT device using Metvixia in the treatment of vulvar Paget disease. The primary end point is the disease control rate at 3 months in 30% of the patients included, defined as stability, partial response, or total response, considering the extent of the lesion. Secondary end points are the disease control rate at 6 months, patient quality of life, level of pain experienced by the patient at each PDT session, severity of erythema, presence of protoporphyrin IX in Paget cells after each PDT session, and overall satisfaction level of the patient. MethodsThe trial is an interventional, exploratory, simple group, nonrandomized, and single center (Lille University Hospital) study. Twenty-four patients will be included according to Simon’s optimal plan. Therapeutic procedure is based on a cycle of two PDT sessions with the PAGETEX medical device at 15-day intervals (Metvixia incubation during 30 minutes and 635 nm red light illumination with a low irradiance for 2 hours and 30 minutes for a total fluence of 12 J/cm²). At the assessment session, 3 months after inclusion, if the control of the disease is partial or null, the patient will complete another cycle of two PDT sessions. A final evaluation will be performed in all patients at 6 months. Analyses will be performed using SAS version 9.4 software (SAS Institute Inc). The characteristics of the patients at baseline will be described; qualitative variables will be described by numbers and percentages, and quantitative variables will be described either by the mean and standard deviation for Gaussian distribution or by the median and interquartile range (ie, 25th and 75th percentiles). The normality of the distributions will be tested by a Shapiro-Wilk test and checked graphically by histograms. ResultsFirst patient was included in September 2019 and clinical investigations are planned until August 2022. The final results of this study are expected to be available in January 2023. ConclusionsThis clinical trial aims to evaluate the efficacy and safety of a new PDT protocol for the treatment of EMPV. The PAGETEX device could become the treatment of choice if it is effective, painless, and easy to implement and use in hospitals. Trial RegistrationClinicalTrials.gov NCT03713203; https://clinicaltrials.gov/ct2/show/NCT03713203 International Registered Report Identifier (IRRID)PRR1-10.2196/15026

Nursery areas of European sea bass (Dicentrarchus labrax, L.) were investigated from spring 2005 to summer 2006 in areas along the French Mediterranean coast of the Gulf of Lion. Nurseries were identified by the presence of settling individuals of sea bass and young juveniles. These nurseries represent different types of sheltered shallow habitats, both natural such as coastal lagoons, estuaries, and artificial such as marinas. Settlement occurred from April to June during both years. The number of settling individuals varied between sites from just a few individuals to several thousand. In one given site, settlement also varied between 2005 and 2006. The size distribution of sampled individuals revealed that several pulses arrived in each nursery. At this stage, sea bass already exhibited a strong orientation capacity but a limited swimming ability. The magnitude of sea bass settlement in marinas requires better environmental management of such artificial areas. [ABSTRACT FROM PUBLISHER]

The paper presents IR spectroscopic data and theoretical frequency calculations, in the C–H and N–H stretch region, on jet-cooled formamide molecules and dimers. By using dipole-bound or quadrupole-bound anion formation, one is able to monitor IR absorption in the neutral beam on mass-selected species. For isolated formamide, resonant IR excitation leads to autodetachment of the excess electron in the dipole-bound anion. For the formamide dimer, the IR spectrum is characteristic from the cyclic dimer, with two neighbouring bonded N–H stretches and a complex spectrum with several lines and a broad absorption band in the C–H region absorption, as for the cyclic formic acid dimer. In this double H-bond configuration, IR absorption cannot lead to vibrational predissociation but it probably produces hot neutral dimers with large-amplitude intermolecular motions that reinforce autodetachment of the nascent weakly bound anions. Thus, the present original IR spectroscopic technique, which allows for rigorous mass-selection of the neutrals, seems to be relevant for any polar neutral species. [ABSTRACT FROM AUTHOR]

Sympatric populations of rainbow smeltOsmerus mordaxof the St Lawrence middle estuary exhibited distinct morphologies suitable for exploiting either pelagic or benthic habitats in the absence of consistent morphological features related to specific diets. The magnitude of morphological differentiation was elevated and constant over 3 years even though statistically significant differences were observed among samples within populations. Both populations were spatially segregated in the estuary but some population mixing occurred at low densities of rainbow smelt. Diet analysis revealed that both populations opportunistically feed on large macrozooplankton. An amended version of Schoener'sDwas developed and used to compare the magnitude of niche overlap. It revealed that the diet of the middle estuary rainbow smelt differed according to the area where samples were collected but no differences existed between populations. The exploitation of ecologically distinct habitats appeared to be effective in maintaining morphologically distinct sympatric populations within an estuarine setting in the absence of diet differentiation. [ABSTRACT FROM AUTHOR]

In the upwelling zone of the northeastern Pacific, cold nutrient-rich conditions alternate with warm nutrient-poor intervals on timescales ranging from months to millennia. In this setting, the abundances of Pacific sardine ( Sardinops sagax) and northern anchovy ( Engraulis mordax) fluctuate by several orders of magnitude, with sardine dominating during warm conditions and anchovy dominating during cool conditions. Two population models can explain the response of these fishes to adverse conditions. Under the basin model, species distributions contract to a central (optimal) range during population crashes. Expectations of this model may include a single range-wide population with a decline in genetic diversity on both sides of a central refuge. In contrast, the self-recruitment model invokes a series of local oceanographic domains that maintain semi-isolated subpopulations. During adverse conditions, some subpopulations cannot complete the life cycle within the local environment and are extirpated. Expectations of this model include some degree of population genetic structure and no clear gradient in genetic diversity. We examined mitochondrial DNA cytochrome  b sequences to assess these competing models for anchovy ( N = 196; 539 bp) and sardine ( N = 107; 425 bp). The mitochondrial DNA gene genealogies are shallow but diverse for both species. Haplotype frequencies are homogeneous among subpopulations, but genetic diversities peak for both species along Baja California and adjacent southern California. Mismatch distributions and Tajima's D-values reveal distinctive signatures of population bottlenecks and expansions. Sardine haplotypes coalesce at ~241 000 years bp, with an initial female effective population size Nf0 = 0 followed by exponential growth to Nf1 = 115 million. Anchovy haplotypes coalesce at ~282 000 years bp, with an initial population size of Nf0 = 14 000, followed by exponential growth to Nf1 = 2.3 million. These results indicate a founder event for sardine and a severe population decline for anchovy in the California Current during the late Pleistocene. Overall, these data support the basin model on decadal timescales, although local recruitment may dominate on shorter timescales. [ABSTRACT FROM AUTHOR]

From a clinical presentation of a 10 years old child, with a follow up in a Therapeutic Day Center, the authors tried to clarify what has been “played out” around the drug prescription for this child during the family consultations. For a long time, the mother wondered if there were a link between the benzodiazepine treatment she took during her pregnancy and the conduct and personality disorders of her son. Having herself a turbulent and a difficult childhood, she built up a theory on the intergenerational transmission of temperaments. This clinical presentation is the occasion for thinking about the different significations a drug prescription could take for the child and his parents. If we keep an eye on the implications of every drug prescription, medication would often be a benefit to the child (and his family), enriching our reflexion without contradicting the psychodynamic work as defined in our Therapeutic Day Center. [Copyright &y& Elsevier]

Commercial catches of two ecologically distinct sympatric smelt (Osmerus mordax) populations segregated along the two shores of the St. Lawrence middle estuary exhibited inverse patterns with periodicities on the order of 30 years. The influence of water level in the St. Lawrence River and air temperature, chosen to reflect variations in hydrology and climate, differed markedly between the two populations. Analyses revealed that both water level and temperature were generally positively related with north-shore smelt landings and negatively related with south-shore smelt landings. For both populations, a number of significant climatic factors contributing to variance in smelt landings were lagged by one to three years relative to the year of landings, indicating that climatic variables influenced smelt recruitment. The contrasting role of hydroclimatic variables in driving these abundance cycles is likely related to differential exploitation of estuarine habitats; the south-shore population is associated with shallow shoal habitat, whereas the north-shore population is associated with deep channel habitat. The responses of the two smelt populations also reflect the fundamental ecological differences existing between shoal and channel habitats, indicating that future climate change may differentially affect other populations or species that are segregated between these two habitats.Les débarquements commerciaux de deux populations d'éperlans (Osmerus mordax) arc-en-ciel sympatriques, distinctes du point de vue écologique et ségréguées le long des deux rives de l'estuaire moyen du Saint-Laurent, montrent des variations cycliques inverses et une périodicité de l'ordre de 30 ans. L'influence du niveau d'eau du fleuve et de la température de l'air, choisis dans l'étude pour refléter les variations du régime hydrologique et du climat, diffèrent de façon marquée pour les deux populations. Les analyses révèlent que le niveau de l'eau et la température sont généralement corrélés positivement aux débarquements de la rive nord et négativement à ceux de la rive sud. Quelques un des principaux facteurs climatiques contribuant pour une grande part aux variations des débarquements des deux rives étaient décalés dans le temps, indiquant que les facteurs climatiques influencent le recrutement des éperlans. L'effet contrasté des variables hydroclimatiques sur les cycles d'abondance est vraisemblablement liée à l'utilisation différentielle des habitats de l'estuaire; la population de la rive sud est associée à un habitat peu profond et celle de la rive nord est à un chenal profond. Les réponses de ces deux populations d'éperlans reflètent aussi des différences écologiques existant entre des habitats peu profonds et un chenal profond, indiquant que les changements climatiques futurs pourraient avoir des effets différents sur d'autres populations ou d'autres espèces, qui sont ségréguées entre ces deux types d'habitats. [ABSTRACT FROM AUTHOR]