Since the first discovery of carbocupration of alkynes in the 1970s a tremendous amount of research has been carried out in this field. The exceptionally high selectivities obtained attribute to the ...great synthetic value of carbocupration reactions. This tutorial review will present the most important features of carbocupration of alkynes and highlight the most relevant reviews. Then a comprehensive review of copper mediated carbometalation of cyclopropenes will follow. The latter method has received much attention over the last decade as it allows the highly selective construction of poly-substituted cyclopropanes which can be transformed into acyclic derivatives bearing one or multiple tertiary or quaternary carbon stereocenters.
Service life and durability of reinforced concrete structures have become crucial issues in all industrialized countries because of their economic and ecological relevance. Limited durability is ...frequently due to deterioration of steel and cement-based materials, such as mortar and concrete, by interactions with water and aggressive aqueous solutions. Neutron imaging has proved to be a powerful non-destructive technique to study quantitatively water content and water movement in porous materials. A neutron beam is much more attenuated by hydrogen in water than by most other elements present in cement-based materials.
In this review, focus is placed on applications of both two-dimensional neutron radiography and three-dimensional neutron tomography to investigate specific aspects of durability and deterioration of cement-based materials. Examples of results obtained by qualitative and quantitative investigations of moisture movement in cracked and uncracked cement-based materials are presented. Self-healing, efficiency of water repellent treatment, internal curing, frost damage, fire spalling, ettringite formation and observations of various reinforced concrete components are addressed. The results obtained by neutron imaging provide a solid basis for better understanding of deterioration mechanisms of cement-based materials. Recent improvements of neutron imaging facilities have allowed unexpected possibilities to study complex processes in cement-based materials. The potential for further research based on this promising technology is outlined and discussed.
Context.
Complex organic molecules are detected in many sources in the warm inner regions of envelopes surrounding deeply embedded protostars. Exactly how these species form remains an open question.
...Aims.
This study aims to constrain the formation of complex organic molecules through comparisons of their abundances towards the Class 0 protostellar binary IRAS 16293–2422.
Methods.
We utilised observations from the ALMA Protostellar Interferometric Line Survey of IRAS 16293–2422. The species identification and the rotational temperature and column density estimation were derived by fitting the extracted spectra towards IRAS 16293–2422 A and IRAS 16293–2422 B with synthetic spectra. The majority of the work in this paper pertains to the analysis of IRAS 16293–2422 A for a comparison with the results from the other binary component, which have already been published.
Results.
We detect 15 different complex species, as well as 16 isotopologues towards the most luminous companion protostar IRAS 16293–2422 A. Tentative detections of an additional 11 isotopologues are reported. We also searched for and report on the first detections of methoxymethanol (CH
3
OCH
2
OH) and trans-ethyl methyl ether (t-C
2
H
5
OCH
3
) towards IRAS 16293–2422 B and the follow-up detection of deuterated isotopologues of acetaldehyde (CH
2
DCHO and CH
3
CDO). Twenty-four lines of doubly-deuterated methanol (CHD
2
OH) are also identified.
Conclusions.
The comparison between the two protostars of the binary system shows significant differences in abundance for some of the species, which are partially correlated to their spatial distribution. The spatial distribution is consistent with the sublimation temperature of the species; those with higher expected sublimation temperatures are located in the most compact region of the hot corino towards IRAS 16293–2422 A. This spatial differentiation is not resolved in IRAS 16293–2422 B and will require observations at a higher angular resolution. In parallel, the list of identified CHD
2
OH lines shows the need of accurate spectroscopic data including their line strength.
Context. The Class 0 protostellar binary IRAS 16293–2422 is an interesting target for (sub)millimeter observations due to, both, the rich chemistry toward the two main components of the binary and ...its complex morphology. Its proximity to Earth allows the study of its physical and chemical structure on solar system scales using high angular resolution observations. Such data reveal a complex morphology that cannot be accounted for in traditional, spherical 1D models of the envelope. Aims. The purpose of this paper is to study the environment of the two components of the binary through 3D radiative transfer modeling and to compare with data from the Atacama Large Millimeter/submillimeter Array. Such comparisons can be used to constrain the protoplanetary disk structures, the luminosities of the two components of the binary and the chemistry of simple species. Methods. We present 13CO, C17O and C18O J = 3–2 observations from the ALMA Protostellar Interferometric Line Survey (PILS), together with a qualitative study of the dust and gas density distribution of IRAS 16293–2422. A 3D dust and gas model including disks and a dust filament between the two protostars is constructed which qualitatively reproduces the dust continuum and gas line emission. Results. Radiative transfer modeling in our sampled parameter space suggests that, while the disk around source A could not be constrained, the disk around source B has to be vertically extended. This puffed-up structure can be obtained with both a protoplanetary disk model with an unexpectedly high scale-height and with the density solution from an infalling, rotating collapse. Combined constraints on our 3D model, from observed dust continuum and CO isotopologue emission between the sources, corroborate that source A should be at least six times more luminous than source B. We also demonstrate that the volume of high-temperature regions where complex organic molecules arise is sensitive to whether or not the total luminosity is in a single radiation source or distributed into two sources, affecting the interpretation of earlier chemical modeling efforts of the IRAS 16293–2422 hot corino which used a single-source approximation. Conclusions. Radiative transfer modeling of source A and B, with the density solution of an infalling, rotating collapse or a protoplanetary disk model, can match the constraints for the disk-like emission around source A and B from the observed dust continuum and CO isotopologue gas emission. If a protoplanetary disk model is used around source B, it has to have an unusually high scale-height in order to reach the dust continuum peak emission value, while fulfilling the other observational constraints. Our 3D model requires source A to be much more luminous than source B; LA ~ 18 L⊙ and LB ~ 3 L⊙.
A neuronal mechanism for motivational control of behavior Courtin, J; Bitterman, Y; Müller, S ...
Science (American Association for the Advancement of Science),
2022-Jan-07, 2022-01-07, 20220107, Letnik:
375, Številka:
6576
Journal Article
Recenzirano
Acting to achieve goals depends on the ability to motivate specific behaviors based on their predicted consequences given an individual’s internal state. However, the underlying neuronal mechanisms ...that encode and maintain such specific motivational control of behavior are poorly understood. Here, we used Ca
imaging and optogenetic manipulations in the basolateral amygdala of freely moving mice performing noncued, self-paced instrumental goal-directed actions to receive and consume rewards. We found that distinct neuronal activity patterns sequentially represent the entire action-consumption behavioral sequence. Whereas action-associated patterns integrated the identity, value, and expectancy of pursued goals, consumption-associated patterns reflected the identity and value of experienced outcomes. Thus, the interplay between these patterns allows the maintenance of specific motivational states necessary to adaptively direct behavior toward prospective rewards.
Context. As the number of complex organic molecules (COMs) detected in the interstellar medium increases, it becomes even more important to place meaningful constraints on the origins and formation ...pathways of such chemical species. The molecular cloud Sagittarius B2(N) is host to several hot molecular cores in the early stage of star formation, where a great variety of COMs are detected in the gas phase. Given its exposure to the extreme conditions of the Galactic center (GC) region, Sgr B2(N) is one of the best targets to study the impact of environmental conditions on the production of COMs. Aims. Our main goal is to characterize the physico-chemical evolution of Sgr B2(N)’s sources in order to explain their chemical differences and constrain their environmental conditions. Methods. The chemical composition of Sgr B2(N)’s hot cores, N2, N3, N4, and N5 is derived by modeling their 3 mm emission spectra extracted from the Exploring Molecular Complexity with ALMA (EMoCA) imaging spectral line survey performed with the Atacama Large Millimeter/submillimeter Array (ALMA). We derived the density distribution in the envelope of the sources based on the masses computed from the ALMA dust continuum emission maps. We used the radiative transfer code RADMC-3D to compute temperature profiles and inferred the current luminosity of the sources based on the COM rotational temperatures derived from population diagrams. We used published results of 3D radiation-magnetohydrodynamical (RMHD) simulations of high-mass star formation to estimate the time evolution of the source properties. We employed the astrochemical code MAGICKAL to compute time-dependent chemical abundances in the sources and to investigate how physical properties and environmental conditions influence the production of COMs. Results. The analysis of the abundances of 11 COMs detected toward Sgr B2(N2-N5) reveals that N3 and N5 share a similar chemical composition while N2 differs significantly from the other sources. We estimate the current luminosities of N2, N3, N4, and N5 to be 2.6 × 105 L⊙, 4.5 × 104 L⊙, 3.9 × 105 L⊙, and 2.8 × 105 L⊙, respectively. We find that astrochemical models with a cosmic-ray ionization rate of 7 × 10−16 s−1 best reproduce the abundances with respect to methanol of ten COMs observed toward Sgr B2(N2-N5). We also show that COMs still form efficiently on dust grains with minimum dust temperatures in the prestellar phase as high as 15 K, but that minimum temperatures higher than 25 K are excluded. Conclusions. The chemical evolution of Sgr B2(N2-N5) strongly depends on their physical history. A more realistic description of the hot cores’ physical evolution requires a more rigorous treatment with RMHD simulations tailored to each hot core.
Context. One of the important questions of astrochemistry is how complex organic molecules, including potential prebiotic species, are formed in the envelopes around embedded protostars. The ...abundances of minor isotopologues of a molecule, in particular the D- and 13C-bearing variants, are sensitive to the densities, temperatures and timescales characteristic of the environment in which they form, and can therefore provide important constraints on the formation routes and conditions of individual species. Aims. The aim of this paper is to systematically survey the deuteration and the 13C content of a variety of oxygen-bearing complex organic molecules on solar system scales toward the “B component” of the protostellar binary IRAS16293–2422. Methods. We have used the data from an unbiased molecular line survey of the protostellar binary IRAS16293−2422 between 329 and 363 GHz from the Atacama Large Millimeter/submillimeter Array (ALMA). The data probe scales of 60 AU (diameter) where most of the organic molecules are expected to have sublimated off dust grains and be present in the gas phase. The deuterated and 13C isotopic species of ketene, acetaldehyde and formic acid, as well as deuterated ethanol, are detected unambiguously for the first time in the interstellar medium. These species are analysed together with the 13C isotopic species of ethanol, dimethyl ether and methyl formate along with mono-deuterated methanol, dimethyl ether and methyl formate. Results. The complex organic molecules can be divided into two groups with one group, the simpler species, showing a D/H ratio of ≈2% and the other, the more complex species, D/H ratios of 4–8%. This division may reflect the formation time of each species in the ices before or during warm-up/infall of material through the protostellar envelope. No significant differences are seen in the deuteration of different functional groups for individual species, possibly a result of the short timescale for infall through the innermost warm regions where exchange reactions between different species may be taking place. The species show differences in excitation temperatures between 125 and 300 K. This likely reflects the binding energies of the individual species, in good agreement with what has previously been found for high-mass sources. For dimethyl ether, the 12C/13C ratio is found to be lower by up to a factor of 2 compared to typical ISM values similar to what has previously been inferred for glycolaldehyde. Tentative identifications suggest that the same may apply for 13C isotopologues of methyl formate and ethanol. If confirmed, this may be a clue to their formation at the late prestellar or early protostellar phases with an enhancement of the available 13C relative to 12C related to small differences in binding energies for CO isotopologues or the impact of FUV irradiation by the central protostar. Conclusions. The results point to the importance of ice surface chemistry for the formation of these complex organic molecules at different stages in the evolution of embedded protostars and demonstrate the use of accurate isotope measurements for understanding the history of individual species.
Data-Driven Finite Elasticity Conti, S.; Müller, S.; Ortiz, M.
Archive for rational mechanics and analysis,
07/2020, Letnik:
237, Številka:
1
Journal Article
Recenzirano
Odprti dostop
We extend to finite elasticity the Data-Driven formulation of geometrically linear elasticity presented in Conti et al. (Arch Ration Mech Anal 229:79–123, 2018). The main focus of this paper concerns ...the formulation of a suitable framework in which the Data-Driven problem of finite elasticity is well-posed in the sense of existence of solutions. We confine attention to deformation gradients
F
∈
L
p
(
Ω
;
R
n
×
n
)
and first Piola-Kirchhoff stresses
P
∈
L
q
(
Ω
;
R
n
×
n
)
, with
(
p
,
q
)
∈
(
1
,
∞
)
and
1
/
p
+
1
/
q
=
1
. We assume that the material behavior is described by means of a material data set containing all the states (
F
,
P
) that can be attained by the material, and develop germane notions of coercivity and closedness of the material data set. Within this framework, we put forth conditions ensuring the existence of solutions. We exhibit specific examples of two- and three-dimensional material data sets that fit the present setting and are compatible with material frame indifference.
•HITRAN2016 molecular spectroscopic database is described.•Dynamic web interface at www.hitran.org is introduced.•HITRAN Application Programming Interface is introduced.•Substantial extent of the ...amount and quality of the data highlighted.•Many new spectroscopic parameters are now available in HITRAN.
This paper describes the contents of the 2016 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2012 and its updates during the intervening years. The HITRAN molecular absorption compilation is composed of five major components: the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, collision-induced absorption data, aerosol indices of refraction, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, added line-shape formalisms, and validity. Moreover, molecules, isotopologues, and perturbing gases have been added that address the issues of atmospheres beyond the Earth. Of considerable note, experimental IR cross-sections for almost 300 additional molecules important in different areas of atmospheric science have been added to the database. The compilation can be accessed through www.hitran.org. Most of the HITRAN data have now been cast into an underlying relational database structure that offers many advantages over the long-standing sequential text-based structure. The new structure empowers the user in many ways. It enables the incorporation of an extended set of fundamental parameters per transition, sophisticated line-shape formalisms, easy user-defined output formats, and very convenient searching, filtering, and plotting of data. A powerful application programming interface making use of structured query language (SQL) features for higher-level applications of HITRAN is also provided.
Forest tree breeding has been successful at delivering genetically improved material for multiple traits based on recurrent cycles of selection, mating, and testing. However, long breeding cycles, ...late flowering, variable juvenile-mature correlations, emerging pests and diseases, climate, and market changes, all pose formidable challenges. Genetic dissection approaches such as quantitative trait mapping and association genetics have been fruitless to effectively drive operational marker-assisted selection (MAS) in forest trees, largely because of the complex multifactorial inheritance of most, if not all traits of interest. The convergence of high-throughput genomics and quantitative genetics has established two new paradigms that are changing contemporary tree breeding dogmas. Genomic selection (GS) uses large number of genome-wide markers to predict complex phenotypes. It has the potential to accelerate breeding cycles, increase selection intensity and improve the accuracy of breeding values. Realized genomic relationships matrices, on the other hand, provide innovations in genetic parameters' estimation and breeding approaches by tracking the variation arising from random Mendelian segregation in pedigrees. In light of a recent flow of promising experimental results, here we briefly review the main concepts, analytical tools and remaining challenges that currently underlie the application of genomics data to tree breeding. With easy and cost-effective genotyping, we are now at the brink of extensive adoption of GS in tree breeding. Areas for future GS research include optimizing strategies for updating prediction models, adding validated functional genomics data to improve prediction accuracy, and integrating genomic and multi-environment data for forecasting the performance of genetic material in untested sites or under changing climate scenarios. The buildup of phenotypic and genome-wide data across large-scale breeding populations and advances in computational prediction of discrete genomic features should also provide opportunities to enhance the application of genomics to tree breeding.
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