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At least 145 records · Page 8

Triphenylborane in Metal-Free Catalysis

The development and application of new organoboron reagents as Lewis acids in synthesis and metal-free catalysis have dramatically expanded over the past 20 years. In this context, we will show the recent uses of the simple and relatively weak Lewis acid BPh 3 —discovered 100 years ago—as a metal-free catalyst for various organic transformations. The first part will highlight catalytic applications in polymer synthesis such as the copolymerization of epoxides with CO 2 , isocyanate, and organic anhydrides to various polycarbonate copolymers and controlled diblock copolymers as well as alternating polyurethanes. This is followed by a discussion of BPh 3 as a Lewis acid component in the frustrated Lewis pair (FLP) mediated cleavage of hydrogen and hydrogenation catalysis. In addition, BPh 3 -catalyzed reductive N-methylations and C-methylations with CO 2 and silane to value-added organic products will be covered as well along with BPh 3 -catalyzed cycloadditions and insertion reactions. Collectively, this mini-review showcases the underexplored potential of commercially available BPh3 in metal-free catalysis.

Lewis acid↗

Discovery of Extended Tidal Tails around the Globular Cluster Palomar 13

We use photometry from the DECam Legacy Survey to detect candidate tidal tails extending ~5° on either side of the Palomar 13 globular cluster. The tails are aligned with the proper motion of Palomar 13 and are consistent with its old, metal-poor stellar population. We identify three RR Lyrae stars (RRLs) that are plausibly associated with the tails, in addition to four previously known in the cluster. From these RRLs, we find that the mean distance to the cluster and tails is 23.6 ± 0.2 kpc and estimate the total (initial) luminosity of the cluster to be , consistent with previous claims that its initial luminosity was higher than its current luminosity. Combined with previously determined proper motion and radial velocity measurements of the cluster, we find that Palomar 13 is on a highly eccentric orbit (e ~ 0.8) with a pericenter of ~9 kpc and an apocenter of ~69 kpc, and a recent pericentric passage of the cluster ~75 Myr ago. We note a prominent linear structure in the interstellar dust map that runs parallel to the candidate tidal features, but conclude that reddening due to dust is unlikely to account for the structure that we observe. If confirmed, the Palomar 13 stellar stream would be one of very few streams with a known progenitor system, making it uniquely powerful for studying the disruption of globular clusters, the formation of the stellar halo, and the distribution of matter within our Galaxy.

79 ASTRONOMY AND ASTROPHYSICS↗

A Multiwavelength Investigation of PSR J2229+6114 and its Pulsar Wind Nebula in the Radio, X-Ray, and Gamma-Ray Bands

Abstract G106.3+2.7, commonly considered to be a composite supernova remnant (SNR), is characterized by a boomerang-shaped pulsar wind nebula (PWN) and two distinct (“head” and “tail”) regions in the radio band. A discovery of very-high-energy gamma-ray emission (E γ > 100 GeV) followed by the recent detection of ultrahigh-energy gamma-ray emission (E γ > 100 TeV) from the tail region suggests that G106.3+2.7 is a PeVatron candidate. We present a comprehensive multiwavelength study of the Boomerang PWN (100″ around PSR J2229+6114) using archival radio and Chandra data obtained two decades ago, a new NuSTAR X-ray observation from 2020, and upper limits on gamma-ray fluxes obtained by Fermi-LAT and VERITAS observatories. The NuSTAR observation allowed us to detect a 51.67 ms spin period from the pulsar PSR J2229+6114 and the PWN emission characterized by a power-law model with Γ = 1.52 ± 0.06 up to 20 keV. Contrary to the previous radio study by Kothes et al., we prefer a much lower PWNB-field (B∼ 3μG) and larger distance (d∼ 8 kpc) based on (1) the nonvarying X-ray flux over the last two decades, (2) the energy-dependent X-ray size of the PWN resulting from synchrotron burn-off, and (3) the multiwavelength spectral energy distribution (SED) data. Our SED model suggests that the PWN is currently re-expanding after being compressed by the SNR reverse shock ∼1000 yr ago. In this case, the head region should be formed by GeV–TeV electrons injected earlier by the pulsar propagating into the low-density environment.

Astronomy & Astrophysics↗

U-Pb ages for sphene in a contact metamorphic zone.

U-Pb ages have been determined on sphene concentrates from the 2700 my old Giants Range Granite at varying distances from the contact with the 1100 my old Duluth gabbro. As the contact is approached the sphene ages become more discordant and plot along a chord between 1100 and 2700 my on a concordia diagram. The U-Pb ages for sphene in the contact aureole are more resistant to thermal metamorphism than are K-Ar ages for hornblende and biotite. The resistance relative to U-Pb ages for zircon is more difficult to interpret because the zircon U-Pb ages may have become discordant prior to or after 1100 my ago, whereas the U-Pb ages for sphene appear to have had episodic discordance only at 1100 my ago.

Hanson, G. N.↗

Excess lead in 'rusty rock' 66095 and implications for an early lunar differentiation

Apollo 16 breccia 66095 contains a remarkably high amount of lead (15 parts per million), 85 percent of which is not supported by uranium and thorium in the rock. An acid leach experiment coupled with separate analyses of the whole rock and mineral fractions for uranium, thorium, and lead indicate that the excess lead has a lunar source and was apparently introduced about 4.0 b.y. ago. The data also suggest that a major lunar crustal differentiation occurred about 4.47 b.y. ago.

Nunes, P. D.↗

U-Th-Pb systematics of some Apollo 16 lunar samples

U, Th, and Pb concentrations and lead isotopic compositions of Apollo 16 samples are interpreted as follows: (1) an early period of lunar differentiation of either global or regional scale occurred about 4.47 b.y. ago; (2) the Imbrian impact event affected many Apollo 16 samples about 3.99 b.y. ago; (3) some Apollo 16 metaclastic rocks and breccias contain a large amount of KREEP-like material; (4) lead produced in the early history of the moon has been concentrated in lunar highland soils yielding high Pb-207/Pb-206 ratios corresponding to apparent ages of more than 4.8 b.y.; and (5) South Ray Crater soils reflect the approximately 2-b.y.-old event previously proposed for the Apollo 12 and 14 samples.

Nunes, P. D.↗

Processes of lunar crater degradation - Changes in style with geologic time

Relative age schemes of crater degradation are calibrated to radiometric dates obtained from lunar samples, changes in morphologic features are analyzed, and the style and rate of lunar surface degradation processes are modeled in relation to lunar geologic time. A comparison of radiometric age scales and the relative degradation of morphologic features for craters larger than about 5 km in diameter shows that crater degradation can be divided into two periods: Period I, prior to about 3.9 billion years ago and characterized by a high meteoritic influx rate and the formation of large multiringed basins, and Period II, from about 3.9 billion years ago to the present and characterized by a much lower influx rate and a lack of large multiringed basins. Diagnostic features for determining the relative ages of craters are described, and crater modification processes are considered, including primary impacts, lateral sedimentation, proximity weathering, landslides, and tectonism. It is suggested that the fundamental degradation of early Martian craters may be associated with erosional and depositional processes related to the intense bombardment characteristics of Period I.

Head, J. W.↗

Geochemistry and the origin of life

The origin of life on earth is examined from a viewpoint stressing the validity of the concept of chemical evolution. The different geological formations supporting the mechanisms of the theory are described; the stage of chemical evolution (preceding that of biological evolution) would have taken place from the time of the origin of the earth and meteorites, 4.6 billion years ago, to the early Precambrian period, about 3.2 billion years ago. Specific aspects of the problem discussed include amino acids from spark discharges and their comparison with the Murchison meteorite amino acids, the properties and theory of genesis of the carbonaceous complex within the cold Bokevelt meteorite, ammonion ion concentration in the primitive ocean, the oxygen isotope chemistry of ancient charts, the origin and rise of oxygen concentration in the earth's atmosphere, Precambrian microorganisms and evolutionary events prior to the origin of vascular plants, and biogenicity and significance of the oldest known stromatolites.

Kvenvolden, K. A.↗

Early impact basins and the onset of plate tectonics

The fundamental crustal dichotomy of the Earth (high and low density crust) was established nearly 4 billion years ago. Therefore, subductable crust was concentrated at the surface of the Earth very early in its history, making possible an early onset for plate tectonics. Simple thermal history calculations spanning 1 billion years show that the basin forming impact thins the lithosphere by at least 25%, and increases the sublithosphere thermal gradients by roughly 20%. The corresponding increase in convective heat transport, combined with the highly fractured nature of the thinned basin lithosphere, suggest that lithospheric breakup or rifting occurred shortly after the formation of the basins. Conditions appropriate for early rifting persisted from some 100,000,000 years following impact. We suggest a very early stage of high temperature, fast spreading "microplate" tectonics, originating before 3.5 billion years ago, and gradually stabilizing over the Archaean into more modern large plate or Wilson Cycle tectonics.

Frey, H.↗

The record of impact cratering on the great volcanic shields of the Tharsis region of Mars

The spatial density of impact craters larger than 100 m on the four great volcanic shields in the Tharsis region is analyzed, assuming that each observed crater population represents the total formed since the local surface was last renewed. Previous investigations of this type are reviewed, problems encountered in those studies are discussed, and an attempt is made to overcome these problems by applying explicit criteria for the separation of craters smaller than approximately 1 km in diameter according to their origin and by ignoring larger craters. Relative ages are determined by comparing crater populations at a common diameter, and such comparisons are carried out for six populations on Arsia Mons, one population on Pavonis Mons, several craters on Ascraeus Mons, and two populations on Olympus Mons. The results, presented in terms of 'crater ages', indicate that most dated surfaces on the great shields range in age from 0.5 to 1.2 billion years, that the eruption patterns of the volcanoes are similar to those of the Hawaiian basaltic shields, and that the most frequently renewed surfaces are on the middle-to-lower flanks as well as within the summit calderas. The youngest surfaces are estimated to date from the period between 0.5 billion years ago and the present; the oldest dated surfaces are shown to suggest that the volcanoes had attained essentially their present sizes over 1 billion years ago.

Blasius, K. R.↗

What's new on the moon. II

Apollo missions and returned lunar samples have provided new information about the moon, the earth, the sun, and the universe. Analyses show that all the planets were formed by the rapid accumulation of small bodies into larger ones about 4.6 billion years ago. The existence of simple molecules formed by reactions between the soil particles and atoms of carbon, oxygen, and nitrogen that have come from the sun, suggests that the basic ingredients for life are common in the universe. The ratio of hydrogen to helium in the solar wind reaching the moon is found to be 20 to 1, whereas the earth-based measurements show this ratio to be 10 to 1. Although the moon does not have any magnetic field at the present, the analyses revealed the existence of such a field three billion years ago. The understanding of the reasons for the disappearance of this field is vital for understanding planetary magnetic fields. The determination of the chemical composition of the whole moon, the explanation of the moon's observed asymmetry, and the understanding of the nature of moon's interior will have to be achieved by future, possibly unmanned, missions.

French, B. M.↗

Early stages in the evolution of the atmosphere and climate on the Earth-group planets

The early evolution of the atmospheres and climate of the Earth, Mars and Venus is discussed, based on a concept of common initial conditions and main processes (besides known differences in chemical composition and outgassing rate). It is concluded that: (1) liquid water appeared on the surface of the earth in the first few hundred million years; the average surface temperature was near the melting point for about the first two eons; CO2 was the main component of the atmosphere in the first 100-500 million years; (2) much more temperate outgassing and low solar heating led to the much later appearance of liquid water on the Martian surface, only one to two billion years ago; the Martian era of rivers, relatively dense atmosphere and warm climate ended as a result of irreversible chemical bonding of CO2 by Urey equilibrium processes; (3) a great lack of water in the primordial material of Venus is proposed; liquid water never was present on the surface of the planet, and there was practically no chemical bonding of CO2; the surface temperature was over 600 K four billion years ago.

Moroz, V. I.↗

Calculations of the moon's thermal history at different concentrations of radioactive elements, taking into account differentiation on melting

Calculations of the thermal history of the moon were done by solving the thermal conductivity equation for the case in which the heat sources are the long lived radioactive elements Th, U, and K-40. The concentrations of these elements were adjusted to give 4 variations of heat flow. Calculations indicated that the moon's interior was heated to melting during the first 0.7 to 2.3 x 10 to the 9th power years. The maximum fusion involved practically the entire moon to a distance from 15 to 45 km beneath the surface, and started 3.5 to 4.0 x 10 to the 9th power years ago, or 2.5 x 3.0 x 10 to the 9th power years ago and continued for 1 to 2 x 10 to the 9th power years. The moon today is cooling. The current thickness of the solid crust is from 150 to 200 km and the heat flow exceeds the stationary value 1.5 fold.

Ornatskaya, O. I.↗

On the age of KREEP

It is noted that the variable Rb-Sr model ages of lunar highland rocks containing a significant amount of KREEP basalt may be best explained by some fractionation of Rb from Sr during metamorphism 3.9 billion years ago, but the uniformity of the KREEP-type trace-element pattern in different highland samples indicates that elements such as the rare earth were hardly fractionated at all during the metamorphic event. Data are presented which show that the Rb/Sr fractionation 3.9 billion years ago was due to Rb mobilization alone in most cases and that this fractionation can be accounted for by coupling of Rb to other, less volatile incompatible elements. Variations of Rb in lunar highland rocks are analyzed, a correction method is applied for the Rb/Sr fractionation, and results are evaluated separately for Apollo 16 VHA and KREEP basalts, Apollo 17 noritic breccias, Apollo 14 KREEP breccias, Apollo 15 KREEP basalts, and Apollo 15-KREEP-enriched breccias. Evidence for volatilization of alkalis from glasses of impact origin is summarized, and an apparent correlation is discussed between meteoritic component (as given by the Ir/Au ratio) and rock type (as given by the U or Rb content) for many lunar highland samples.

Palme, H.↗

Noble gas evidence for the depositional and irradiational history of 60010-60009 core soils

Isotopic abundances of the noble gases have been determined in grain size separates of eleven soils from different depths in the 60010-60009 double drive tube and in magnetic and plagioclase separates from a few of these soils. Data for the 60010 core are presented here. The entire core was deposited a maximum of approximately 125 m.y. ago as deduced from the Ar-38 cosmic ray exposure age of soil 60009,457. Soils in the topmost 12 cm of the core show loss of cosmogenic He-3 and Ne-21 and gain of trapped solar gases in proportion to the degree of surface reworking by micrometeorites as deduced from FMR data. A variety of compositional and irradiational evidence suggests that soils in the core were formed by mixing of three or more components during or immediately prior to core deposition less than about 125 m.y. ago. Based on cosmogenic noble gases and a variety of other data soils 60009,457 and 60010,3107 are similar (and possibly identical) to two of the end member soils which formed the mixture. More mature soils in the core, however, could not have matured in situ from these two soils because of significant differences in noble gas abundances and chemical composition.

Bogard, D. D.↗

Tabular comparisons of the Flynn Creek impact crater, United States, Steinheim impact crater, Germany and Snowball explosion crater, Canada

A tabular outline of comparative data is presented for 340 basic dimensional, morphological, and structural parameters and related aspects for three craters of the flat-floored, central uplift type, two of which are natural terrestrial impact craters and one is a large-scale experimental explosion crater. The three craters are part of a general class, in terms of their morphology and structural deformation that is represented on each of the terrestrial planets including the moon. One of the considered craters, the Flynn Creek Crater, was formed by a hypervelocity impact event approximately 360 m.y. ago in what is now north central Tennessee. The impacting body appears to have been a carbonaceous chondrite or a cometary mass. The second crater, the Steinheim Crater, was formed by an impact event approximately 14.7 m.y. ago in what is now southwestern Germany. The Snowball Crater was formed by the detonation of a 500-ton TNT hemisphere on flat-lying, unconsolidated alluvium in Alberta, Canada.

Roddy, D. J.↗

Rb-Sr ages and initial Sr-87/Sr-86 for Apollo 17 basalts and KREEP basalt 15386

The Rb-Sr data reported for Apollo 17 mare basalts and for KREEP basalt 15386 is used to determine mineral isochrons. The weighted average age of four Apollo 17 basalts is 3.76 + or - 0.06 AE, while the age determined for 15386 is 3.94 + or - 0.04 AE. The isotopic data for the Apollo 17 basalts are discussed in the context of Sm and Eu data for the same samples. The Sr-isotopic data are fit best by a three-stage model evolution involving evolution of Sr-87/Sr-86 in an environment with Rb/Sr greater than in the basalts, production of mare basalt source regions of lower but variable Rb/Sr sometime in the interval 4.6 to 3.75 AE ago, and extraction of lavas from these sources 3.75 AE ago. Other possibilities are considered.

Nyquist, L. E.↗

Regolith depositional history at Shorty Crater

Nuclear particle track measurements in the 68 cm double drive tube 74002-74001 indicate that the whole core was deposited in one event some 10 m.y. ago. Significant reworking of the soil only occurred down to a few cm from the lunar surface since this event. Complementary investigations in this core by other groups are discussed. Most of the evidence available leads to a two stage model in which the orange and black soils collected at Shorty Crater were first irradiated for approximately 25 m.y. at some depth and then were deposited only a few m.y. ago as an overturned ejecta blanket.

Crozaz, G.↗