scholarly journals On the compositional variability of dalyite, K2ZrSi6O15: a new occurrence from Terceira, Azores

2016 ◽  
Vol 80 (4) ◽  
pp. 547-565 ◽  
Author(s):  
A. J. Jeffery ◽  
R. Gertisser ◽  
R. A. Jackson ◽  
B. O'Driscoll ◽  
A. Kronz
Keyword(s):  
Solid State ◽  
Late Stage ◽  
Octahedral Site ◽  
Pore Wall ◽  
Zirconium Silicate ◽  
Quantitative Analyses ◽  
Compositional Variability ◽  
First Time ◽  
Potassic Rocks ◽  
Bimodal Variation

AbstractThe rare potassium zirconium silicate dalyite has been identified for the first time on Terceira, Azores, within syenitic ejecta of the Caldeira-Castelinho Ignimbrite Formation. New quantitative analyses of this dalyite were combined with the small number of published analyses from various locations worldwide to evaluate the mineral's compositional variability. Additionally, solid-state modelling has been applied to assess the site allocations of substituting elements. The new analyses yield the average formula (K1.84Na0.15)∑=1.99(Zr0.94Ti0.012Hf0.011Fe0.004)∑=0.967Si6.03O15. Model results predict the placement of substituting Hf and Ti in the octahedral site, and highlight the overall complexity in the incorporation of Fe, Mg and Ba. The combined dataset reveals that dalyite found within peralkaline granites and syenites is generally defined by higher Na↔K substitution and lower Ti↔Zr substitution relative to dalyite from highly potassic rocks. The Terceira dalyite exhibits a bimodal variation in the degree of Na↔K substitution which is attributed to a K-enrichment trend induced by late-stage pore wall crystallization and albitization, coupled with the control of pore size upon the degree of supersaturation required to initiate nucleation of dalyite in pores of varying size.

The Total Synthesis of Rhabdastrellic Acid A

2018 ◽  
Author(s):  
Yaroslav Boyko ◽  
Christopher Huck ◽  
David Sarlah
Keyword(s):  
Total Synthesis ◽  
Late Stage ◽  
Cross Coupling ◽  
Side Chains ◽  
General Strategy ◽  
Modular Approach ◽  
Linear Sequence ◽  
Generating Sequence ◽  
First Time

<div>The first total synthesis of rhabdastrellic acid A, a highly cytotoxic isomalabaricane triterpenoid, has been accomplished in a linear sequence of 14 steps from commercial geranylacetone. The prominently strained <i>trans-syn-trans</i>-perhydrobenz[<i>e</i>]indene core characteristic of the isomalabaricanes is efficiently accessed in a selective manner for the first time through a rapid, complexity-generating sequence incorporating a reductive radical polyene cyclization, an unprecedented oxidative Rautenstrauch cycloisomerization, and umpolung 𝛼-substitution of a <i>p</i>-toluenesulfonylhydrazone with in situ reductive transposition. A late-stage cross-coupling in concert with a modular approach to polyunsaturated side chains renders this a general strategy for the synthesis of numerous family members of these synthetically challenging and hitherto inaccessible marine triterpenoids.</div>

Spider diversity in the Bukit Timah Nature Reserve, Singapore

2019 ◽  
Vol 71 ((suppl.1)) ◽  
pp. 209-243
Author(s):  
J.K.H. Koh ◽  
D.J. Court
Keyword(s):  
Nature Reserve ◽  
New Records ◽  
Secondary Forest ◽  
Distinct Species ◽  
Primary Forest ◽  
Preliminary Results ◽  
Vegetation Zones ◽  
Comprehensive Survey ◽  
Quantitative Analyses ◽  
First Time

This paper discusses the preliminary results of the first comprehensive survey of the spiders of the Bukit Timah Nature Reserve (BTNR) in Singapore. Two plots were established in each of the three zones of vegetation, viz., primary forest, old secondary forest, and maturing secondary forest. They were repeatedly sampled over an 18-month period. Sorting of the collection so far suggests that the three vegetation zones harbour rather different spider assemblages. Only ~9% of the total spider fauna recovered was shared by all three zones. The results have also yielded a preliminary picture of dominance, abundance and rarity. Although first intended to obtain a baseline for future quantitative analyses, the survey became a testing ground to modify and refine methodology so as to conduct future quantitative surveys with greater scientific rigour. Taxonomic work on the samples so far shows that the spiders in the BTNR span over 43 families, of which six families are listed for the first time in Singapore. The tally is summarised in an interim checklist of BTNR spiders. The checklist, with a total of 317 entries, shows that there are 158 described species of spiders in BTNR, of which 25 species are new records for Singapore. Another 159 morphospecies are provisionally recognised as distinct species, some of which may be new to science. Our observations during the survey have allowed us to provide a narrative of BTNR spider diversity against a backdrop of their microhabitat specialisation.

Bis(1-phenyl-1-propyne) complexes of tungsten(II): crystal structures of [WI2(CO)(NCR)(η2-MeC2Ph)2] (R = Me, Et, or Ph)

2001 ◽  
Vol 79 (3) ◽  
pp. 263-271
Author(s):  
Paul K Baker ◽  
Michael GB Drew ◽  
Deborah S Evans
Keyword(s):  
Carbon Monoxide ◽  
Solid State ◽  
Crystal Structures ◽  
Octahedral Geometry ◽  
X Ray ◽  
X Ray Crystallography ◽  
Alkyne Complexes ◽  
First Time

Reaction of [WI2(CO)3(NCMe)2] with two equivalents of 1-phenyl-1-propyne (MeC2Ph) in CH2Cl2, and in the absence of light, gave the bis(1-phenyl-1-propyne) complex [WI2(CO)(NCMe)(η2-MeC2Ph)2] (1) in 77% yield. Treatment of equimolar quantities of 1 and NCR (R = Et, i-Pr, t-Bu, Ph) in CH2Cl2 afforded the nitrile-exchanged products, [WI2(CO)(NCR)(η2-MeC2Ph)2] (2-5) (R = Et (2), i-Pr (3), t-Bu (4), Ph (5)). Complexes 1, 2, and 5 were structurally characterized by X-ray crystallography. All three structures have the same pseudo-octahedral geometry, with the equatorial sites being occupied by cis and parallel alkyne groups, which are trans to the cis-iodo groups. The trans carbon monoxide and acetonitrile ligands occupy the axial sites. In structures 1 and 2, the methyl and phenyl substituents of the 1-phenyl-1-propyne ligands are cis to each other, whereas for the bulkier NCPh complex (5), the methyl and phenyl groups are trans to one another. This is the first time that this arrangement has been observed in the solid state in bis(alkyne) complexes of this type.Key words: bis(1-phenyl-1-propyne), carbonyl, nitrile, diiodo, tungsten(II), crystal structures.

Gold(I) Complexes Bearing P∩N-Ligands: An Unprecedented Twelve-membered Ring Structure Stabilized by Aurophilic Interactions

2009 ◽  
Vol 64 (11-12) ◽  
pp. 1513-1524 ◽  
Author(s):  
Uwe Monkowius ◽  
Manfred Zabel ◽  
Michel Fleck ◽  
Hartmut Yersin
Keyword(s):  
Solid State ◽  
Ring Structure ◽  
Phosphine Ligands ◽  
X Ray Crystallography ◽  
Aggregation Pattern ◽  
Elemental Analyses ◽  
High Yields ◽  
First Time ◽  
Solid State Structures ◽  
Aurophilic Interactions

The P∩N-ligands Ph2Pqn, 1, Ph2 Piqn, 2, Ph2 Ppym, 3, and the As∩N-ligands Ph2Asqn, 4, Ph2Asiqn, 5, (Ph = phenyl, qn = 8-quinoline, iqn = 1-isoquinoline, pym = 2-pyrimidine) have been synthesized, the ligands 2 and 5 for the first time. Their ligand properties were probed by the synthesis of gold(I) complexes. Reaction with (tht)AuCl (tht = tetrahydrothiophene) yielded the chlorogold complexes Ph2RP-Au-Cl (R = qn, 6; iqn, 7; pym, 8) and Ph2RAs-Au-Cl (R = qn, 9; iqn, 10) in high yields. Further treatment of 7 and 8 with one equivalent of AgBF4 provided the complexes [(Ph2Piqn)Au]BF4, 11, [(Ph2Ppym)Au]BF4, 12, and [(Ph2Piqn)Au(tht)]BF4, 14. For comparison, the previously reported complex [(Ph2Ppy)Au]BF4 (py = pyridine), 13, was re-investigated. The compounds were characterized by elemental analyses, mass spectrometry and NMR spectroscopy. In addition, the solid-state structures of 2, 3, 6, 7, 9 - 14 have been determined by X-ray crystallography. The chloro-gold compounds crystallize in the common rod-like structure known from R3EAuCl (R = aryl, E = P, As) complexes without further aggregation via aurophilic interactions. In all cases the phosphine acts as a monodentate ligand. In the solid state compounds 11 - 13 feature an unprecedented cyclic trinuclear aggregation pattern, in which the Au(I) atoms are linearly coordinated by the bridging phosphine ligands forming a cyclic (P-Au-N)3 arrangement. The resulting twelvemembered ring is further stabilized by Au · · · Au interactions. Due to the presence of these Au · · · Au contacts, 11 - 13 are emissive in the solid state but not in solution

Metal–organic cage-based nanoagent for enhanced photodynamic antitumor therapy

2021 ◽  
Author(s):  
Yu-Bin Dong ◽  
Wen-Yan Li ◽  
Chaowei Zhao ◽  
Yue-Feng Zhang ◽  
Qun Guan ◽  
...  
Keyword(s):  
Solid State ◽  
Indocyanine Green ◽  
Anion Exchange ◽  
Near Infrared ◽  
Antitumor Therapy ◽  
Metal Organic ◽  
First Time

Herein we report, for the first time, a Pd6L8(NO3)5.4(ICG)6.6 (ICG = indocyanine green) cage-based hexagonal nanoplate (3) via a combined nanoprecipitation and solid-state anion-exchange approach. 3 possesses near infrared (NIR)...

scholarly journals Antimony and Nickel Impurities in Blue and Green Copper Pigments

Minerals ◽  
2021 ◽  
Vol 11 (11) ◽  
pp. 1236
Author(s):  
Sylwia Svorová Pawełkowicz ◽  
Barbara Wagner ◽  
Jakub Kotowski ◽  
Grażyna Zofia Żukowska ◽  
Bożena Gołębiowska ◽  
...  
Keyword(s):  
Inductively Coupled Plasma ◽  
Ore Deposits ◽  
Copper Ore ◽  
Inductively Coupled ◽  
Parish Church ◽  
Icp Ms ◽  
Plasma Mass Spectrometry ◽  
Quantitative Analyses ◽  
First Time

Impurities in paint layers executed with green and blue copper pigments, although relatively common, have been studied only little to date. Yet, their proper identification is a powerful tool for classification of paintings, and, potentially, for future provenance studies. In this paper, we present analyses of copper pigments layers from wall paintings situated in the vicinity of copper ore deposits (the palace in Kielce, the palace in Ciechanowice, and the parish church in Chotków) located within the contemporary borders of Poland. We compare the results with the analyses of copper minerals from three deposits, two local, and one historically important for the supply of copper in Europe, i.e., Miedzianka in the Holy Cross Mountains, Miedzianka in the Sudetes, and, as a reference, Špania Dolina in the Slovakian Low Tatra. Optical (OM) and electron microscopy (SEM-EDS), Raman spectroscopy, and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have been used for a detailed investigation of the minute grains. Special attention has been devoted to antimony and nickel phases, as more unusual than the commonly described iron oxides. Analyses of minerals from the deposits helped to interpret the results obtained from the paint samples. For the first time, quantitative analyses of copper pigments’ impurities have been described.

scholarly journals Late-Stage β-C(sp3)–H Deuteration of Carboxylic Acids

2021 ◽  
Author(s):  
Alexander Uttry ◽  
Sourjya Mal ◽  
Manuel van Gemmeren
Keyword(s):  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Late Stage ◽  
Bioactive Molecules ◽  
Wide Range ◽  
Catalyst Systems ◽  
First Time

Carboxylic acid moieties are highly abundant in bioactive molecules. In this study we describe the late-stage β-C(sp<sup>3</sup>)–H deuteration of free carboxylic acids. Based on our finding that the C–H activation with our catalyst systems is reversible, the de-deuteration process was first optimized. The resulting conditions involve ethylenediamine-based ligands, which, amongst other positions, for the first time enables the functionalization of non-activated methylene β-C(sp<sup>3</sup>)–H bonds and can be used to achieve the desired deuteration when using a deuterated solvent. The reported method allows for the functionalization of a wide range of free carboxylic acids with diverse substitution patterns, as well as the late-stage deuteration of bioactive molecules and related frameworks.

scholarly journals Revisiting the bis(dimethylamido) metallocene complexes of thorium and uranium: improved syntheses, structure, spectroscopy, and redox energetics of (C5Me5)2An(NMe2)2 (An = Th, U)

2017 ◽  
Vol 46 (34) ◽  
pp. 11208-11213 ◽  
Author(s):  
K. A. Erickson ◽  
B. D. Kagan ◽  
B. L. Scott ◽  
D. E. Morris ◽  
J. L. Kiplinger
Keyword(s):  
Solid State ◽  
Uv Visible ◽  
First Time ◽  
Solid State Structures ◽  
Metallocene Complexes

In addition to improved syntheses, the solid-state structures, voltammetric data and UV-visible–NIR spectra of (C5Me5)2An(NMe2)2 (An = Th, U) complexes are presented for the first time.

Niobium-bearing arsenides and germanides from elemental mixtures not involving niobium: a new twist to an old problem in solid-state synthesis

2018 ◽  
Vol 74 (5) ◽  
pp. 623-627 ◽  
Author(s):  
Sviatoslav Baranets ◽  
Hua He ◽  
Svilen Bobev
Keyword(s):  
High Temperature ◽  
Solid State ◽  
Diffraction Data ◽  
Alkaline Earth ◽  
Alkaline Earth Metals ◽  
X Ray Diffraction ◽  
X Ray ◽  
High Temperature Reactions ◽  
First Time ◽  
Synthetic Work

Three isostructural transition-metal arsenides and germanides, namely niobium nickel arsenide, Nb0.92(1)NiAs, niobium cobalt arsenide, NbCoAs, and niobium nickel germanide, NbNiGe, were obtained as inadvertent side products of high-temperature reactions in sealed niobium containers. In addition to reporting for the very first time the structures of the title compounds, refined from single-crystal X-ray diffraction data, this article also serves as a reminder that niobium containers may not be suitable for the synthesis of ternary arsenides and germanides by traditional high-temperature reactions. Synthetic work involving alkali or alkaline-earth metals, transition or early post-transition metals, and elements from groups 14 or 15 under such conditions may yield Nb-containing products, which at times could be the major products of such reactions.

Influence of mixing energy on the solid-state behavior and clay fraction threshold of PA12/C30B® nanocomposites

2019 ◽  
Vol 39 (6) ◽  
pp. 565-572
Author(s):  
Nourredine Aït Hocine ◽  
Pascal Médéric ◽  
Hanaya Hassan
Keyword(s):  
Solid State ◽  
Mechanical Energy ◽  
Three Dimensional ◽  
Clay Fraction ◽  
Critical Value ◽  
Processing Conditions ◽  
State Behavior ◽  
Mixing Energy ◽  
End Use ◽  
First Time

Abstract This study focuses on the influence of mixing energy on the solid-state behavior and clay fraction threshold of nanocomposites. Thus, three polyamide12/clay (PA12/C30B®) nanocomposites exhibiting different nanostructures were prepared from three sets of processing conditions. Then, thermal and dynamical viscoelastic properties of these nanocomposites were analyzed, in relationship with the material nanostructure and processing conditions. For the first time, the solid-state properties of the nanocomposites revealed the existence of a critical specific mixing mechanical energy. Below this critical value, an increase of mechanical energy refines the structure, improving some end-use properties of the nanocomposite. Above this value, a high mixing energy supply is necessary in order to significantly modify the structure. They also highlighted that the clay fraction threshold, which is commonly attributed to the formation of a three-dimensional percolated network, decreases with increasing specific mixing energy, less significantly when this energy is superior to its critical value.

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