Pseudopolymorphism in Brucine: Brucine-Water (1/2), The Third Crystal Hydrate of Brucine

The structure of the third pseudopolymorphic hydrate of brucine, brucine-water (1/2) [systematic name 2,3-dimethoxystrychnidin-10-one-water (1/2)], C23H26N2O4 . 2H2O, has been determined at 130 K. The asymmetric unit comprises two independent brucine molecules and four water molecules of solvation. The four water molecules form uncommon cyclic hydrogen-bonded homomolecular R2/2(8) tetramer rings, which then form primary hydrogen-bonded chain substructures, extending down the 21 screw axis in the unit cell. The two brucine molecules are linked peripherally to these substructures by either single O-H...O(brucine) or O-H...N(brucine) hydrogen bonds

Sulphur-bearing molecules in diffuse molecular clouds: new results from SOFIA/GREAT and the IRAM 30 m telescope

We have observed five sulphur-bearing molecules in foreground diffuse molecular clouds lying along the sight-lines to five bright continuum sources. We have used the GREAT instrument on SOFIA to observe the 1383 GHz $^2\Pi_{3/2} J=5/2-3/2$ transitions of SH towards the star-forming regions W31C, G29.96-0.02, G34.3+0.1, W49N and W51, detecting foreground absorption towards all five sources; and the EMIR receivers on the IRAM 30m telescope at Pico Veleta to detect the H$_2$S 1(10)-1(01), CS J=2-1 and SO 3(2)-2(1) transitions. In nine foreground absorption components detected towards these sources, the inferred column densities of the four detected molecules showed relatively constant ratios, with N(SH)/N(H$_2$S) in the range 1.1 - 3.0, N(CS)/N(H$_2$S) in the range 0.32 - 0.61, and N(SO)/N(H$_2$S) in the range 0.08 - 0.30. The observed SH/H$_2$ ratios - in the range (0.5-2.6) $\times 10^{-8}$ - indicate that SH (and other sulphur-bearing molecules) account for << 1% of the gas-phase sulphur nuclei. The observed abundances of sulphur-bearing molecules, however, greatly exceed those predicted by standard models of cold diffuse molecular clouds, providing further evidence for the enhancement of endothermic reaction rates by elevated temperatures or ion-neutral drift. We have considered the observed abundance ratios in the context of shock and turbulent dissipation region (TDR) models. Using the TDR model, we find that the turbulent energy available at large scale in the diffuse ISM is sufficient to explain the observed column densities of SH and CS. Standard shock and TDR models, however, fail to reproduce the column densities of H$_2$S and SO by a factor of about 10; more elaborate shock models - in which account is taken of the velocity drift, relative to H$_2$, of SH molecules produced by the dissociative recombination of H$_3$S$^+$ - reduce this discrepancy to a factor ~ 3.Comment: 30 pages, accepted for publication in A&

Crystal structures of N ′-Aminopyridine-2-carboximidamide and N ′-{[1-(pyridin-2-yl)ethylidene]amino}pyridine-2-carboximidamide

© Eya'ane Meva et al. 2017. The crystal structures of N,-Aminopyridine-2-carboximidamide (C 6 H 8 N 4 ), 1, and N,-{[1-(pyridin-2-yl)ethylidene]amino}pyridine-2-carboximidamide (C 13 H 13 N 5 ), 2, are described. The non-H atoms in compound 1 are nearly planar (r.m.s. deviation from planarity = 0.0108 Å ), while 2 is twisted about the central N-N bond by 17.8 (2)-. Both molecules are linked by intermolecular N-H·N hydrogen-bonding interactions; 1 forms a two-dimensional hydrogen-bonding network and for 2 the network is a one-dimensional chain. The bond lengths of these molecules are similar to those in other literature reports of azine and diimine systems

Molecular Line Observations of Carbon-Chain-Producing Regions L1495B and L1521B

We present the first comprehensive study on physical and chemical properties of quiescent starless cores L1495B and L1521B, which are known to be rich in carbon-chain molecules like the cyanopolyyne peak of TMC-1 and L1521E. We have detected radio spectral lines of various carbon-chain molecules such as CCS, C$_{3}$S, C$_{4}$H, HC$_{3}$N, and HC$_{5}$N. On the other hand, the NH$_{3}$ lines are weak and the N$_{2}$H$^{+}$ lines are not detected. According to our mapping observations of the HC$_{3}$N, CCS, and C$_{3}$S lines, the dense cores in L1495B and L1521B are compact with the radius of 0.063 and 0.044 pc, respectively, and have a simple elliptical structure. The distributions of CCS seem to be different from those of well-studied starless cores, L1498 and L1544, where the distribution of CCS shows a shell-like structure. Since the H$^{13}$CO$^{+}$, HN$^{13}$C, and C$^{34}$S lines are detected in L1495B and L1521B, the densities of these cores are high enough to excite the NH$_{3}$ and N$_{2}$H$^{+}$ lines. Therefore, the abundances of NH$_{3}$ and N$_{2}$H$^{+}$ relative to carbon-chain molecules are apparently deficient, as observed in L1521E. We found that longer carbon-chain molecules such as HC$_{5}$N and C$_{4}$H are more abundant in TMC-1 than L1495B and L1521B, while those of sulfur-bearing molecules such as C$^{34}$S, CCS, and C$_{3}$S are comparable. Both distributions and abundances of the observed molecules of L1495B and L1521B are quite similar to those of L1521E, strongly suggesting that L1495B and L1521B is in a very early stage of physical and chemical evolution.Comment: 19 pages, 6 figures, accepted to The Astrophysical Journa

Evidence for a regulatory idiotypic network in the in vivo response to H-2 antigens.

Treatment of BALB/c mice with purified pig antiidiotype to 11-4.1 (anti-H-2Kk) monoclonal antibody has been found previously to induce the appearance of idiotype-bearing molecules (Id') in the serum of these mice, in the absence of detectable antigen-binding activity. In the present study we examined the effect of subsequent immunization of such antiidiotype-primed mice with the original H-2Kk antigen. Skin grafting of virgin BALB/c mice with BALB.K skin did not generate any detectable Id' antibodies when tested by enzyme-linked immunosorbent assay (ELISA). In contrast, grafting of antiidiotype-primed mice with BALB.K skin specifically boosted ther serum level of Id' molecules. Challenge of antiidiotype-primed mice with either B10.D2 or rat skin had no effect on the production of such Id' molecules. Absorption studies demonstrated that the majority of Id' molecules induced by H-2Kk antigenic stimulus and detected in ELISA are antigen-nonbinding molecules, thus indicating specific restimulation by the original H-2Kk antigen of nonbinding idiotype-positive B cell clones. The relevance of these findings to the existence of network interactions in the immune response to H-2 antigens is discussed

ALMA Observations of Ethyl Formate toward Orion KL

Orion KL is one of the prime templates of astrochemical and prebiotic chemical studies. We wish to explore more organic molecules with increasing complexity in this region. In particular, we have searched for one of the most complex organic molecules detected in space so far, ethyl formate (C$_{2}$H$_{5}$OCHO). This species is the next step in chemical complexity after the simplest member of esters (methyl formate, CH$_{3}$OCHO). The mechanisms leading to its formation are still poorly known. We have used high angular resolution ($\sim$ 1.$^{\prime\prime}$5) ALMA observations covering a large bandwidth from 214 to 247 GHz. We have detected 82 unblended lines of C$_{2}$H$_{5}$OCHO (49 and 33 of the trans and gauche conformers, respectively). The line images showed that C$_{2}$H$_{5}$OCHO arises mainly from the compact ridge and the hot core-southwest regions. The derived rotational temperatures and column densities are 122 $\pm$ 34 K, (0.9 $\pm$ 0.3) $\times$ 10$^{16}$ cm$^{-2}$ for the hot core-SW, and 103 $\pm$ 13 K, (0.6 $\pm$ 0.3) $\times$ 10$^{16}$ cm$^{-2}$ for the compact ridge. The comparison of spatial distribution and abundance ratios with chemically related molecules (methyl formate, ethanol and formic acid) indicates that C$_{2}$H$_{5}$OCHO is likely formed on the surface of dust grains by addition of CH$_{3}$ to functional-group radicals (CH$_{2}$OCHO) derived from methyl formate (CH$_{3}$OCHO)

Polymer adhesion: first-principles calculations of the adsorption of organic molecules onto Si surfaces

The structures and energetics of organic molecules adsorbed onto clean and H-passivated Si(001)-(2$\times$1) surfaces have been calculated using density functional theory. For benzene adsorbed on the clean Si surface the tight-bridge structure was found to be stable and the butterfly structure metastable. Both carbonic acid H$_2$CO$_3$ and propane C$_3$H$_8$ dissociate on contact with the surface. Passivation of the Si surface with H-atoms has a dramatic effect on the surface properties. The passivated surface is very inert and the binding energy of all the molecules is very weak.Comment: 8 pages, 13 figure