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Towards an understanding of the propensity for crystalline hydrate formation by molecular compounds.

ABSTRACT: Hydrates are technologically important and ubiquitous yet they remain a poorly understood and understudied class of molecular crystals. In this work, we attempt to rationalize propensity towards hydrate formation through crystallization studies of molecules that lack strong hydrogen-bond donor groups. A Cambridge Structural Database (CSD) survey indicates that the statistical occurrence of hydrates in 124 molecules that contain five- and six-membered N-heterocyclic aromatic moieties is 18.5%. However, hydrate screening experiments on a library of 11 N-heterocyclic aromatic compounds with at least two acceptor moieties and no competing hydrogen-bond donors or acceptors reveals that over 70% of this group form hydrates, suggesting that extrapolation from CSD statistics might, at least in some cases, be deceiving. Slurrying in water and exposure to humidity were found to be the most effective discovery methods. Electrostatic potential maps and/or analysis of the crystal packing in anhydrate structures was used to rationalize why certain molecules did not readily form hydrates.

SUBMITTER: Bajpai A

PROVIDER: S-EPMC5094445 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Towards an understanding of the propensity for crystalline hydrate formation by molecular compounds.

Bajpai Alankriti A Scott Hayley S HS Pham Tony T Chen Kai-Jie KJ Space Brian B Lusi Matteo M Perry Miranda L ML Zaworotko Michael J MJ

IUCrJ 20161018 Pt 6

Hydrates are technologically important and ubiquitous yet they remain a poorly understood and understudied class of molecular crystals. In this work, we attempt to rationalize propensity towards hydrate formation through crystallization studies of molecules that lack strong hydrogen-bond donor groups. A Cambridge Structural Database (CSD) survey indicates that the statistical occurrence of hydrates in 124 molecules that contain five- and six-membered <i>N</i>-heterocyclic aromatic moieties is 18 ...[more]

PMID: 27840682

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Project description:The propensity of molecular organic compounds to form stoichiometric or nonstoichiometric crystalline hydrates remains a challenging aspect of crystal engineering and is of practical relevance to fields such as pharmaceutical science. In this work, we address the propensity for hydrate formation of a library of eight compounds comprised of 5- and 6-membered N-heterocyclic aromatics classified into three subgroups: linear dipyridyls, substituted Schiff bases, and tripodal molecules. Each molecular compound studied possesses strong hydrogen bond acceptors and is devoid of strong hydrogen bond donors. Four methods were used to screen for hydrate propensity using the anhydrate forms of the molecular compounds in our library: water slurry under ambient conditions, exposure to humidity, aqueous solvent drop grinding (SDG), and dynamic water vapor sorption (DVS). In addition, crystallization from mixed solvents was studied. Water slurry, aqueous SDG, and exposure to humidity were found to be the most effective methods for hydrate screening. Our study also involved a structural analysis using the Cambridge Structural Database, electrostatic potential (ESP) maps, full interaction maps (FIMs), and crystal packing motifs. The hydrate propensity of each compound studied was compared to a compound of the same type known to form a hydrate through a previous study of ours. Out of the eight newly studied compounds (herein numbered 4-11), three Schiff bases were observed to form hydrates. Three crystal structures (two hydrates and one anhydrate) were determined. Compound 6 crystallized as an isolated site hydrate in the monoclinic space group P21/a, while 7 and 10 crystallized in the monoclinic space group P21/c as a channel tetrahydrate and an anhydrate, respectively. Whereas we did not find any direct correlation between the number of H-bond acceptors and either hydrate propensity or the stoichiometry of the resulting hydrates, analysis of FIMs suggested that hydrates tend to form when the corresponding anhydrate structure does not facilitate intermolecular interactions.

Project description:The tergal gland is a structure exclusive of adult male cockroaches that produces substances attractive to the female and facilitates mating. It is formed de novo in tergites 7 and 8 during the transition from the last nymphal instar to the adult. Thus, the tergal gland can afford a suitable case study to investigate the molecular basis of a morphogenetic process occurring during metamorphosis. Using Blattella germanica as model, we constructed transcriptomes from male tergites 7-8 in non-metamorphosing specimens, and from the same tergites in metamorphosing specimens. We performed a de novo assembly all available transcriptomes to construct a reference transcriptome and we identified transcripts by homology. Finally we mapped all reads into the reference transcriptome in order to perform analysis of differentially expressed genes and a GO-enrichment test. A total of 5,622 contigs appeared to be overrepresented in the transcriptome of metamorphosing specimens with respect to those specimens that did not metamorphose. Among these genes, there were six GO-terms with a p-value lower than 0.05 and among them GO: 0003676 (“nucleic acid binding”) was especially interesting since it included transcription factors (TFs). Examination of TF-Pfam-motifs revealed that the transcriptome of metamorphosing specimens contains the highest diversity of these motifs, with 29 different types (seven of them exclusively expressed in this stage) compared with that of non-metamorphosing specimens, which contained 24 motif types. Transcriptome comparisons suggest that TFs are important drivers of the process of tergal gland formation during metamorphosis. We sequenced the mRNA from the tergites 7-8 (where the tergal gland appears in the male adult individuals) with Roche 454 GS Junior System, in 4 different developmental stages; in nymph 5 during the ecdysone peak when flat tergites are being produced; in nymph 6 day 1 when the adult program its being initiated; nymph 6 day 1 treated with Juvenil Hormone that inhibits the adult program; and in nymph 6 during the ecdysone peak when tergal gland its being formed. Different transcription factors were found to play a crucial role in TG morphogenesis.

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Towards an understanding of the propensity for crystalline hydrate formation by molecular compounds.

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Towards an understanding of the propensity for crystalline hydrate formation by molecular compounds.

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