Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Solid-state-trapped reactive ammonium carbamate self-derivative salts of prolinamide.

ABSTRACT: Single crystals for two polymorphs of the ammonium carbamate self-derivative salt of prolinamide have been successfully obtained and characterized. Decarbonation of the carbamate salts was monitored by calorimetry, confirming stabilization of the reactive carbonated adducts in the solid state. Sublimation of the salts afforded crystals of prolinamide, leading to the first crystal structure of this otherwise common molecule. Reactivity of the ammonium carbamate self-derivative salt is further illustrated by the observation of a series of derived products, including dehydroprolinamide, a methylene-bridged prolinamide, and a bicyclic derivative. Crystal structures of these products display distinct amidic and/or non-amidic hydrogen bonding. This study emphasizes the reactivity of carbonated amines stabilized in the solid and opens perspectives for a systematic study of (solid-state) reactions involving these trapped reactive species.

SUBMITTER: Tilborg A

PROVIDER: S-EPMC3892199 | biostudies-literature | 2013 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Solid-state-trapped reactive ammonium carbamate self-derivative salts of prolinamide.

Tilborg Anaëlle A Lanners Steve S Norberg Bernadette B Wouters Johan J

ChemistryOpen 20130812 5-6

Single crystals for two polymorphs of the ammonium carbamate self-derivative salt of prolinamide have been successfully obtained and characterized. Decarbonation of the carbamate salts was monitored by calorimetry, confirming stabilization of the reactive carbonated adducts in the solid state. Sublimation of the salts afforded crystals of prolinamide, leading to the first crystal structure of this otherwise common molecule. Reactivity of the ammonium carbamate self-derivative salt is further ill ...[more]

PMID: 24551566

Similar Datasets

Anticancer activity and toxicity of new quaternary ammonium geldanamycin derivative salts and their mixtures with potentiators.

Project description:Geldanamycin (GDM) has been modified by different type neutral/acidic/basic substituents (1-7) and by quinuclidine motif (8), transformed into ammonium salts (9-13) at C(17). These compounds have been characterised by spectroscopic and x-ray methods. Derivative 8 shows better potency than GDM in MCF-7, MDA-MB-231, A549 and HeLa (IC50s = 0.09-1.06 µM). Transformation of 8 into salts 9-13 reduces toxicity (by 11-fold) at attractive potency, e.g. MCF-7 cell line (IC50∼2 µM). Our studies show that higher water solubility contributes to lower toxicity of salts than GDM in healthy CCD39Lu and HDF cells. The use of 13 mixtures with potentiators PEI and DOX enhanced anticancer effects from IC50∼2 µM to IC50∼0.5 µM in SKBR-3, SKOV-3, and PC-3 cancer cells, relative to 13. Docking studies showed that complexes between quinuclidine-bearing 8-13 and Hsp90 are stabilised by extra hydrophobic interactions between the C(17)-arms and K58 or Y61 of Hsp90.

| S-EPMC8344233 | biostudies-literature

Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal.

Project description:Crystal-to-crystal transformations have been crucial in the understanding of solid-state processes, since these may be studied in detail by means of single crystal X-ray diffraction (SCXRD) techniques. The description of the mechanisms and potential intermediates of those processes remains very challenging. In fact, solid-state transient states have rarely been observed, at least to a sufficient level of detail. We have investigated the process of guest extrusion from the non-porous molecular material [Fe(bpp)(H2L)](ClO4)2·1.5C3H6O (bpp = 2,6-bis(pyrazol-3-yl)pyridine; H2L = 2,6-bis(5-(2-methoxyphenyl)-pyrazol-3-yl)pyridine; C3H6O = acetone), which occurs through ordered diffusion of acetone in a crystal-to-crystal manner, leading to dramatic structural changes. The slow kinetics of the transition allows thermal trapping of the system at various intermediate stages. The transiting single crystal can be then examined at these points through synchrotron SCXRD, offering a window upon the mechanism of the transformation at the molecular scale. These experiments have unveiled the development of an ordered intermediate phase, distinct from the initial and the final states, coexisting as the process advances with either of these two phases or, at a certain moment with both of them. The new intermediate phase has been structurally characterized in full detail by SCXRD, providing insights into the mechanism of this diffusion triggered solid-state phenomenon. The process has been also followed by calorimetry, optical microscopy, local Raman spectroscopy and powder X-ray diffraction. The discovery and description of an intermediate ordered state in a molecular solid-state transformation is of great interest and will help to understand the mechanistic details and reaction pathways underlying these transformations.

| S-EPMC6054035 | biostudies-literature

Ab initio molecular dynamic study of solid-state transitions of ammonium nitrate.

Project description:High-pressure polymorphism and phase transitions have wide ranging consequences on the basic properties of ammonium nitrate. However, the phase diagram of ammonium nitrate at high pressure and high temperature is still under debate. This study systematically investigates the phase transitions and structural properties of ammonium nitrate at a pressure range of 5-60 GPa and temperature range of 250-400 K by ab initio molecular dynamics simulations. Two new phases are identified: one corresponds to the experimentally observed phase IV' and the other is named AN-X. Simultaneously, the lattice strains play a significant role in the formation and stabilization of phase IV', providing a reasonable explanation for experimental observation of phase IV-IV' transition which only appears under nonhydrostatic pressure. In addition, 12 O atoms neighboring the NH (N atom in ammonium cation) atom are selected as reference system to clearly display the tanglesome rotation of ammonium cation.

| S-EPMC4709593 | biostudies-literature

Anti-Fouling and Anti-Biofilm Performance of Self-Polishing Waterborne Polyurethane with Gemini Quaternary Ammonium Salts.

Project description:Biofilms are known to be difficult to eradicate and control, complicating human infections and marine biofouling. In this study, self-polishing and anti-fouling waterborne polyurethane coatings synthesized from gemini quaternary ammonium salts (GQAS), polyethylene glycol (PEG), and polycaprolactone diol (PCL) demonstrate excellent antibiofilm efficacy. Their anti-fouling and anti-biofilm performance was confirmed by a culture-based method in broth media, with the biofilm formation factor against Gram-positive (S. aureus) and Gram-negative bacterial strains (E. coli) for 2 days. The results indicate that polyurethane coatings have excellent anti-biofilm activity when the content of GQAS reached 8.5 wt% against S. aureus, and 15.8 wt% against E. coli. The resulting waterborne polyurethane coatings demonstrate both hydrolytic and enzymatic degradation, and the surface erosion enzymatic degradation mechanism enables them with good self-polishing capability. The extracts cyto-toxicity of these polyurethane coatings and degradation liquids was also systematically studied; they could be degraded to non-toxic or low toxic compositions. This study shows the possibility to achieve potent self-polishing and anti-biofilm efficacy by integrating antibacterial GQAS, PEG, and PCL into waterborne polyurethane coatings.

| S-EPMC9865321 | biostudies-literature

Self-trapped state enabled filterless narrowband photodetections in 2D layered perovskite single crystals.

Project description:Filterless narrowband photodetectors can realize color discrimination without filter or bulk spectrometer, thus greatly reducing the system volume and cost for many imaging applications. Charge collection narrowing has been demonstrated to be a successful approach to achieve filterless narrowband photodetections; nevertheless, it sacrifices the sensitivity of the photodetectors. Here we show a highly tunable narrowband photodetector based on two-dimensional perovskite single crystals with high external quantum efficiency (200%), ultralow dark current (10-12 A), and high on-off ratio (103). The spectral response of the narrowband photodetectors can be continuously tuned from red to blue with all full-width at half-maximum < 60 nm and especially < 20 nm in blue wavelength range. The excellent performance can be ascribed to self-trapped states within bandgap and extremely low electrical conductivity in the out-of-plane direction. Our findings open the exciting potential of 2D perovskites for next-generation optoelectronics.

| S-EPMC6379360 | biostudies-other

Chasing Self-Assembly of Thioether-Substituted Flavylium Salts in Solution and Bulk State.

Project description:Two series of flavylium triflates carrying alkoxy side chains in the A-ring (benzo unit of chromylium salt) and thioethers in the B ring (phenyl unit) (On -Fla-Sm ) as well as thioethers at both A and B ring (Sn -Fla-Sm ) were synthesized in order to understand the effect of thioether functionalization on their self-assembly and electronic properties. Concentration-dependent and diffusion ordered (DOSY) NMR experiments of O1 -iV-Fla-S3 indicate the formation of columnar H-aggregates in solution with antiparallel intracolumnar stacking of the AC unit (chromylium) of the flavylium triflate, in agreement with the solid state structure of O1 -V-Fla-S1 . Thioether substitution on the B ring changes the linear optical properties in solution, whereas it has no effect on the A ring. According to differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction bulk self-assembly of these ionic liquid crystals (ILCs) depends on the total number of side chains, yielding SmA and LamCol phases for ILCs with 2-3 chains and Colro , Colh phases for ILCs with 3-6 chains. Thus, we demonstrated that thioethers are a useful design tool for ILCs with tailored properties.

| S-EPMC9400860 | biostudies-literature

Study of Ground State Interactions of Enantiopure Chiral Quaternary Ammonium Salts and Amides, Nitroalkanes, Nitroalkenes, Esters, Heterocycles, Ketones and Fluoroamides.

Project description:Chiral phase-transfer catalysis provides high level of enantiocontrol, however no experimental data showed the interaction of catalysts and substrates. 1 H NMR titration was carried out on Cinchona and Maruoka ammonium bromides vs. nitro, carbonyl, heterocycles, and N-F containing compounds. It was found that neutral organic species and quaternary ammonium salts interacted via an ensemble of catalyst + N-C-H and (sp2 )C-H, specific for each substrate studied. The correspondent BArF salts interacted with carbonyls via a diverse set of + N-C-H and (sp2 )C-H compared to bromides. This data suggests that BArF ammonium salts may display a different enantioselectivity profile. Although not providing quantitative data for the affinity constants, the data reported proofs that chiral ammonium salts coordinate with substrates, prior to transition state, through specific C-H positions in their structures, providing a new rational to rationalize the origin of enantioselectivity in their catalyses.

| S-EPMC8453964 | biostudies-literature

Spontaneous knotting of self-trapped waves.

Project description:We describe theory and simulations of a spinning optical soliton whose propagation spontaneously excites knotted and linked optical vortices. The nonlinear phase of the self-trapped light beam breaks the wave front into a sequence of optical vortex loops around the soliton, which, through the soliton's orbital angular momentum and spatial twist, tangle on propagation to form links and knots. We anticipate similar spontaneous knot topology to be a universal feature of waves whose phase front is twisted and nonlinearly modulated, including superfluids and trapped matter waves.

| S-EPMC3480719 | biostudies-literature

15N solid-state NMR provides a sensitive probe of oxidized flavin reactive sites.

Project description:Flavins are central to the reactivity of a wide variety of enzymes and electron transport proteins. There is great interest in understanding the basis for the different reactivities displayed by flavins in different protein contexts. We propose solid-state nuclear magnetic resonance (SS-NMR) as a tool for directly observing reactive positions of the flavin ring and thereby obtaining information on their frontier orbitals. We now report the SS-NMR signals of the redox-active nitrogens N1 and N5, as well as that of N3. The chemical shift tensor of N5 is over 720 ppm wide, in accordance with the predictions of theory and our calculations. The signal of N3 can be distinguished on the basis of coupling to 1H absent for N1 and N5, as well as the shift tensor span of only 170 ppm, consistent with N3's lower aromaticity and lack of a nonbonding lone pair. The isotropic shifts and spans of N5 and N1 reflect two opposite extremes of the chemical shift range for "pyridine-type" N's, consistent with their electrophilic and nucleophilic chemical reactivities, respectively. Upon flavin reduction, N5's chemical shift tensor contracts dramatically to a span of less than 110 ppm, and the isotropic chemical shift changes by approximately 300 ppm. Both are consistent with loss of N5's nonbonding lone pair and decreased aromaticity, and illustrate the responsiveness of the 15N chemical shift principal values to electronic structure. Thus. 15N chemical shift principal values promise to be valuable tools for understanding electronic differences that underlie variations in flavin reactivity, as well as the reactivities of other heterocyclic cofactors.

| S-EPMC5993988 | biostudies-literature

Novel Bis-Ammonium Salts of Pyridoxine: Synthesis and Antimicrobial Properties.

Project description:A series of 108 novel quaternary bis-ammonium pyridoxine derivatives carrying various substituents at the quaternary nitrogen's and acetal carbon was synthesized. Thirteen compounds exhibited antibacterial and antifungal activity (minimum inhibitory concentration (MIC) 0.25-16 µg/mL) comparable or superior than miramistin, benzalkonium chloride, and chlorhexidine. A strong correlation between the lipophilicity and antibacterial activity was found. The most active compounds had logP values in the range of 1-3, while compounds with logP > 6 and logP < 0 were almost inactive. All active compounds demonstrated cytotoxicity comparable with miramistin and chlorhexidine on HEK-293 cells and were three-fold less toxic when compared to benzalkonium chloride. The antibacterial activity of leading compound 5c12 on biofilm-embedded Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli or Pseudomonas aeruginosa was comparable or even higher than that of the benzalkonium chloride. In vivo 5c12was considerably less toxic (LD50 1705 mg/kg) than benzalkonium chloride, miramistine, and chlorhexidine at oral administration on CD-1 mice. An aqueous solution of 5c12 (0.2%) was shown to be comparable to reference drugs efficiency on the rat's skin model. The molecular target of 5c12 seems to be a cellular membrane as other quaternary ammonium salts. The obtained results make the described quaternary bis-ammonium pyridoxine derivatives promising and lead molecules in the development of the new antiseptics with a broad spectrum of antimicrobial activity.

| S-EPMC7570726 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data