Browse
Submit Data
Databases
API
Help

Dataset Information

17 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Bicyclo[3.2.0]heptane mechanophores for the non-scissile and photochemically reversible generation of reactive bis-enones.

ABSTRACT: Force-induced transformations of polymer-bound functionalities have the potential to produce a rich array of stress-responsive behavior. One area of particular interest is the activation of non-scissile mechanophores in which latent reactivity can be unveiled that, under the appropriate conditions, could lead to constructive bond formation in materials exposed to typically destructive stress. Here, the mechanical activation of a bicyclo[3.2.0]heptane (BCH) mechanophore is demonstrated via selective labeling of bis-enone products. BCH ring-opening produces large local elongation (>4 Å) and products that are reactive to conjugate additions under mild conditions. Subsequent photocyclization regenerates the initial BCH functionality, providing switchable structure and reactivity along the polymer backbone in response to stress and visible light.

SUBMITTER: Kean ZS

PROVIDER: S-EPMC3511912 | biostudies-literature | 2012 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Bicyclo[3.2.0]heptane mechanophores for the non-scissile and photochemically reversible generation of reactive bis-enones.

Kean Zachary S ZS Black Ramirez Ashley L AL Yan Yufan Y Craig Stephen L SL

Journal of the American Chemical Society 20120725 31

Force-induced transformations of polymer-bound functionalities have the potential to produce a rich array of stress-responsive behavior. One area of particular interest is the activation of non-scissile mechanophores in which latent reactivity can be unveiled that, under the appropriate conditions, could lead to constructive bond formation in materials exposed to typically destructive stress. Here, the mechanical activation of a bicyclo[3.2.0]heptane (BCH) mechanophore is demonstrated via select ...[more]

PMID: 22817476

Similar Datasets

3-(2,6-Dioxopiperidin-3-yl)-3-aza-bicyclo-[3.2.0]heptane-2,4-dione.

Project description:The title mol-ecule, C(11)H(12)N(2)O(4), consists of a 3-aza-bicyclo-[3.2.0]heptane group containing a nearly planar cyclo-butane ring (r.m.s. deviation of fitted atoms is 0.0609?Å), fused to a pyrrolidine ring, bonded to a 2,6-dioxopiperidine ring at the 3-position. The angle between the mean planes of the cyclo-butane and fused pyrrolidine ring is 67.6?(6)°. The dihedral angles between the mean planes of the pyrrolidine and cyclo-butane rings and the dioxopiperidine ring are 73.9?(2) and 62.4?(4)°, respectively. The pyrrolidine and dioxopiperidine rings are twisted about the 3-yl group [torsion angles = -55.0?(1) and 115.0?(1)°] in a nearly perpendicular manner. Crystal packing is influenced by extensive inter-molecular C-H?O and N-H?O inter-actions between all four carbonyl O atoms and H atoms from the cyclo-butane and dioxopiperidine rings, as well as between the N atom and an H atom from the cyclo-butane ring. In addition, weak ?-ring interactions also occur between H atoms from the cyclobutane ring and the five-membered pyrrolidine ring. As a result, mol-ecules are linked into infinite chains diagonally along the [101] plane of the unit cell in an alternate inverted pattern.

| S-EPMC2968123 | biostudies-literature

Genotoxic effect of 2,2'-bis(bicyclo[2.2.1] heptane) on bacterial cells.

Project description:The toxic effect of strained hydrocarbon 2,2'-bis (bicyclo[2.2.1]heptane) (BBH) was studied using whole-cell bacterial lux-biosensors based on Escherichia coli cells in which luciferase genes are transcriptionally fused with stress-inducible promoters. It was shown that BBH has the genotoxic effect causing bacterial SOS response however no alkylating effect has been revealed. In addition to DNA damage, there is an oxidative effect causing the response of OxyR/S and SoxR/S regulons. The most sensitive to BBH lux-biosensor was E. coli pSoxS-lux which reacts to the appearance of superoxide anion radicals in the cell. It is assumed that the oxidation of BBH leads to the generation of reactive oxygen species, which provide the main contribution to the genotoxicity of this substance.

| S-EPMC7444485 | biostudies-literature

2-Hydr-oxy-6,6-dimethyl-bicyclo-[3.1.1]heptane-2-carboxylic acid.

Project description:The title compound, C(10)H(16)O(3), with a bicyclo-[3.1.1]heptane unit, was obtained by oxidation of ?-pinene. The asymmetric unit contains two independent mol-ecules with similar geometry: the six-membered rings in both mol-ecules adopt envelope conformations. In the crystal, the independent mol-ecules exist as O-H?O hydrogen-bonded dimers. The dimers are linked into helical chains along the b axis by O-H?O hydrogen bonds.

| S-EPMC2971213 | biostudies-literature

N,N,2,5,7-Penta-phenyl-2,5,7-triaza-bicyclo-[2.2.1]heptane-3,6-diamine.

Project description:In the title compound, C(34)H(31)N(5), the observed molecular geometry suggests that anomeric effects are present in terms of short C-N bond lengths and reduced pyramidality of the N atoms.

| S-EPMC2977394 | biostudies-literature

Azaruthena(II)-bicyclo[3.2.0]heptadiene: Key Intermediate for Ruthenaelectro(II/III/I)-catalyzed Alkyne Annulations.

Project description:A ruthenium-catalyzed electrochemical dehydrogenative annulation reaction of imidazoles with alkynes has been established, enabling the preparation of various bridgehead N-fused [5,6]-bicyclic heteroarenes through regioselective electrochemical C-H/N-H annulation without chemical metal oxidants. Novel azaruthenabicyclo[3.2.0]heptadienes were fully characterized and identified as key intermediates. Mechanistic studies are suggestive of an oxidatively induced reductive elimination pathway within a ruthenium(II/III) regime.

| S-EPMC7317209 | biostudies-literature

Proton-Stabilized Photochemically Reversible E/ Z Isomerization of Spiropyrans.

Project description:Spiropyrans undergo Cspiro-O bond breaking to their ring-open protonated E-merocyanine form upon protonation and irradiation via an intermediate protonated Z-merocyanine isomer. We show that the extent of acid-induced ring opening is controlled by matching both the concentration and strength of the acid used and with strong acids full ring opening to the Z-merocyanine isomer occurs spontaneously allowing its characterization by 1H NMR spectroscopy as well as UV/vis spectroscopy, and reversible switching between Z/ E-isomerization by irradiation with UV and visible light. Under sufficiently acidic conditions, both E- and Z-isomers are thermally stable. Judicious choice of acid such that its p Ka lies between that of the E- and Z-merocyanine forms enables thermally stable switching between spiropyran and E-merocyanine forms and hence pH gating between thermally irreversible and reversible photochromic switching.

| S-EPMC6150689 | biostudies-literature

catena-Poly[[diaqua-copper(II)]-?-7-oxa-bicyclo-[2.2.1]heptane-2,3-dicarboxyl-ato].

Project description:In the crystal structure of the title compound, [Cu(C(8)H(8)O(5))(H(2)O)(2)](n), the Cu(II) cation is in a Jahn-Teller distorted six-coordination by two O atoms from water molecules, by the bridging O atom from the bicyclo moiety, by two carboxylate O atoms from two different carboxylate groups and by one carboxylate O atom from a symmetry-related bridging ligand.The polymeric structure is made up from double-strands propagating parallel to the c axis that are held together via inter-molecular O-H?O hydrogen bonds.

| S-EPMC2968279 | biostudies-literature

tert-Butyl 3-oxo-2-oxa-5-aza-bicyclo-[2.2.1]heptane-5-carboxyl-ate.

Project description:The title compound, C(10)H(15)NO(4), also known as N-tert-butyl-oxycarbonyl-allohydr-oxy-l-proline lactone, is quite similar to N-acetyl-allohydr-oxy-l-proline lactone [Lenstra, Petit & Geise (1979 ?). Cryst. Struct. Commun. 8, 1023-1029], whereby both carbonyl groups point roughly in the same direction because of the trans conformation of the peptide bond.

| S-EPMC2959344 | biostudies-literature

rac-(rel-1R,2R,4S)-Spiro-[bicyclo-[2.2.1]heptane-2,3'-indol]-2'-amine.

Project description:In the racemic title compound, C(14)H(16)N(2), the aromatic ring component of the amino-indoline system occupies the endo cavity of the norbornane component. The aromatic ring lies at an angle of 74.12?(5)° to the plane defined by the four C atoms that comprises the rigid part of the boat-shaped six-membered ring of the norbornane unit. Pairs of mol-ecules assemble in the crystal structure, forming centrosymmetric hydrogen-bonded dimers via pairs of N-H?N hydrogen bonds through the syn H atom of the amine group.

| S-EPMC3051556 | biostudies-other

Crystal structure of benzyl 3-oxo-2-oxa-5-aza-bicyclo-[2.2.1]heptane-5-carboxyl-ate.

Project description:The title compound, C13H13NO4 (also known as N-benzyl-oxycarbonyl-4-hy-droxy-l-proline lactone), crystallizes with two mol-ecules in the asymmetric unit. They have slightly different conformations: the fused ring systems almost overlap, but different C-O-C-C torsion angles for the central chains of -155.5 (2) and -178.6 (2)° lead to different twists for the terminal benzene ring. In the crystal, the mol-ecules are linked by C-H⋯O inter-actions, generating a three-dimensional network. The absolute structure was established based on an unchanging chiral centre in the synthesis.

| S-EPMC4518953 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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