Linked Life Data

7306486

Source:http://linkedlifedata.com/resource/pubmed/id/7306486

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
21
pubmed:dateCreated
1982-2-12
pubmed:abstractText
Differential scanning calorimetry and X-ray diffraction of anhydrous and hydrated N-palmitoylgalactosylsphingosine (NPGS) show evidence of complex polymorphic behavior and interconversions between stable and metastable structural forms. Anhydrous NPGS exhibits three lamellar crystal forms (A, B, and B') at temperatures below 143 degrees C and a liquid-crystal form between 143 and 180 degrees C before melting to an isotropic liquid at 180 degrees C. The crystal B leads to liquid-crystal transition is accompanied by an enthalpy change, delta H, of 11.2 kcal/mol of NPGS, while a relatively small enthalpy change (delta H = 0.8 kcal/mol) marks the liquid-crystal leads to liquid transition. The A and B' crystal forms do not hydrate readily at room temperature. When heated, crystal form A in the presence of water undergoes an exothermic transition at 52 degrees C to produce a thermodynamically stable hydrated crystal E form. X-ray diffraction shows that this stable bilayer crystal form has a highly ordered hydrocarbon chain packing arrangement; melting to the bilayer liquid-crystal form occurs at 82 degrees C with a large enthalpy change, delta H = 17.5 kcal/mol of NPGS. A complex liquid-crystal leads to crystal transition is observed on cooling; the cooling rate independent exotherm involves the transition of the hydrated liquid crystal to an intermediate metastable crystal form identical with anhydrous crystal form A. The subsequent cooling rate dependent step involves the conversion of the metastable crystal form A to the stable crystal form E. We suggest that hydrated crystal form E is stabilized by both a highly ordered chain packing mode and a lateral intermolecular hydrogen bonding network involving the sphingosine backbone, the galactosyl group, and interbilayer water molecules. Although disruption of both the specific hydrogen chain packing and H-bonding networks occurs at the high enthalpy transition to the bilayer liquid-crystal L alpha form, these two types of interactions are not reestablished simultaneously on cooling. First, recrystallization of the hydrocarbon chain accompanies removal of water from the lipid interface, leading to "dehydrated" metastable crystal form A. This is followed by a time-dependent, temperature-dependent hydration process which allows a rearrangement of the hydrogen-bonding matrix. Alterations in the NPGS-NPGS and NPGS-water interactions accompany further changes in the hydrocarbon chain packing and lead to the formation of the stable E form.
pubmed:grant
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Oct
pubmed:issn
0006-2960
pubmed:author
pubmed:issnType
Print
pubmed:day
13
pubmed:volume
20
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
5957-66
pubmed:dateRevised
2007-11-14
pubmed:meshHeading
pubmed:year
1981
pubmed:articleTitle
X-ray diffraction and calorimetric study of anhydrous and hydrated N-palmitoylgalactosylsphingosine (cerebroside).
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, P.H.S., Research Support, U.S. Gov't, Non-P.H.S., Research Support, Non-U.S. Gov't