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Synthesis of Polyhydroxylated Surfactants: Comparison of Surfactant Stereoisomers and Investigation of Haemolytic Activity
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2005 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [sv]

I den här avhandlingen har vi studerat hur man kan göra nya tensider. En tensid är en speciell molekyl som har förmågan att lösa sig i både vatten och olja.

Man kan göra följande experiment hemma: Fyll en glasburk till hälften med vatten och tillsätt en droppe matolja. Oljan bildar en droppe ovanpå vattnet, därför att vatten och olja inte är blandbara. Vatten är polärt och olja är opolärt. Om man rör om med en sked kommer oljedroppen förvisso att dela upp sig i mindre droppar, men så snart man slutar att röra kommer dessa att lägga sig på vattenytan igen. Sätt nu en droppe diskmedel till blandningen och rör om. Nu sprider sig oljedropparna mycket bättre i vattnet, och de lägger sig heller inte på vattenytan lika fort när man slutar att röra. Det här beror på att diskmedel innehåller en tensid, som har en polär och en opolär del. Den polära delen passar ihop med det polära vattnet, medan den opolära delen passar ihop med den opolära oljan. På så vis kan tensiden hjälpa till att lösa upp opolära ämnen i polära vätskor.

Den aktiva delen av ett läkemedel består ofta av opolära ämnen, vilka inte löser sig i polära vätskor såsom vatten. Eftersom kroppen består till stor del av vatten måste man ändå försöka få läkemedlet vattenlösligt, för att möjliggöra transport via blodet till problemområdet. Det kan man uppnå genom att tillsätta tensider. Om läkemedel-tensidblandningen ska ges till djur eller människor får inte tensiden orsaka någon skada i kroppen.

Vi har försökt framställa tensider som ska kunna användas för att just lösa läkemedel i vatten. För att kunna framställa nya tensider måste man ha kunskap i organisk syntes. Det betyder att man måste veta hur man från små intermediat (”byggstenar”) successivt kan bygga upp nya molekyler som har de önskvärda egenskaperna. Genom olika typer av organisk syntes har vi byggt upp tre nya tensidtyper, vars egenskaper vi studerat med olika mätningar. Ingen av dessa tensider lämpade sig som tillsats till läkemedel, men vårt arbete har givit mycket ny kunskap om hur framtida tensidmolkyler kan tillverkas och vilka egenskaper de får.

Abstract [en]

This thesis deals with the synthesis and characterization of new polyhydroxy surfactants. The first part describes the synthesis of three new surfactant classes, and the second part concerns the surface chemical characterization of the synthesized surfactants.

A stereodivergent route for preparation of hydrophilic head groups was developed, that featured consecutive stereoselective dihydroxylations of a diene. This method provided in total four different polyhydroxylated head groups. These surfactant head groups were natural and unnatural sugar analogues, and were used for the coupling with two different hydrophobic tail groups.

Another approach took advantage of a metathesis reaction and provided a polyhydroxylated compound that was coupled to 12-hydroxy stearic acid

The third class of surfactants contained an amide linkage between the hydrophilic and the hydrophobic parts. The hydrophilic part consisted of two glucose units, and 12-hydroxy stearic acid was used as the hydrophobic part. The hydroxy moiety in the tail group was further functionalized as aliphatic esters, which provided in total four different surfactants.

A selection of the surfactants was used to investigate the chiral discrimination in Langmuir monolayers at an air-water interface. The isotherms showed a remarkable difference in compressibility between diastereomeric surfactants and also a pronounced chiral discrimination between racemic and enantiomerically pure surfactants, favoring heterochiral discrimination. The monolayers were also investigated with Brewster angle microscopy (BAM) and grazing incidence X-ray diffraction (GIXD). It was not possible to observe any chirality dependent features from the BAM images, but the GIXD measurement supported the conclusion that heterochiral discrimination governed the intermolecular forces within the racemic monolayer.

The third class of surfactants, containing an amide linkage between the glucose units and 12-hydroxy stearic acid was evaluated with respect to the CMC and the haemolytic activity. These surfactants were all haemolytic close to their respective CMC.

Place, publisher, year, edition, pages
Stockholm: KTH , 2005. , 57 p.
Series
Trita-IOK, ISSN 1100-7974 ; 2005:98
Keyword [en]
Polyhydroxy surfactants, Sugar surfactants, Dihydroxylation, Metathesis, Langmuir monolayers, Chiral discrimination, Haemolysis
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-461ISBN: 91-7178-162-5 (print)OAI: oai:DiVA.org:kth-461DiVA: diva2:13076
Public defence
2005-11-04, Salongen, KTHB, Osquars backe 31, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20101015Available from: 2005-10-21 Created: 2005-10-21 Last updated: 2010-10-15Bibliographically approved
List of papers
1. Stereoselective Synthesis of Polyhydroxyl Surfactants. Stereochemical Influence on Langmuir Monolayers
Open this publication in new window or tab >>Stereoselective Synthesis of Polyhydroxyl Surfactants. Stereochemical Influence on Langmuir Monolayers
2004 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 69, no 11, 3746-3752 p.Article in journal (Refereed) Published
Abstract [en]

Herein is described the synthesis of surfactants featuring polyhydroxylated head groups. Three head groups were prepared via consecutive stereoselective dihydroxylations of a diene. By coupling of these with lipophilic tail groups six novel surfactants have been prepared. The monolayers prepared from four of these have been investigated at the air-water interface. Significant differences were observed between monolayers consisting of enantiomerically pure surfactants contra racemates as well as between diastereomers.

Keyword
Interfaces (materials), Isomers, Monolayers, Stereochemistry, Synthesis (chemical), article, diastereoisomer, enantiomer, hydroxylation, lipophilicity, racemic mixture, stereochemistry, synthesis
National Category
Organic Chemistry Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-7903 (URN)10.1021/jo0357566 (DOI)000221624900018 ()2-s2.0-2442704158 (Scopus ID)
Note

QC 20100930

Available from: 2005-10-21 Created: 2005-10-21 Last updated: 2017-12-14Bibliographically approved
2. A Metathesis Approach for the Preparation of Polyhydroxylated Compounds as Head Groups in Surfactant Synthesis
Open this publication in new window or tab >>A Metathesis Approach for the Preparation of Polyhydroxylated Compounds as Head Groups in Surfactant Synthesis
2006 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 4, 978-985 p.Article in journal (Refereed) Published
Abstract [en]

Starting from methyl-a-D-glucopyranoside, an efficient protocol for the preparation of polyhydroxylated surfactant head-groups is demonstrated and applied in the synthesis of a typical surfactant. The key transformation is a metathesis reaction between two monosaccharide residues to afford an octahydroxydecen. The importance of a strategic protecting-group constellation for a successful metathesis reaction is also investigated.

Keyword
carbohydrates, metathesis, protecting groups, surfactants, polyols
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-7904 (URN)10.1002/ejoc.200500614 (DOI)000235404000019 ()2-s2.0-33144457171 (Scopus ID)
Note
Uppdaterad från manuskript till artikel: 20101015. QC 20101015Available from: 2005-10-21 Created: 2005-10-21 Last updated: 2017-12-14Bibliographically approved
3. Synthesis of New Sugar-Based Surfactants and Evaluation of their Haemolytic Activities
Open this publication in new window or tab >>Synthesis of New Sugar-Based Surfactants and Evaluation of their Haemolytic Activities
Show others...
2006 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, no 9, 3623-3626 p.Article in journal (Other academic) Published
Abstract [en]

The synthesis of four sugar-based surfactants derived from glucose and (R)-12-hydroxystearic acid is described. The surfactants have a hydroxy group in the hydrophobic part, which is either free or acylated using acetyl chloride, hexanoyl chloride, or myristoyl chloride. Three of the synthesized surfactants are water-soluble and are evaluated with respect to their CMCs and hemolytic activities. The fourth surfactant has limited water solubility and is not further included in the study. The investigated surfactants are all hemolytic close to their respective CMC indicating that their use in parenteral formulations may be limited. Nevertheless, surfactants having the proposed structure appear as promising alternatives to existing solubilizing agents for pharmaceutical applications.

Keyword
nonionic surfactants, solubilization, erythrocytes, amphiphiles, tension
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-7905 (URN)10.1021/jo051904b (DOI)000237027000042 ()2-s2.0-33646249655 (Scopus ID)
Note
Uppdaterad från manuskript till artikel: 20101015. QC 20101015Available from: 2005-10-21 Created: 2005-10-21 Last updated: 2017-12-14Bibliographically approved
4. Influence of Surfactant Stereochemistry on Intermolecular Forces in Langmuir Monolayers
Open this publication in new window or tab >>Influence of Surfactant Stereochemistry on Intermolecular Forces in Langmuir Monolayers
(English)Manuscript (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-7906 (URN)
Note
QC 20101015Available from: 2005-10-21 Created: 2005-10-21 Last updated: 2010-10-15Bibliographically approved

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