Glycolipids applications, hydrophobic balance rules them all Germn - - PowerPoint PPT Presentation

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Glycolipids applications, hydrophobic balance rules them all Germn - - PowerPoint PPT Presentation

Jun 27, 2023 198 likes •667 views

Glycolipids applications, hydrophobic balance rules them all Germn Gnther S. Laboratorio de Cintica y Fotoqumica Departamento de Qumica Orgnica y Fsico Qumica Facultad de Ciencias Qumicas y Farmacuticas. Universidad de

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Glycolipids applications, hydrophobic balance rules them all

Germán Günther S.

Laboratorio de Cinética y Fotoquímica Departamento de Química Orgánica y Físico Química Facultad de Ciencias Químicas y Farmacéuticas. Universidad de Chile

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Glycolipids applications, hydrophobic balance rules them all

Susana Sánchez D.

Departamento de Polímeros Facultad de Cs. Químicas. Universidad de Concepción

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Catalina Sandoval A.

  • Depto. de Qca. Org. y Fco. Qca.

Facultad de Cs. Qcas. y Farm. Universidad de Chile

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Glycolipids: Biomolecules lipid chain (lipophilic) plus a monosaccharide/oligosaccharide (hydrophilic) The most common contain: galactose, mannose, fucose, glucose, glucosamine, galactosamine, or sialic acid as sugar

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Glycolipids:

Involved in cell-cell interactions (signaling, recognition and adhesion) are modulated by sugar molecules located on the surface of cell as glycoconjugates.

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1 Sucrose Esters (Monoacyl) 2 Lactose Derivatives 3 Mannose Derivatives galactose, mannose, fucose, glucose, glucosamine, galactosamine, or sialic acid as sugar

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Families of Compounds Studied

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  • 1. Sucrose

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Sucrose esterification

Position 6-O Position 6’-O Position 1’-O

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General estructure of 6-O sucrose esters

O O H O H OH O O O H OH O H O H RCOO

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Sucrose derivatives

CLAFQO 2017 Substituent name Molecule MOS MDS MLS MMS MPS 9

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2 4 6 8 10 12

  • 0,25
  • 0,20
  • 0,15
  • 0,10
  • 0,05

0,00 0,05

GP [MMS] / [POPC]

I II III

∆GPsat

1.1 Three Stage Model of Solubilization

I Saturation II Solubilization III Mixed Micelles

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350 400 450 500 550 600 100000 200000 300000 400000 500000 600000 700000 800000

Intensidad / u.a. Longitud de onda / nm

Laurdan

blue red blue red

I I GP I I − = +

CH3 O N CH3 C H3

Iblue = 440nm Ired = 490nm

Laurdan GP on Cuvette

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70 60 50 40 30 20 10 % Transmittance 600 550 500 450 400 350 Wavelength (nm) 140x10

3

120 100 80 60 40 20 Fluorescence (au)

ch1 Blue filter ch1 Red filter

Corrected Emission Spectra of Laurdan in DMSO

ch1 ch2 GP(1-2/1+2) GP histogram

Measurement of Laurdan GP in the GUVs using Sim-FCS program

GP on the two-channel microscope

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2 4 6 8 10 12

  • 0,25
  • 0,20
  • 0,15
  • 0,10
  • 0,05

0,00 0,05

GP [MMS] / [POPC]

I II III

∆GPsat

1.1 Three Stage Model of Solubilization

I Saturation II Solubilization III Mixed Micelles

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2 4 6 8 10 12

  • 0,25
  • 0,20
  • 0,15
  • 0,10
  • 0,05

0,00 0,05

GP [MMS] / [POPC]

I

∆GPsat

1.1 Three Stage Model of Solubilization

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8 12 16

  • 0.4
  • 0.2

0.0 0.2 0.4 0.6

GP sat Methylene Units

GPsat for DODAC SUV`s (○) and DPPC vesicles (●) with the series of sucrose esters at 25 ̊ C

Effect of methylene units on GPsat

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1.2Sucrose ester Micelles

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1.2 Effect on the Palisade of Direct Mixed Micelles

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1.2 Effect on the Palisade of Direct Mixed Micelles

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CLAFQO 2017 20 Sucrose esters

χTriton X-100

k0 /106seg-1 k- /106seg-1 kq /106seg-1 1 4.26 3.32 6.42 MCS 0.8 3.92 9.55 7.59 0.6 3.97 7.77 2.32 0.5 3.95 7.43 4.29 3,57

  • 1.11

MLS 0.8 4.51 2.60 6.37 0.6 4.43 2.35 6.34 0.5 4.45 1.91 6.29 4.09 0.44 7.10 MPS 0.8 4.14 3.94 7.75 0.6 4.36 7.67 12.8 0.5 4.22 9.41 15.3 4.05

  • 3.71

Effect of sucrose esters in the quenching process of pyrene by dodecylpyridinium chloride (DPC) in pure and mixed Triton X-100 micelles.

Direct Mixed Micelles

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Direct Mixed Micelles

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The disturbing effect on the micelle core, consequence of the difference in size of both hydrophobic tails (Triton X-100 and SE), plays an important role, and the blocking effect can be overcame when the hydrophobic tails of SEs are too short or too long compared with Triton alkyl chain.

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2 Lactose Derivatives

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Lactose

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Lactose Reaction

Anomeric Position

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Lactose Derivatives

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DOL DLL DPL

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From: Bagatolli, L. A. (2006). "To see or not to see: Lateral organization of biological membranes and fluorescence microscopy." Biochimica Et Biophysica Acta-Biomembranes 1758(10): 1541-1556.

Photoselection effect in Laurdan emission in GUVs

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Hydrophobic mismatch in the lipid matrix

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Hydrophobic mismatch heads

DPPC:DPPE 3:7

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  • L. A. Bagatolli and E. Gratton, Biophysical Journal 78: 290 (2000)
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DLPC:DPLC 1:1

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  • L. A. Bagatolli and E. Gratton, Biophysical Journal 78: 290 (2000)

Hydrophobic mismatch tails

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  • L. A. Bagatolli and E. Gratton, Biophysical Journal 78: 290 (2000)

Hydrophobic mismatch

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GUVs

POPC:DPL (36% POPC) GUVs 30oC

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top top center Intensity GP Image GP Image

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3 Mannose Derivatives

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Mannose

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Mannose Reaction

Anomeric Position

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Mannose Products

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DOM DLM DPM MOM MLM MPM

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Monoalkyl Mannose

But longer ones ¡¡¡

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Spontaneous Curvature

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Monoalkyl Mannose

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Agglutination

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Agglutination

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Interaction Affects Membrane

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And now, Mannose plus a probe

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We hope

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Acknowledments

The authors thank Fondecyt-Chile 1120196 (G.G.) 1140454 (S.S)

  • C. Sandoval-Altamirano thanks to Conicyt Beca Doctorado

Nacional 21120554

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And also Thank you