Figure 1.
Structures of molecules used in the work. (A) Optical switches based on cis/trans isomerism (E/Z-switches). OHBP, trans1,1’,2,2’,3,3’,4,4’ octahydro 4,4’ biphenanthrylidene (an overcrowded alkene); NAIP, Nalkylated indanylidene pyrroline (retinal analog); GFP, green fluorescent protein fluorophore; NABP, Nalkylated benzylidene pyrroline (retinal analog). (B) Optical switches based on ring open/closed reaction (O/C-switches). DASA, donor-acceptor Stenhause adducts. For the sake of simplicity merocyanine and fulgide are named as open forms of spyropyran and spyrooxazine, respectively.
Figure 1.
Structures of molecules used in the work. (A) Optical switches based on cis/trans isomerism (E/Z-switches). OHBP, trans1,1’,2,2’,3,3’,4,4’ octahydro 4,4’ biphenanthrylidene (an overcrowded alkene); NAIP, Nalkylated indanylidene pyrroline (retinal analog); GFP, green fluorescent protein fluorophore; NABP, Nalkylated benzylidene pyrroline (retinal analog). (B) Optical switches based on ring open/closed reaction (O/C-switches). DASA, donor-acceptor Stenhause adducts. For the sake of simplicity merocyanine and fulgide are named as open forms of spyropyran and spyrooxazine, respectively.
Figure 2.
(A) Lateral pressure profile in the hydrophobic region. (B) Schematic representation of a molecule in the lipid layer; (C) same as (B), top view. The area of a molecule projection onto the plane perpendicular to normal bilayer should be minimal.
Figure 2.
(A) Lateral pressure profile in the hydrophobic region. (B) Schematic representation of a molecule in the lipid layer; (C) same as (B), top view. The area of a molecule projection onto the plane perpendicular to normal bilayer should be minimal.
Figure 3.
Algorithm of the projection area calculation. (A) Optimized geometry of cis stilbene. (B) cis stilbene with accurate van der Waals radii and its projections onto three planes. (C) Change in the projection area upon the molecule rotation around the X (angle ) and Y (angle ) axes.
Figure 4.
Optimized geometries of photoswitches in trans, cis (A), and open/closed (B) configurations.
Figure 4.
Optimized geometries of photoswitches in trans, cis (A), and open/closed (B) configurations.
Figure 5.
The space of the projection areas A (Å) of the molecules onto plane obtained upon scanning of the projection area upon rotation of the molecule over and . (A) E/Z-switches. (B) O/C-switches.
Figure 6.
Predicted structures of efficient optical switches for lipid membranes.
Table 1.
Characteristics of E/Z optical switches in cis and trans configurations.
Isomer | Parameter | Stilbene | Stiff-Stilbene | OHBP | Azobenzene | NAIP | NABP | GFP | Hemithioindigo |
---|
Trans | (Å) | 78.04 | 93.44 | 107.3 | 76.28 | 77.78 | 67.72 | 69.02 | 90.23 |
- | (Å) | 21.21 | 30.87 | 61.73 | 21.27 | 46.79 | 28.22 | 22.61 | 24.89 |
- | | 3.68 | 3.03 | 1.74 | 3.59 | 1.66 | 2.4 | 3.05 | 3.63 |
Cis | (Å) | 68.65 | 84.95 | 96.05 | 59.6 | 78.01 | 78.03 | 68.1 | 86.49 |
- | (Å) | 35.30 | 40.38 | 65.06 | 36.55 | 43.18 | 28.71 | 22.28 | 24.63 |
- | | 1.94 | 2.1 | 1.48 | 1.63 | 1.81 | 2.54 | 3.06 | 3.51 |
Table 2.
Characteristics of O/C optical switches in open and closed configurations.
Isomer | Parameter | DASA | Diarylethene | Spirooxazine | Spiropyran |
---|
Open | (Å) | 97.22 | 82.29 | 74.53 | 85.90 |
- | (Å) | 39.10 | 62.18 | 46.65 | 46.75 |
- | | 2.49 | 1.32 | 1.60 | 1.84 |
Close | (Å) | 94.75 | 85.75 | 78.19 | 82.18 |
- | (Å) | 49.90 | 50.41 | 41.89 | 44.88 |
- | | 1.90 | 1.70 | 1.87 | 1.83 |
Table 3.
Change of the geometry upon the cis/trans transition.
| Stilbene | Stiff-Stilbene | OHBP | Azobenzene | NAIP | NABP | GFP | Hemithioindigo |
---|
S | 1.66 | 1.31 | 1.05 | 1.72 | 0.92 | 1.02 | 0.99 | 0.99 |
(Å) | 12.09 | 9.51 | 3.33 | 15.28 | 3.61 | 0.49 | 5.94 | 0.26 |
Table 4.
Change of the geometry upon the open/closed transition.
| DASA | Diarylethene | Spirooxazine | Spiropyran |
---|
S | 1.28 | 0.81 | 0.90 | 0.96 |
(Å) | 10.0 | 11.77 | 4.76 | 1.87 |
Table 5.
Geometry of the isomerizable double bond in optical switches.
Isomer | Parameter | Stilbene | Stiff-Stilbene | OHBP | Azobenzene | NAIP | NABP | GFP | Hemithioindigo |
---|
Trans | Dihedral angle (1-2-3-4) | 180 | 179.8 | 155 | 180 | 167.1 | 178.6 | 180.0 | 180.0 |
- | Angle (1-2-3) | 127.1 | 125.1 | 123.4 | 116.6 | 126.4 | 128.9 | 130.3 | 119.5 |
- | Angle (2-3-4) | 127.1 | 125.1 | 123.4 | 116.6 | 130.5 | 126.4 | 122.3 | 132.6 |
Cis | Dihedral angle (1-2-3-4) | 4.5 | 9.9 | 16.9 | 5.4 | 10.3 | 2.0 | 0.1 | 0 |
- | Angle (1-2-3) | 129.7 | 123.2 | 123.6 | 124.4 | 131.4 | 129.0 | 134.9 | 131.8 |
- | Angle (1-2-3) | 129.7 | 123.2 | 123.6 | 124.4 | 133.1 | 132.2 | 132.6 | 136.2 |
Table 6.
Characteristics of predicted optical switches (depicted in
Figure 6) in
cis and
trans configurations.
Isomer | Parameter | Dimethyl mono | Dimethyl bis | Cyclopentyl mono | Cyclopentyl bis | Cyclohexyl mono | Cyclohexyl bis |
---|
Trans | (Å) | 85.71 | 99.56 | 87.03 | 98.65 | 92.66 | 108.41 |
- | (Å) | 26.83 | 28.92 | 28.32 | 32.73 | 30.20 | 33.73 |
- | | 3.19 | 3.44 | 3.07 | 3.01 | 3.07 | 3.21 |
Cis | (Å) | 70.27 | 79.44 | 73.09 | 80.94 | 78.22 | 93.04 |
- | (Å) | 42.47 | 50.1 | 42.24 | 52.71 | 44.12 | 51.21 |
- | | 1.65 | 1.59 | 1.73 | 1.54 | 1.77 | 1.82 |
- | S | 1.58 | 1.73 | 1.49 | 1.61 | 1.46 | 1.52 |
- | (Å) | 15.44 | 21.18 | 13.92 | 19.98 | 13.92 | 17.48 |