Part 2.3: Dipole Moments and Optical Activity 1. Nonaxial (no rotation) - C 1, C s, C i Cyclic (rotational) -C n, C nv, C nh, S n Dihedral ( ⊥ C 2 ) -

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Presentation transcript:

Part 2.3: Dipole Moments and Optical Activity 1

Nonaxial (no rotation) - C 1, C s, C i Cyclic (rotational) -C n, C nv, C nh, S n Dihedral ( ⊥ C 2 ) - D n, D nd, D nh Polyhedral - T, T h, T d, O, O h, I, I h Linear - C ∞v, D ∞h Types of Point Groups 2

3 Outline Dipole Moment/Polarity Dipole and Symmetry Dipole and Crystals Chirality Circular Dichroism Optical Activity and Symmetry Dynamic Molecules Applications of CD

4 Polarity/Dipole Moment Polarity- a separation of electric charge leading to a molecule or its chemical groups having an electric dipole moment. Dipole moment- magnitude of charges and the distance of separation between the charges. A molecule will have a dipole moment (that is, it will be polar) if the bond dipole moments do not cancel each other out. Molecular Dipole Moment Polar

5 Dipole Moment and Symmetry A molecule will have a dipole moment (that is, it will be polar) if the bond dipole moments do not cancel each other out. Molecular dipole is dependent on symmetry! 1)Any molecule with an inversion center (i) cannot have a dipole (or be polar). 2)Any molecule with a C 2 ⊥ to C n cannot have a dipole (or be polar). 3)Any molecule with a  h cannot have a dipole (or be polar).

6 1)Any molecule with an inversion center (i) cannot have a dipole (or be polar). Dipole Moment and Symmetry 2)Any molecule with a C 2 ⊥ to C n cannot have a dipole (or be polar). i 3)Any molecule with a  h cannot have a dipole (or be polar). x z y Can have a dipole in z or –z unless there is a ⊥ C 2 or a  h Only C 1, C s, C n, C ∞v and C nv can have a molecular dipole and be polar.

7 Dipole Moment and Symmetry Only C 1, C s, C n, C ∞v and C nv can have a molecular dipole and be polar. 1)Any molecule with an inversion center (i) cannot have a dipole (or be polar). 2)Any molecule with a C 2 ⊥ to C n cannot have a dipole (or be polar). 3)Any molecule with a  h cannot have a dipole (or be polar).

8 Dipole Moment and Symmetry Only C 1, C s, C n, and C nv can have a molecular dipole and be polar. Symmetry does not tell you the direction or the magnitude of the dipole moment. x z y x z y Direction- C 1 could be any direction (no axis) C s could be direction except ⊥ to  h C n and C nv must be z or -z

9 Dipole Moment and Symmetry Only C 1, C s, C n, and C nv can have a molecular dipole and be polar. Symmetry does not tell you the direction or the magnitude of the dipole moment. Direction- C s could be any direction (no axis) C s could be direction except ⊥ to  h C n and C nv must be z or -z Magnitude- Depends on the atoms, lone pairs and bond dipoles NH 3 NF 3 ? Bond Dipole Lone pair Molecular Dipole

10 Dipole Moment and Symmetry Why symmetry and dipole moment matter? 1)Solubility 2)Miscibility 3)Boiling/melting points 4)pK a 5)Vibrational Transitions 6)Crystal Structure/Property Acetanilide p-chloroacetanilide

11 Dipole Moment and Symmetry Acetanilide- Form pairs related by an inversion center. Cancelation of dipoles. p-chloroacetanilide- Head to tail alignment. Aligned dipoles.

12 Dipole Moment and Symmetry Non-polar crystalPolar crystal Symmetry Through the Eyes of a Chemist

13 Dipole Moment and Symmetry Non-polar crystalPolar crystal Symmetry Through the Eyes of a Chemist 1)Solid/gas reactions 2)Melting temp 3)Hardness 4)Conductivity 5)Optical Polarity 6)Pyroelectricity -must have dipole 7)Piezoelectricity

14 1)Any molecule with an inversion center (i) cannot have a dipole (or be polar). Dipole Moment and Symmetry 2)Any molecule with a C 2 ⊥ to C n cannot have a dipole (or be polar). i 3)Any molecule with a  h cannot have a dipole (or be polar). x z y Can have a dipole in z or –z unless there is a ⊥ C 2 or a  h Only C 1, C s, C n, C ∞v and C nv can have a molecular dipole and be polar.

15 Optical Activity and Symmetry Chirality Circular Dichroism Optical Activity and Symmetry Dynamic Molecules Applications of CD

Chiral Molecules 16

17 DNA is right handed Amino acids are L Carbohydrates are D Alpha Helix is right handed Origin/Evolution of life Drug delivery/processing Olfactory receptors Why Chirality Matters

Importance of Chiral Molecules 18

19 (+) –rotates the plane polarized light clockwise (when viewing towards the light source) (-) –rotates the plane polarized light counterclockwise R / S system- requires no reference molecule (Cahn–Ingold–Prelog priority rules) D / L system- referenced vs glyceraldehyde. (+)/(−) system- related to the direction to which it rotates plane polorized light. Naming Conventions R / S, D / L and (+)/(−) are not related.

Optical Activity h Sample Transmittance: T = P/P 0 Absorbance: A = -log T = log P 0 /P h P0P0 Sample (power in) P (power out) We don’t measure absorbance. We measure transmittance. 20

The Beer-Lambert Law ( specific): A = absorbance (unitless, A = log 10 P 0 /P)  = molar absorptivity (L mol -1 cm -1 ) l = path length of the sample (cm) c = concentration (mol/L or M) Beer’s Law P0P0 ConcentrationAbsorbance A =  c l Path lengthAbsorbance Molar Abs.Absorbance Sample (power in) P (power out) l in cm 21

Sample Detector End View UV-Vis Spectroscopy Unpolarized Light 22

Polarizers 23

Polarization of Light Side View End View Vertically Polarized Horizontally Polarized 24

Light + Molecules Source Strong Absorption Weak Absorption 25

Orientation Dependent Absorption Angew. Chem. Int. Ed. 2005, 44, 6564 –6568 a axis b axis 26

Adding Polarized Light In phase (peak at the same time) + same amplitude Vertical + Horizontal = 45° diagonal 27

Adding Polarized Light Green peaks when red baselines. Sum (blue) is always 1. ¼ (90°) out of phase + same amplitude Vertical + Horizontal = Circular 28

/4 Wave Plate Polarizer 29

Polarization of Light Side View End View left-circularly polarized right-circularly polarized 30

Adding Polarized Light In phase (peak at the same time) + same amplitude left circular + right circular = vertical Green peaks when red peaks. 31

Absorption Spectroscopy Absorbance: A = -log T = log P 0 /P P0P0 (power in) P (power out) P0P0 P 32

Optically Active Molecules 33

The Beer-Lambert Law: A = absorbance (unitless, A = log 10 P 0 /P)  = molar absorptivity (L mol -1 cm -1 ) l = path length of the sample (cm) c = concentration (mol/L or M) A =  c l  is the same for D and L If C are equal: 50:50 D to L 100% D 100% L Then A is the same. Assuming the light is unpolarized! Absorption Spectroscopy 34

P0P0 (power in) P (power out) left-circularly polarized right-circularly polarized Circular Absorption Absorbs more Smaller P Absorbs Less Larger P 35

Circular Absorption Absorbance: A (left) = log P 0(left) /P (left) A (right) = log P 0(right) /P (right) P0P0 (power in) P (power out) P 0(left) P (left) 36

Circular Dichroism CD measures the difference between the absorption of left and right handed cirularly-polarized light:  is typically <100 M -1 cm -1  is typically > 10,000 cm -1  = 3298 Δε. CD spectra reported in ellipticity (  ) or   in L/mol cm (liters mol -1 centimeters -1 )  in degrees cm 2 /dmol -1 (degrees centimeters 2 mol -1 ) 37

Polarizer Prism Source Circular Dichroism Process: 1) Unpolarized white light 2) Monochrometer 3) Plane polarizer 4) left-right modulator 5) left (then right) through sample 6) measure P for right (then left) through sample 38

CD Spectrometer AVIV 202 CD spectrometer Institute of Molecular Biophysics nm -10 o C to 110 o C titrator attachment 39

40 Optical Activity and Symmetry Molecules are optically active if it contains at least one chiral center. Many molecules have no chiral centers and yet are optically active.

41 Optical Activity and Symmetry Which molecules are expected to be optically active? Molecules with no improper axis of rotation (S n ) are optically active. Note S 1 = σ and S 2 = i. C 1, C n, and D n Nonaxial (no rotation) - C 1, C s, C i Cyclic (rotational) -C n, C nv, C nh, S n Dihedral ( ⊥ C 2 ) - D n, D nd, D nh Polyhedral - T, T h, T d, O, O h, I, I h Linear - C ∞v, D ∞h Chiral molecules lack an improper axis of rotation (S n ), a center of symmetry (i) or a mirror plane (σ)! Also T, O, and I

42 Optical Activity and Symmetry Chiral molecules lack an improper axis of rotation (S n ), a center of symmetry (i) or a mirror plane (σ)! C 1, C n, and D n

43 Optical Activity and Symmetry Chiral molecules lack an improper axis of rotation (S n ), a center of symmetry (i) or a mirror plane (σ)! C 1, C n, and D n Also T, O, and I

Spectra Absorption Circular Dichroism 44

45 Optical Activity and Dynamic Molecules 10 ^10 per second CD spectra-average of both isomers (at room temperature).

46 Photoreaction h ?

47 UV-Vis or CD source h ? Optical Activity and Symmetry

48 Optical Activity and Symmetry AbsorptionCD spectrum time h ?

49 Photoisomerization Decomposition Optical Activity and Symmetry

Determination of secondary structure of proteins Investigations of protein-protein interactions Investigation of the effect of drug binding Protein structure in a membrane Stereoselective synthesis Dynamic processes - protein folding - reaction dynamics DNA denaturation Applications GCN4-p1 coiled–coil 50

51 Side Note