describe and use chromatography to separate and identify chloroplast pigments (reference should be made to Rf values in identification of chloroplast pigments)

Photosynthesis – Energy Transfer Process (Cambridge International AS & A Level Biology 9700)

Assessment‑Objective (AO) Mapping

Learning ObjectiveAO1 – Knowledge & UnderstandingAO2 – Application & AnalysisAO3 – Practical Skills & Evaluation
State the overall photosynthetic equation.
Describe the light‑dependent reactions (PS II & PS I, electron flow, ATP/NADPH formation).✓ (explain why non‑cyclic flow produces O₂)
Describe the Calvin‑Benson (light‑independent) cycle.✓ (calculate ATP/NADPH consumption per CO₂ fixed)
Identify the major chloroplast pigments and interpret their absorption spectra.✓ (match peaks to pigments, discuss antenna function)
Carry out paper chromatography to separate chloroplast pigments and use Rf values for identification.✓ (analyse chromatograms, calculate Rf)✓ (design, execute, evaluate the practical)
Explain how light intensity, CO₂ concentration, temperature and water availability limit photosynthetic rate.✓ (predict direction of change, interpret data)
Design and evaluate simple experiments to measure photosynthetic rate (O₂ evolution or CO₂ uptake).
Link photosynthesis to cellular respiration, describe photo‑respiration and calculate respiratory quotient (RQ).✓ (interpret RQ values, discuss energy balance)

1. Overall Photosynthetic Equation

6 CO2 + 6 H2O + light energy → C6H12O6 + 6 O2

Photons are captured by pigment molecules in the thylakoid membranes; the energy is stored in ATP and NADPH, which then drive CO₂ fixation in the Calvin‑Benson cycle.

2. Chloroplast Structure (relevant to the syllabus)

  • Double‑membrane envelope – encloses the organelle.
  • Stroma – fluid matrix where the Calvin‑Benson cycle occurs; contains DNA, ribosomes and enzymes.
  • Thylakoid system

    • Stacked discs = grana; sites of the light‑dependent reactions.
    • Unstacked thylakoids = stroma lamellae; connect grana and house ATP synthase.
    • Thylakoid membrane houses photosystems, electron carriers and the oxygen‑evolving complex.

3. Light‑Dependent Reactions

  • Location: Thylakoid membranes (grana & stroma lamellae).
  • Key components: PS II (P680), plastoquinone (PQ), cytochrome b6f, plastocyanin (PC), PS I (P700), ferredoxin (Fd), NADP⁺‑reductase, ATP synthase.
  • Non‑cyclic electron flow (most common):

    1. Light excites P680 → electron ejection.
    2. H₂O is split (photolysis) → O₂ + 2H⁺ (lumen) + 2e⁻.
    3. e⁻ travel via PQ → cytochrome b₆f → PC → P700.
    4. Second photon excites P700 → e⁻ reduce NADP⁺ → NADPH.
    5. Proton gradient (H⁺) drives ATP synthesis (photophosphorylation).

  • Cyclic photophosphorylation (PS I only): Excited e⁻ from P700 return to PQ, generating extra ATP but no NADPH or O₂.

4. Light‑Independent Reactions (Calvin‑Benson Cycle)

PhaseKey StepsProducts
Carbon fixationRubisco catalyses CO₂ + RuBP → 2 × 3‑PGA2 × 3‑PGA
Reduction3‑PGA + ATP + NADPH → G3PG3P (some leaves cycle, some forms glucose)
Regeneration5 G3P + 3 ATP → 3 RuBPRuBP restored for the next turn

For every 3 CO₂ fixed the cycle consumes 9 ATP and 6 NADPH, producing one G3P that can be converted to glucose.

4.1. C₃, C₄ and CAM Pathways (brief comparison)

FeatureC₃C₄CAM
Initial CO₂ fixation enzymeRubisco (carboxylase)PEP carboxylase (mesophyll)PEP carboxylase (night)
Primary site of Calvin cycleMesophyll chloroplastsBundle‑sheath chloroplastsMesophyll chloroplasts (day)
Adaptation toTemperate, moderate lightHigh light, high temperature, low CO₂Arid, water‑limited environments
Limiting factor under droughtStomatal closure → photo‑respirationCO₂ concentration in bundle sheath maintainedStomata open at night → water loss reduced

5. Chloroplast Pigments, Absorption & Action Spectra

  • Pigments absorb specific wavelengths and transfer excitation energy to the reaction‑centre chlorophyll a.
  • Accessory pigments broaden the usable spectrum and protect against excess light.

5.1. Typical Absorption Peaks (nm)

PigmentPeak(s)Role
Chlorophyll a430, 662Primary donor in both photosystems
Chlorophyll b453, 642Extends absorption; funnels energy to chlorophyll a
β‑Carotene450‑500Absorbs blue‑green; transfers energy; quenches triplet chlorophyll
Lutein / Violaxanthin / Neoxanthin (xanthophylls)470‑500Photoprotection (xanthophyll cycle) & supplemental harvesting

5.2. Interpreting an Absorption Spectrum (example box)

Task: A graph shows absorbance vs wavelength with peaks at 430 nm, 452 nm, 662 nm and a broad band 470‑500 nm.

  • 430 nm → chlorophyll a (blue region)
  • 452 nm → chlorophyll b (blue‑green region)
  • 662 nm → chlorophyll a (red region)
  • 470‑500 nm → carotenoids (β‑carotene & xanthophylls)

Students should state which pigments are present and explain how their combined absorption matches the action spectrum of photosynthesis (maximal activity ≈ 430‑660 nm).

6. Paper Chromatography of Chloroplast Pigments

6.1. Principle

Pigments are separated on cellulose paper (stationary phase) by a solvent (mobile phase). The distance a pigment travels relative to the solvent front is expressed as the retardation factor (Rf).

Rf = (distance travelled by pigment) ÷ (distance travelled by solvent front)

Each pigment has a characteristic Rf range under standard conditions, allowing identification.

6.2. Materials (Cambridge standard)

  • Whatman No. 1 chromatography paper (or equivalent)
  • Solvent: petroleum ether : acetone (90 : 10 v/v)
  • Fresh spinach (or other green plant material)
  • Mortar & pestle, 80 % (v/v) acetone for extraction
  • Capillary tubes or micropipettes
  • Pencil, ruler, sealed chromatography chamber

6.3. Step‑by‑Step Procedure

  1. Cut paper into strips 2 cm × 15 cm.
  2. Draw a faint pencil line 2 cm from the bottom (origin).
  3. Grind ~0.5 g fresh spinach with 5 ml 80 % acetone to a uniform green paste.
  4. Spot 1–2 µl of the extract onto the origin line; let dry. Repeat 2–3 times to concentrate.
  5. Place the strip in the chamber so that the solvent level is ~0.5 cm below the origin. Seal the chamber.
  6. Allow the solvent to ascend the paper until it is ~1 cm from the top (≈15 min). Do not disturb.
  7. Remove the strip, immediately mark the solvent front, and dry in a fume cupboard.
  8. Measure distances from origin to each pigment band and to the solvent front; calculate Rf values.

6.4. Typical Rf Values (Petroleum ether : acetone = 90 : 10)

PigmentVisible colourTypical Rf rangePrimary role
β‑CaroteneOrange0.85 – 0.90Absorbs blue‑green; photoprotection
LuteinYellow‑orange0.75 – 0.80Accessory pigment; xanthophyll cycle
ViolaxanthinYellow‑orange0.70 – 0.75Photoprotection (xanthophyll cycle)
Chlorophyll bBlue‑green0.55 – 0.60Extends absorption; transfers energy to chlorophyll a
Chlorophyll aDark blue‑green0.45 – 0.50Primary pigment for charge separation

6.5. Interpreting the Chromatogram (AO2 + AO3)

  • Match each measured Rf with the reference range (±0.02 acceptable).
  • Order of migration reflects polarity: non‑polar carotenes travel farthest; the most polar pigment (chlorophyll a) travels least.
  • Band intensity gives a qualitative estimate of relative pigment abundance – useful when discussing antenna size.
  • Unexpected bands may indicate minor pigments (e.g., neoxanthin) or experimental errors (over‑loading, solvent impurity).
  • For quantitative work, densitometry can be used to calculate the proportion of each pigment; relate this to light‑harvesting efficiency.

7. Photo‑respiration

  • Cause: Rubisco can act as an oxygenase, fixing O₂ instead of CO₂.
  • Pathway: O₂ + RuBP → 1 × 3‑PGA + 1 × 2‑phosphoglycolate → (peroxisome, mitochondrion) → CO₂ + NH₃ (energy‑costly).
  • Consequences:

    • Loss of previously fixed carbon (CO₂ release).
    • Consumption of ATP and NADPH without net carbohydrate gain.
    • Reduced photosynthetic efficiency, especially at high temperature and low CO₂.

  • Relevance to the syllabus: Explains why C₃ plants are more affected by drought and high temperature than C₄ plants.

8. Linking Pigment Composition to Energy‑Transfer Efficiency

  • Accessory pigments increase the quantum yield by harvesting photons that chlorophyll a cannot absorb.
  • The “antenna size” (total pigment per reaction centre) can be estimated from band intensities on a chromatogram; larger antennas improve light capture under low irradiance but increase heat loss under excess light.
  • Carotenoids (β‑carotene, xanthophylls) protect the photosystems by dissipating excess energy as heat (non‑photochemical quenching).
  • Students may calculate the % contribution of each pigment (e.g., β‑carotene ≈ 30 % of total absorbance) and discuss how a shift in this proportion would affect the rate of ATP/NADPH production.

9. Limiting Factors in Photosynthesis (Syllabus 13.2)

FactorEffect on RateTypical Experimental Test
Light intensityRate rises until light‑saturation; then plateaus.Vary distance of a lamp from leaf discs; measure O₂ evolution.
CO₂ concentrationRate increases to a saturation point; limited by Rubisco activity.Inject known volumes of CO₂ into a sealed chamber with leaf material.
TemperatureRate rises to an optimum (~25 °C for many C₃ plants) then falls due to enzyme denaturation.Place leaf samples in water baths at different temperatures; record O₂ evolution.
Water availabilityStomatal closure reduces CO₂ entry; severe drought damages the photosynthetic apparatus.Expose plants to progressive drought; measure gas exchange.

10. Measuring Photosynthetic Rate (AO3 – Practical Skills)

10.1. Oxygen‑Evolution (Water‑Displacement) Method

  1. Insert a leaf disc (or a small spinach piece) into a sealed syringe filled with water.
  2. Expose the leaf to a known light intensity.
  3. O₂ produced displaces water; record the volume change over time.
  4. Calculate rate (mL O₂ min⁻¹) and, if required, convert to µmol O₂ g⁻¹ FW min⁻¹.

10.2. Carbon‑Dioxide Uptake Using an Infrared Gas Analyzer (IRGA)

  1. Clamp a leaf in a sealed cuvette connected to the IRGA.
  2. Measure the decline in CO₂ concentration under controlled light and temperature.
  3. Express the rate as µmol CO₂ m⁻² s⁻¹.

10.3. Qualitative Starch Test

  • Expose leaves to light for a set period.
  • Boil in water, de‑colourise with ethanol, then add iodine solution.
  • Blue‑black colour = starch (photosynthetic activity); colourless = no starch.

11. Link to Cellular Respiration & Respiratory Quotient (RQ)

  • During daylight, photosynthesis supplies ATP and NADPH; respiration consumes O₂ and releases CO₂.
  • Respiratory Quotient (RQ) = CO₂ produced ÷ O₂ consumed.

    • Carbohydrate oxidation: RQ ≈ 1.0 (C₆H₁₂O₆ + 6 O₂ → 6 CO₂ + 6 H₂O).
    • Fat oxidation: RQ ≈ 0.7 (more O₂ required per CO₂).

  • Example calculation: If a leaf disc consumes 0.30 mmol O₂ min⁻¹ and produces 0.28 mmol CO₂ min⁻¹, RQ = 0.28 ÷ 0.30 ≈ 0.93, indicating predominately carbohydrate metabolism.
  • Comparing RQ values under light and dark conditions helps students understand the balance between photosynthetic production and respiratory consumption of gases.

12. Summary of Key Points

  • Photosynthesis converts light energy into chemical energy (ATP, NADPH) and stores it as carbohydrate.
  • Light‑dependent reactions occur in thylakoid membranes; the Calvin‑Benson cycle occurs in the stroma.
  • Chlorophyll a is the primary pigment; chlorophyll b and carotenoids extend the absorption range and protect the system.
  • Paper chromatography separates pigments; identification is based on characteristic Rf values (β‑carotene ≈ 0.88, lutein ≈ 0.78, chlorophyll b ≈ 0.58, chlorophyll a ≈ 0.48).
  • Photo‑respiration reduces efficiency, especially in C₃ plants under high temperature/low CO₂.
  • Limiting factors (light, CO₂, temperature, water) can be investigated experimentally; results are interpreted using AO2‑style data analysis.
  • Linking photosynthesis to respiration via RQ provides a quantitative view of plant energy balance.