Vibronic resonances facilitate excited state coherence in light harvesting proteins at room temperature

Until recently it was believed that photosynthesis, a fundamental process for life on earth, could be fully understood with semi-classical models. However, puzzling quantum phenomena have been observed in several photosynthetic pigment-protein complexes, prompting questions regarding the nature and role of these effects. Recent attention has focused on discrete vibrational modes that are resonant or quasi-resonant with excitonic energy splittings and strongly coupled to these excitonic states. Here we unambiguously identify excited state coherent superpositions in photosynthetic light-harvesting complexes using a new experimental approach. Decoherence on the timescale of the excited state lifetime allows low energy (56 cm-1) oscillations on the signal intensity to be observed. In conjunction with an appropriate model, these oscillations provide clear and direct experimental evidence that the persistent coherences observed require strong vibronic mixing among excited states

Quantitative investigations of quantum coherence for a light-harvesting protein at conditions simulating photosynthesis

Recent measurements using two-dimensional electronic spectroscopy (2D ES) have shown that the initial dynamic response of photosynthetic proteins can involve quantum coherence. We show how electronic coherence can be differentiated from vibrational coherence in 2D ES. On that basis we conclude that both electronic and vibrational coherences are observed in the phycobiliprotein light-harvesting complex PC645 from Chroomonas sp. CCMP270 at ambient temperature. These light-harvesting antenna proteins of the cryptophyte algae are suspended in the lumen, where the pH drops significantly under sustained illumination by sunlight. Here we measured 2D ES of PC645 at increasing levels of acidity to determine if the change in pH affects the quantum coherence; quantitative analysis reveals that the dynamics are insensitive to the pH change.We acknowledge financial support from DARPA under the QuBE program, the United States Air Force Office of Scientific Research under contract number FA9550-10-1-0260, and the Natural Sciences and Engineering Research Council of Canada. We thank Min-Duk Seo and Mitsuhiko Ikura for assistance with the CD measurements and Philip Johnson, Alexei Halpin, and Jurgen Hauer for helpful conversations regarding the 2D ES apparatus

Flow of excitation energy in the cryptophyte light-harvesting antenna phycocyanin 645.

We report a detailed description of the energy migration dynamics in the phycocyanin 645 (PC645) antenna complex from the photosynthetic alga Chroomonas CCMP270. Many of the cryptophyceae are known to populate greater depths than most other algal families, having developed a 99.5% efficient light-harvesting system. In this study, we used femtosecond time-resolved spectroscopy and global analysis to characterize the excited-state dynamics of PC645. Several different pump colors were selected to excite different fractions of the four phycobiliprotein pairs present in the complex. Measurements were also performed at cryogenic temperature to enhance spectral resolution and selectively promote downhill energy transfers. Upon excitation of the highest-energy bilins (dihydrobiliverdins), energy is transferred from the core of the complex to the periphery within 0.82 ps. Four bilins (mesobiliverdin (MBV) A/B and phycocyanobilins (PCB) 158C/D), which are responsible for the central band of the absorption spectrum, show concerted spectral dynamics. These chromophores show a biphasic decay with lifetimes of 0.6 ps (MBV) and 5-7 ps (PCB 158) to the lowest bilin pair (PCB 82C/D) absorbing around 650-657 nm. Within this lifetime of several picoseconds, the excitations reach the PCB 82 bilins on the two poles at the smaller sides of PC645. A slow 44-46 ps energy transfer step to the lowest-energy PCB 82 bilin concludes the dynamics. © 2011 Biophysical Society

Disentangling electronic and vibrational coherence in the phycocyanin-645 light-harvesting complex (series: Springer proceedings in physics) / Kaoru Yamanouchi, Steven Cundiff, Regina de Vivie-Riedle, Makoto Kuwata-Gonokami, Louis DiMauro (eds.)

We selectively excite coherence pathways in the light-harvesting complex PC645 and with wavelength and polarization control identify contributions from both electronic and vibrational coherences. Insight into the interactions between excited electronic and vibrational states follows

Coherence dynamics in light-harvesting complexes with two-colour spectroscopy

We investigate coherent dynamics in the cryptophyte light-harvesting complex Phycocyanin-645 (PC-645). A two-colour four-wave mixing experiment allows us to isolate a coherence pathway and observe its evolution in the absence of other signals. We measured a decoherence time of 540fs for the coherence [1]. Additionally oscillations in the signal pathway give evidence for the coherent excitation of states outside the bandwidth of the laser pulse. This suggests strong coupling between the excited states and phonon modes [1]

Effect of caloric restriction with or without n-3 polyunsaturated fatty acids on insulin sensitivity in obese subjects: a randomized placebo controlled trial

BackgroundCaloric restriction and n-3 polyunsaturated fatty acid (PUFA) supplementation protect from some of the metabolic complications. The aim of this study was to assess the influence of a low calorie diet with or without n-3 PUFA supplementation on glucose dependent insulinotropic polypeptide (GIP) output and insulin sensitivity markers in obese subjects.MethodsObese, non-diabetic subjects (BMI 30–40 kg/m2 and aged 25–65 yr.) were put on low calorie diet (1200–1500 kcal/day) supplemented with either 1.8 g/day n-3 PUFA (DHA/EPA, 5:1) (n = 24) or placebo capsules (n = 24) for three months in a randomized placebo controlled trial. Insulin resistance markers and GIP levels were analysed from samples obtained at fasting and during an oral glucose tolerance test (OGTT).ResultsCaloric restriction with n-3 PUFA led to a decrease of insulin resistance index (HOMA-IR) and a significant reduction of insulin output as well as decreased GIP secretion during the OGTT. These effects were not seen with caloric restriction alone. Changes in GIP output were inversely associated with changes in red blood cell EPA content whereas fasting GIP level positively correlated with HOMA-IR index. Blood triglyceride level was lowered by caloric restriction with a greater effect when n-3 PUFA were included and correlated positively with fasting GIP level.ConclusionsThree months of caloric restriction with DHA + EPA supplementation exerts beneficial effects on insulin resistance, GIP and triglycerides.General significanceCombining caloric restriction and n-3 PUFA improves insulin sensitivity, which may be related to a decrease of GIP levels.AbbreviationsAUC, area under curve; BMI, body mass index; DHA, docosapentaenoic acid; EPA, eicosapentaenoic acid; GIP, glucose dependent insulinotropic polypeptide; IGI, insulinogenic index; NEFA, non esterified fatty acids; OGIS, oral glucose insulin sensitivity index; OGTT, oral glucose tolerance test; PC, phosphatidylcholine; PUFA, polyunsaturated fatty acid

Phycocyanin Sensitizes both Photosystem I and Photosystem II in Cryptophyte Chroomonas CCMP270 Cells

This article presents an investigation of the energy migration dynamics in intact cells of the unicellular photosynthetic cryptophyte Chroomonas CCMP270 by steady-state and time-resolved fluorescence measurements. By kinetic modeling of the fluorescence data on chlorophyll and phycocyanin 645 excitation (at 400 and 582 nm respectively), it has been possible to show the excited state energy distribution in the photosynthetic antenna of this alga. Excitation energy from phycocyanin 645 is distributed nearly equally between photosystem I and photosystem II with very high efficiency on a 100-ps timescale. The excitation energy trapping times for both photosystem I (∼30 ps) and photosystem I (200 and ∼540 ps) correspond well to those obtained from experiments on isolated photosystems. The results are compared with previous results for another cryptophyte species, Rhodomonas CS24, and suggest a similar membrane organization for the cryptophytes with the phycobiliproteins tightly packed in the thylakoid lumen around the periphery of the photosystems

Effect of caloric restriction with or without n-3 polyunsaturated fatty acids on insulin sensitivity in obese subjects: A randomized placebo controlled trial

Background: Caloric restriction and n-3 polyunsaturated fatty acid (PUFA) supplementation protect from some of the metabolic complications. The aim of this study was to assess the influence of a low calorie diet with or without n-3 PUFA supplementation on glucose dependent insulinotropic polypeptide (GIP) output and insulin sensitivity markers in obese subjects. Methods: Obese, non-diabetic subjects (BMI 30–40 kg/m2) and aged 25–65 yr. were put on low calorie diet (1200–1500 kcal/day) supplemented with either 1.8 g/day n-3 PUFA (DHA/EPA, 5:1) (n = 24) or placebo capsules (n = 24) for three months in a randomized placebo controlled trial. Insulin resistance markers and GIP levels were analysed from samples obtained at fasting and during an oral glucose tolerance test (OGTT). Results: Caloric restriction with n-3 PUFA led to a decrease of insulin resistance index (HOMA-IR) and a significant reduction of insulin output as well as decreased GIP secretion during the OGTT. These effects were not seen with caloric restriction alone. Changes in GIP output were inversely associated with changes in red blood cell EPA content whereas fasting GIP level positively correlated with HOMA-IR index. Blood triglyceride level was lowered by caloric restriction with a greater effect when n-3 PUFA were included and correlated positively with fasting GIP level. Conclusions: Three months of caloric restriction with DHA + EPA supplementation exerts beneficial effects on insulin resistance, GIP and triglycerides. General significance: Combining caloric restriction and n-3 PUFA improves insulin sensitivity, which may be related to a decrease of GIP levels