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v17n01.pdfJournal of Porphyrins and Phthalocyanines J. Porphyrins Phthalocyanines 2013; 17: 1–164
See Thanh-Tuan Bui, Aude Escande, Christian Philouze, Gianluca Cioci, Sudip Ghosh, Eric Saint-Aman, Jong Min Lim, Jean-Claude Moutet, Jonathan L. Sessler*, Dongho Kim* and Christophe Bucher* pp. 27–35
The cover picture displays the structure of a cyclo[6]pyrrole[3]thiophene derivative, which is a new member of the cyclo[n]pyrrole class of expanded porphyrins. It was produced in solution at an electrode interface and characterized by inter alia X-ray diffraction analysis. This electrode-based synthesis is represented schematically via a massive metallic disk surrounded by oligopyrrole building blocks, which are dis- solved in the electrolyte. The background picture was taken by one of the corres- ponding authors (C.B.) at Crozet Lake in the “Belledone” mountains (French Alps) overlooking Grenoble.
About the Cover
pp. 1–15 Extending the limits of natural photosynthesis and implications for technical light harvesting Min Chen* and Hugo Scheer*
The solar spectrum reaching the surface of the earth (blue line) contains the finger- prints of absorption by water, oxygen and ozone. Under a cover of vegetation, most of the visible light is removed by the absorption of chlorophyll a (Chl a) and other pigments (blue shaded area). Under these conditions, organisms that are capable of performing photosynthesis with near-infrared light by the use of specialized chlo- rophylls with red-shifted absorption maxima have evolved. The cyanobacterium, Acaryochloris marina, contains chlorophyll d (Chl d); it absorbs light down to ~725 nm (green shaded area). Two recently discovered organisms contain the even more red-shifted chlorophyll f (Chl f) that allows oxygenic photosynthesis at even lon- ger wavelengths. Dedicated searching for such organisms suggests that ecological niches for such organisms are quite abundant on earth, and that such specialized light-harvesting techniques contribute substantially to photosynthesis.
pp. 16–26 Nanotechnology-based photodynamic therapy Hee-Jae Yoon and Woo-Dong Jang*
The combination of nanotechnology with photodynamic therapy may provide effective platform for the selective delivery and excitation of photosensitizers, combination therapy, and multifunctional treatment of malignant tumors.
pp. 56–62
ethoxy-phosphorus(V)porphyrin Kazutaka Hirakawa*, Keito Azumi, Yoshinobu Nishimura, Tatsuo Arai, Yoshio Nosaka and Segetoshi Okazaki
DiethoxyP(V)porphyrin and its axial fluorinated derivative induce protein photo- oxidation via singlet oxygen generation and the electron transfer. The estimated contributions of the electron transfer mechanism are 0.57 and 0.44 for the fluori- nated and non-fluorinated P(V)porphyrins, respectively. The total quantum yield of the protein photo-oxidation was slightly enhanced by this axial fluorination.
pp. 44–55 Shape-persistent poly-porphyrins assembled by a cen- tral truxene: synthesis, structure, and singlet energy transfer behaviors Hai-Jun Xu, Bin Du, Claude P. Gros*, Philippe Richard, Jean- Michel Barbe and Pierre D. Harvey*
-methyl groups preventing conjugation are used to design shape-persistent mono- and trisporphyrin-truxenes for the study of S1 energy transfers truxene
porphyrin units. The rates are temperature independent and compare to other parent dyads exhibiting rotational flexibility about the truxene-porphyrin C–C bond but are also sterically hindered by the hexyl chains.
pp. 36–43 Cancer cells uptake porphyrins via heme carrier protein 1 Kazuhiro Hiyama, Hirofumi Matsui*, Masato Tamura, Osamu Shimokawa, Mariko Hiyama, Tsuyoshi Kaneko, Yumiko Nagano, Ichinosuke Hyodo, Junko Tanaka, Yoshihiro Miwa, Tetsuo Ogawa, Takeo Nakanishi and Ikumi Tamai
Increasing a newly reported transporter, heme carrier protein 1 (HCP1), ex- pression increased porphyrin accumulation and the efficacy of photodynamic therapy. Several kinds of cancer cell-lines highly expressed HCP1 and decreas- ing HCP1 expression decreased porphyrin accumulation in these cancer cells. We conclude that HCP1 is a transporter of porphyrins in cancer cells. We also demonstrated that the expression of HCP1 causes the cytotoxic effect of photo- dynamic therapy.
pp. 27–35 X-ray structure and properties of a cyclo[6]pyrrole[3]thio phene Thanh-Tuan Bui, Aude Escande, Christian Philouze, Gianluca Cioci, Sudip Ghosh, Eric Saint-Aman, Jong Min Lim, Jean-Claude Moutet, Jonathan L. Sessler*, Dongho Kim* and Christophe Bucher*
A cyclo[6]pyrrole[3]thiophene derivative could be prepared from a thiophene-contai ning terpyrrole precursor through use of a mild electrochemical oxidative procedure. A definitive proof of structure of this new member of the cyclo[n]pyrrole class featuring nine hetero- cyclic subunits directly connected through their , -positions was obtained via a single crystal X-ray diffraction analysis carried out using synchrotron radiation. Four individual macrocycles are found within the unit cell. These appear as two distinct self-assembled sandwich-like structures held together through a variety of apparent noncovalent interac- tions, including van der Waals, electrostatic forces, and a network of hydrogen bonds.
J. Porphyrins Phthalocyanines 2013; 17: 1–164
pp. 63–72 Reaction of ferric Caldariomyces fumago chloro peroxi- dase with meta-chloroperoxybenzoic acid: sequential formation of compound I, compound II and regeneration of the ferric state using one reactant Daniel P. Collins, Issa S. Isaac, Eric D. Coulter, Paul W. Hager, David P. Ballou* and John H. Dawson*
In the present study, both CCPO Fe(IV)-oxo intermediates Compound I and II formed, but unlike most CCPO reactions, they are formed using the same reactant, mCPBA. Thus, the peracid is used as an oxo donor to produce Cpd I and then as a reductant to reduce Cpd I to Cpd II and finally to the ferric state. The observation of saturation kinetics with respect to mCPBA concentration for each step is consistent with the formation of CCPO-mCPBA complexes in each phase of the reaction.
pp. 73–85 Synthesis and evaluation of cationic bacteriochlorin amphi philes with effective in vitro photodynamic acti vity against cancer cells at low nanomolar concentration Sulbha K. Sharma, Michael Krayer, Felipe F. Sperandio, Liyi Huang, Ying-Ying Huang, Dewey Holten, Jonathan S. Lindsey* and Michael R. Hamblin*
Three new bacteriochlorins, each bearing a single side-chain containing one or two positive char- ges, exhibited a high level of in vitro PDT activity against HeLa human cancer cells upon activata- tion with NIR light. The bacteriochlorins localized in mitochondria, lysosomes and endoplasmic reticulum as shown by organelle specific fluorescent probes. Cell death was via apoptosis as shown by cell morphology and nuclear condensation. Taken together, the results show the im- portance of appropriate peripheral groups about a photosensitizer for effective PDT applications.
pp. 92–98 Electrochemistry and spectroelectrochemistry of car- boxy-phenylethynyl porphyrins Pei-Shang Chao, Ming-Yu Kuo, Chen-Fu Lo, Min-Hsu Hsieh, Yu- Hsiang Cheng, Chin-Li Wang, Hsiu-Yu Lu, Hshin-Hui Kuo, Yen-Ni Hsiao, Chieh-Ming Wang and Ching-Yao Lin*
Electrochemical studies suggest that the first reduction of PE1 porphyrins are the reduction reaction of the anchoring group proton. In addition, we demonstrate that the positions of long alkyl chains at the phenyl substituents greatly affect the potentials and the reversibilities of the redox reactions of the PE1 porphyrins.
pp. 86–91 Meso–meso directly linked dipyrrolyl ligand dimer that shows the formation of metal-coordination polymers Hiromitsu Maeda*, Hiroaki Kobayashi and Ryo Akuta
A novel dipyrrolyl metal-coordination ligand dimer directly connected at the meso positions showed the formation of a ZnII-bridged coordina- tion polymer and the spontaneous transformation to a meso–meso- and singly β–β-fused tetra pyrrolyl molecule in solution by C–C bond forma- tion and concomitant proton migration.
pp. 99–103 2+ ion
Hui He, Jian-Yong Liu and Dennis K.P. Ng*
A silicon(IV) phthalocyanine with two axial bis(2-picolyl)amino moieties has been prepared and characterized. Its spectroscopic response toward various me- tal ions have been examined in MeCN and mixtures of H2O/MeCN. The results show that this compound exhibits a high sensitivity and moderate selectivity toward Zn2+ ion.
pp. 104–117 Design and synthesis of protoporphyrin IX/vita- min B12 molecular hybrids via CuAAC reaction
An approach towards the synthesis of molecular hybrids composed of protoporphyrin IX (PPIX) and vitamin B12 via copper catalyzed alkyne azide cycloaddition reaction is described. New, clickable aminoazide and aminoalkyne linkers were prepared and subsequently attached to PPIX (via vinyl group) and to vitamin B12 giving “clicable” building blocks.
pp. 118–124
tures: structure and characterization of [Fe(TalkylP) (OClO3)] and [Fe(TPrP)(THF)2]ClO4 (alkyl = Ethyl, Et and n-Propyl, Pr) Ming Li, Allen G. Oliver, Teresa J. Neal, Charles E. Schulz* and W. Robert Scheidt*
The preparation and characterization of three iron(III) porphyrinates with meso- alkyl substituents are reported. The species show distinct features of S = 3/2 states.
pp. 125–134 Advanced photodynamic agent from chondroitin sul- fate/zinc phthalocyanine conjugate Song Yi Baek and Kun Na*
In order to improve the therapeutic effect of zinc phthalocyanine (ZnPc), a nano- drug was prepared with acetylated chondroitin sulfate (AcCS), utilizing a simple chemical method. AcCS/ZnPc nanodrugs exhibited enhancing cellular interna- lization efficiency and phototoxicity compared to that of free ZnPc. Therefore, we suggest that AcCS/ZnPc nanodrugs may have promising possibilities as new photodynamic agents for the clinical treatment of various tumors.
J. Porphyrins Phthalocyanines 2013; 17: 1–164
pp. 135–141 Dechlorination of DDT catalyzed by visible- light-driven system composed of vitamin B12 derivative and Rhodamine B Keishiro Tahara, Kumiko Mikuriya, Takahiro Masuko, Jun-ichi Kikuchi and Yoshio Hisaeda*
A new catalytic system composed of a vitamin B12 derivative and Rhodamine B dechlorinated 1,1-bis(4-chlorophenyl)-2,2,2-trichlo- roethane (DDT) and 1,1-bis(4-chlorophenyl)-2,2-dichloroethane (DDD) via a noble-metal-free and visible-light-driven process.
pp. 142–149 Electron self-exchange of cytochrome c measu- red via 13C detected protonless NMR Stefano Cacciatore, Mario Piccioli and Paola Turano*
Exchange peaks measured in the new 13C-EXSY experiment (COCO- EXSY) are stronger than those observed in conventional 1H- and 15N-based EXSY experiments. The use of 13C directed detection may be essential for all those cases where T2 relaxation is detrimental. The experiment has been tested by measu ring electron self-exchage rates between diamagnetic reduced and paramagnetic oxidized human cyto- chrome c.
pp. 150–156
antiCEA bioconjugate for imaging of colorectal cancer Inder Sehgal, Hairong Li, Benson Ongarora, Daniel Devillier and M. Graça H. Vicente*
The conjugation of two zinc(II) phthalocyanines with a monoclonal antibody directed against carcinoembryonic antigen (CEA) is reported. Studies in human colorectal HT-29 cells show 37-fold increase in the immunoconjugate targeting compared with unconjugated ZnPc.
Synthesis, spectral, electrochemical and photophysical properties of BF2- oxasmaragdyrin-BODIPY and BF2-oxasmaragdyrin-ferrocene dyads are des- cribed.
AUTHOR INDEX (cumulative)
A Akuta, Ryo 86 Arai, Tatsuo 56 Azumi, Keito 56
B Baek, Song Yi 125 Ballou, David P. 63 Barbe, Jean-Michel 44 Bucher, Christophe 28 Bui, Thanh-Tuan 28
C Cacciatore, Stefano 142 Chao, Pei-Shang 92 Cheng, Yu-Hsiang 92 Chen, Min 1 Cioci, Gianluca 27 Collins, Daniel P. 63 Coulter, Eric D. 63
D Dawson, John H. 63 Devillier, Daniel 150 Du, Bin 44
E Escande, Aude 27
G Ghosh, Sudip 27 Gros, Claude P. 44 Gryko, Dorota 104
H Hager, Paul W. 63 Hamblin, Michael R. 73 Harvey, Pierre D. 44 He, Hui 99 Hirakawa, Kazutaka 56 Hisaeda, Yoshio 135 Hiyama, Kazuhiro 36 Hiyama, Mariko 36 Holten, Dewey 73 Hsiao, Yen-Ni 92 Hsieh, Min-Hsu 92
Huang, Liyi 73 Huang, Ying-Ying 73 Hyodo, Ichinosuke 36
I Isaac, Issa S. 63
J Jang, Woo-Dong 16 Janiga, Anita 104
K Kaneko, Tsuyoshi 36 Kikuchi, Jun-ichi 135 Kim, Dongho 27 Kobayashi, Hiroaki 86 Krayer, Michael 73 Kuo, Hshin-Hui 92 Kuo, Ming-Yu 92
L Li, Hairong 150 Li, Ming 118 Lim, Jong Min 27 Lindsey, Jonathan S. 73 Lin, Ching-Yao 92 Liu, Jian-Yong 99 Lo, Chen-Fu 92 Loska, Rafa 104 Lu, Hsiu-Yu 92
M Maeda, Hiromitsu 86 Masuko, Takahiro 135 Matsui, Hirofumi 36 Mikuriya, Kumiko 135 Miwa, Yoshihiro 36 Moutet, Jean-Claude 27
N Na, Kun 125 Nagano, Yumiko 36 Nakanishi, Takeo 36 Neal, Teresa J. 118 Ng, Dennis K.P. 99 Nishimura, Yoshinobu 56
Nosaka, Yoshio 56
O Ogawa, Tetsuo 36 Okazaki, Segetoshi 56 Oliver, Allen G. 118 Ongarora, Benson 150
P Pareek, Yogita 157 Philouze, Christian 27 Piccioli, Mario 142
R Ravikanth, Mangalampalli
157 Richard, Philippe 44
S Saint-Aman, Eric 27 Scheer, Hugo 1 Scheidt W. Robert 118 Schulz, Charles E. 118 Sehgal, Inder 150 Sessler, Jonathan L. 27 Sharma, Sulbha K. 73 Shimokawa, Osamu 36 Sperandio, Felipe F. 73
T Tahara, Keishiro 135 Tamai, Ikumi 36 Tamura, Masato 36 Tanaka, Junko 36 Turano, Paola 142
V Vicente, M. Graça H. 150
W Wang, Chieh-Ming 93 Wang, Chin-Li 93
X Xu, Hai-Jun 44
Y Yoon, Hee-Jae 16
Journal of Porphyrins and Phthalocyanines J. Porphyrins Phthalocyanines 2013; 17: 1–164
JPP Volume 17 - Numbers 1&2 - Pages 1–164
A alkynes 104 antibody 150 apoptosis 73 azides 104
B bacteriochlorins 73 BF2-smaragdyrin 157 bio-imaging 16 bis(2-picolyl)amine 99
C 13C direct detection 142 cancer 36 carboxyphenylethyne 92 carcinoembryonic antigen 150 chloroperoxidase 63 chlorophyll 1 chondroitin sulfate 125 click chemistry 104 colorectal cancer 150 compound I 63 compound II 63 confocal microscopy 73 coordination polymers 86 CuAAC 104 cyclopyrrole 27 cytochrome c 142
D DDT 135 dechlorination 135 dipyrrins 86
E ecophysiology 1 electrochemical synthesis 27 electrochemistry 92 electron self-exchange 142
electron transfer 56, 157 energy transfer 1, 157 expanded porphyrin 27 EXSY 142
F fluorescence 43, 150 fluorescent sensor 99 fluorination 56
H HeLa cancer cells 73 heme carrier protein 1 36
I iron (III) 118
M meso–meso linkage 86 meta-chloroperoxybenzoic acid
64 molecular hybrids 105
N nano-devices 16 nanodrug 125 nanotechnology 16 near-infrared 99 nonaphyrin 27
O organic photosensitizer 135
P peracid, rapid-scan stopped-flow
photosensitizer 56 photosynthesis 1 phototoxicity 125 photovoltaic 1 phthalocyanine 99, 150 porphyrin 36, 44, 92 protein oxidation 56 protonless NMR 142 protoporphyrin IX 104 P(V)porphyrin 56
R red-shifted chlorophyll 1 Rhodamine B 135 ring fusion 86
S saturation kinetics 63 selective delivery 16 singlet energy transfer 44 singlet oxygen 56 smaragdyrin 157 spectroelectrochemistry 92 subcellular localization 73 synchrotron radiation 27
T truxene 44
W weak-field ligands 118
KEYWORD INDEX (cumulative)
DOI: 10.1142/S1088424612300108
Sunlight has proved inexhaustible over geological time and the amount impinging on the earth’s surface vastly surpasses the biological energy needs of all life forms on earth, including man. Photosynthesis is the biological process by which light energy is harvested and transduced into energy-rich molecules, ATP and NADPH, the latter then reducing CO2 to form carbohydrates. Oxygenic photosynthetic organisms evolved 2.7–3.5 × 109 years ago providing the energy for most life forms on earth while generating the oxygen we breathe. Harvesting the sun is also, increasingly, becoming an option for sustainable energy for mankind’s needs: directly by improving biomass production of photosynthetic organisms, indirectly, by coupling it to the production of hydrogen fuel or, conceptually, by using photosynthetic
strategies for technological solutions based on non- biological or hybrid materials. We discuss the light- harvesting process of photosynthesis and its implications for technology, arising from the discovery of novel chlorophyll (Chl) pigments that extend the spectrum of oxygenic photosynthesis into the near-infrared (NIR) spectral region.
1.A. Light quality and quantity reaching a photosynthetic organism vary in time and space
The solar spectrum at the top of the atmosphere is, largely, that of a black body at a temperature of ~5800 K, with an intensity maximum in the green spectral region (λ ~ 550 nm) (Fig. 1). If the sun is in the zenith, the integrated intensity amounts to ~1.4 kW.m-2. The light quality and quantity reaching the earth’s surface are both changed and modified by lower solar altitudes,
Extending the limits of natural photosynthesis
and implica tions for technical light harvesting
Min Chen*a and Hugo Scheer*b
a School of Biological Sciences, University of Sydney, Sydney NSW 2006, Australia b Dept-Biologie 1, Botanik, Universität München, 80638 München, Germany
Received 16 July 2012 Accepted 24 August 2012
ABSTRACT: Photosynthetic organisms provide, directly or indirectly, the energy that sustains life on earth by harvesting light from the sun. The amount of light impinging on the surface of the earth vastly surpasses the energy needs of life including man. Harvesting the sun is, therefore, an option for a sustainable energy source: directly by improving biomass production, indirectly by coupling it to the production of hydrogen for fuel or, conceptually, by using photosynthetic strategies for technological solutions based on non-biological or hybrid materials. In this review, we summarize the various light climates on earth, the primary reactions responsible for light harvesting and transduction to chemical energy in photosynthesis, and the mechanisms of competitively adapting the photosynthetic apparatus to the ever-changing light conditions. The focus is on oxygenic photosynthesis, its adaptation to the various light-climates by specialized pigments and on the extension of its limits by the evolution of red-shifted chlorophylls. The implications for potential technical solutions are briefly discussed.
KEYWORDS: photosynthesis, chlorophyll, ecophysiology, red-shifted chlorophyll, photovoltaic, energy transfer, light-harvesting, light climate.
SPP full member in good standing
*Correspondence to: Hugo Scheer, email: [email protected] and Min Chen, email: [email protected]
Copyright © 2013 World Scientific Publishing Company J. Porphyrins Phthalocyanines 2013; 17: 2–15
and by absorption and scattering of the atmosphere through clouds and overlaying vegetation (Fig. 1). With clear skies and at latitudes around 45°, the maximum integrated intensity reaching the surface is ~0.5–1 kW.m-2. On cloudy days under a canopy of vegetation the photon flux can, however, be reduced by 3–4 orders of magnitude and its spectral composition changed. Oxygenic photosynthetic organisms can only use light in the spectral region of 300–750 nm, corresponding to photon energies of 400–160 kJ.mol-1. The physical limits of oxygenic photosynthesis are set by the absorption of their light-harvesting pigments and the energetics of water oxidation. The maximum integrated intensity in this spectral region (200–400 W.m-2 depending on the latitude) corresponds to a photon flux of ~1,000–2,000 μmol.m-2.s-1
. The temporal and spatial variations of the light flux and its spectral composition pose considerable problems to photosynthetic organisms, especially if they occur on short time scales when, for example, the sun breaks through clouds or a forest canopy. Photosynthetic organisms have to compete for light but, at the same time, must avoid damage by excess light. The energy of visible photons is high compared with that of typical “high energy” bio-molecules and any overload of the photosynthetic apparatus is, therefore, potentially deleterious (see Section 2A). This balance between starvation and being scorched is maintained by a modular composition of the photosynthetic apparatus and a regulatory network. The most important aspect in the scope of this short review is the functional division between the primary processes of light-harvesting complexes (LHC) in the photosynthetic antennas, and the energy transduction occurring in the reaction centers (RC).
Light intensity and quality are even more strongly modified in aqueous (marine) environments where ~50% of global photosynthesis occurs [1]. The increased
absorption and scattering by water quickly reduces the light intensity and narrows the spectral distribution as the depth increases. In clear oceanic waters, the maximal spectral transmission occurs around ~475 nm, but the bandwidth is drastically reduced: shorter (blue, UV) wavelengths are removed by scattering and longer (yellow to IR) wavelengths by absorption. At 200 m depth, the intensity of ~0.05 μmol.m-2.s-1 is only < 0.005% when compared with that at the surface: this defines the lower limit where specialized photosynthetic organisms like Prochlorococcus CCMP1375 are still found [2]. In coastal or sediment-rich water, the light intensity is more quickly reduced with depth and the spectral maximum shifted to the red with scattering by particulate matter and gas bubbles and, also, with absorption by brown pigments arising mainly from decaying vegetation. Turbid coastal waters have a maximal transmission around 570 nm and, in heavily silt-loaded waters, it can be even further red-shifted into the NIR. Aquatic photosynthesizing organisms have adapted to these conditions by developing specialized pigments with appropriate absorption properties (see Sections 2B and 3), which at the same time modify, in a more complex fashion, the light quality and quantity available to organisms in deeper marine layers than on the terrestrial surface. Particularly extreme light gradients occur inside the microbial mats sometimes encountered in symbiotic systems (see Section 3D).
1.B. Photosynthesis has maximized quantum effici- ency at the cost of energetic efficiency
The overall efficiency of photosynthesis, measured in biomass production, is quite low (~1%) [3]. The efficiency of the primary reactions is, by contrast, near the theoretical limits. It relies firstly on the efficiency
Fig. 1. Solar spectrum at the top of the atmosphere and on the earth surface, and spectra of several photosynthetic pigments in…

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