Chlorophylls: A Personal Snapshot.

Chlorophylls provide the basis for photosynthesis and thereby most life on Earth. Besides their involvement in primary charge separation in the reaction center, they serve as light-harvesting and light-sensing pigments, they also have additional functions, e.g., in inter-system electron transfer. Chlorophylls also have a wealth of applications in basic science, medicine, as colorants and, possibly, in optoelectronics. Considering that there has been more than 200 years of chlorophyll research, one would think that all has been said on these pigments. However, the opposite is true: ongoing research evidenced in this Special Issue brings together current work on chlorophylls and on their carotenoid counterparts. These introductory notes give a very brief and in part personal account of the history of chlorophyll research and applications, before concluding with a snapshot of this year's publications.

Intracellular bound chlorophyll residues identify 1 Gyr-old fossils as eukaryotic algae.

The acquisition of photosynthesis is a fundamental step in the evolution of eukaryotes. However, few phototrophic organisms are unambiguously recognized in the Precambrian record. The in situ detection of metabolic byproducts in individual microfossils is the key for the direct identification of their metabolisms. Here, we report a new integrative methodology using synchrotron-based X-ray fluorescence and absorption. We evidence bound nickel-geoporphyrins moieties in low-grade metamorphic rocks, preserved in situ within cells of a ~1 Gyr-old multicellular eukaryote, Arctacellularia tetragonala. We identify these moieties as chlorophyll derivatives, indicating that A. tetragonala was a phototrophic eukaryote, one of the first unambiguous algae. This new approach, applicable to overmature rocks, creates a strong new proxy to understand the evolution of phototrophy and diversification of early ecosystems.

A tribute to Robert John Porra (august 7, 1931-may 16, 2019).

Robert John Porra (7.8.1931-16.5.2019) is probably best known for his substantial practical contributions to plant physiology and photosynthesis by addressing the problems of both the accurate spectroscopic estimation and the extractability of chlorophylls in many organisms. Physiological data and global productivity estimates, in particular of marine primary productivity, are often quoted on a chlorophyll basis. He also made his impact by work on all stages of tetrapyrrole biosynthesis: he proved the C5 pathway to chlorophylls, detected an alternative route to protoporphyrin in anaerobes and the different origin of the oxygen atoms in anaerobes and aerobes. A brief review of his work is supplemented by personal memories of the authors.

From δ-aminolevulinic acid to chlorophylls and every step in between: in memory of Constantin (Tino) A. Rebeiz, 1936-2019.

Constantin A. (Tino) Rebeiz, a pioneer in the field of chlorophyll biosynthesis, and a longtime member of the University of Illinois community of plant biologists, passed away on July 25, 2019. He came to the USA at a time that was difficult for members of minority groups to be in academia. However, his passion for the complexity of the biochemical origin of chlorophylls drove a career in basic sciences which extended into applied areas of environmentally friendly pesticides and treatment for skin cancer. He was a philanthropist; in retirement, he founded the Rebeiz Foundation for Basic Research which recognized excellence and lifetime achievements of selected top scientists in the general area of photosynthesis research. His life history, scientific breakthroughs, and community service hold important lessons for the field.

Eugene I. Rabinowitch: A prophet of photosynthesis and of peace in the world.

More than 45 years have passed since Eugene I. Rabinowitch died, on May 15, 1973, at the age of 75, but many still remember him as a photosynthesis giant, the author of a 2000-page "Bible" on photosynthesis, a great chemist and physicist, a discoverer of several basic photoreactions, one of the founders of modern biophysics, a peacemaker, a poet, an architect, an artist, a wonderful human being, and above all a great mentor. Sir John Rotblatt cited Eugene Rabinowitch, together with Bertrand Russell, for their key contributions that led to the Nobel Peace Prize awarded in 1995 jointly to Rotblatt and the Pugwash Conferences on Science and World Affairs "for their efforts to diminish the part played by nuclear arms in international politics and, in the longer run, to eliminate such arms." Already in 1965, Eugene Rabinowitch had received the prestigious Kalinga Prize from UNESCO "in recognition of his work to encourage international cooperation among scientists and to bring to light the potential dangers of science to the public."

Photosynthesis: From De Saussure To Liebig.

The dawn of photosynthesis, characterized by the research of Priestley, Ingen- Housz and Senebier, culminated in 1804 with a historical essay of Théodore De Saussure. According to the historians, during the first half of the nineteenth century in which the genesis of the cell theory started off, the research on photosynthesis met a phase of stagnation. Indeed, the literature review of the period does not report particular innovation; however, several scientists (botanists, physiologists, and chemists) supported the thesis of De Saussure with a series of analyses that, in our opinion, deserve to be known. Mirbel, De Candolle, Raspail, Berzelius, Payen, Dutrochet, von Mohl, and other scholars attempted to expand knowledge on photosynthesis but were not able to arrive at a theory that was consistent with a functional mechanism, nor with a suitable chemical model to explain the transformation of the water and carbon dioxide into sugars. A classic case of such inadequacy concerns the discovery of chlorophyll. This compound, isolated in 1818 by Pelletier and Caventou, remained an enigma for many years and was never put in relation with the synthesis of starch. The accurate research of von Mohl led this scientist to believe that the granules of chlorophyll were entirely independent of starch granules, although in many cases these latter were observable inside the granules of chlorophyll. Only in the early forties, Justus von Liebig realized that the assimilation of carbon and hydrogen required a series of chemical reactions that, starting from some organic acids, ended in the formation of sugar. In conclusion, our analysis does not lead to define this period as stagnation but rather as transition, in which the concept of photosynthesis was clear, even though difficult to treat under physiological and chemical views. From the sixties, the researches of Julius von Sachs will open a new road, thanks also to the research carried out in the transition period.

Trends in ocean colour and chlorophyll concentration from 1889 to 2000, worldwide.

Marine primary productivity is an important agent in the global cycling of carbon dioxide, a major 'greenhouse gas', and variations in the concentration of the ocean's phytoplankton biomass can therefore explain trends in the global carbon budget. Since the launch of satellite-mounted sensors globe-wide monitoring of chlorophyll, a phytoplankton biomass proxy, became feasible. Just as satellites, the Forel-Ule (FU) scale record (a hardly explored database of ocean colour) has covered all seas and oceans--but already since 1889. We provide evidence that changes of ocean surface chlorophyll can be reconstructed with confidence from this record. The EcoLight radiative transfer numerical model indicates that the FU index is closely related to chlorophyll concentrations in open ocean regions. The most complete FU record is that of the North Atlantic in terms of coverage over space and in time; this dataset has been used to test the validity of colour changes that can be translated to chlorophyll. The FU and FU-derived chlorophyll data were analysed for monotonously increasing or decreasing trends with the non-parametric Mann-Kendall test, a method to establish the presence of a consistent trend. Our analysis has not revealed a globe-wide trend of increase or decrease in chlorophyll concentration during the past century; ocean regions have apparently responded differentially to changes in meteorological, hydrological and biological conditions at the surface, including potential long-term trends related to global warming. Since 1889, chlorophyll concentrations have decreased in the Indian Ocean and in the Pacific; increased in the Atlantic Ocean, the Mediterranean, the Chinese Sea, and in the seas west and north-west of Japan. This suggests that explanations of chlorophyll changes over long periods should focus on hydrographical and biological characteristics typical of single ocean regions, not on those of 'the' ocean.