Bicarbonate is a key regulator but not a substrate for O2 evolution in Photosystem II.

Photosystem II (PSII) uses light energy to oxidize water and to reduce plastoquinone in the photosynthetic electron transport chain. O2 is produced as a byproduct. While most members of the PSII research community agree that O2 originates from water molecules, alternative hypotheses involving bicarbonate persist in the literature. In this perspective, we provide an overview of the important roles of bicarbonate in regulating PSII activity and assembly. Further, we emphasize that biochemistry, spectroscopy, and structural biology experiments have all failed to detect bicarbonate near the active site of O2 evolution. While thermodynamic arguments for oxygen-centered bicarbonate oxidation are valid, the claim that bicarbonate is a substrate for photosynthetic O2 evolution is challenged.

Bifunctional Catalysts for CO2 Reduction and O2 Evolution: A Pivotal for Aqueous Rechargeable Zn-CO2 Batteries.

The quest for the advancement of green energy storage technologies and reduction of carbon footprint is determinedly rising toward carbon neutrality. Aqueous rechargeable Zn-CO2 batteries (ARZCBs) hold the great potential to encounter both the targets simultaneously, i.e., green energy storage and CO2 conversion to value-added chemicals/fuels. The major descriptor of ARZCBs efficiency is allied with the reactions occurring at cathode during discharging (CO2 reduction) and charging (O2 evolution) which own different fundamental mechanisms and hence mandate the employment of two different catalysts. This presents an overall complex and expensive battery system which requires a concrete solution, while the development and application of a bifunctional cathode catalyst toward both reactions could reduce the complexity and cost and thus can be a pivotal for ARZCBs. However, despite the increasing research interest and ongoing research, a systematic evaluation of bifunctional catalysts is rarely reported. In this review, the need of bifunctional cathode catalysts for ARZCBs and associated challenges with strategies have been critically assessed. A detailed progress examination and understanding toward designing of bifunctional catalyst for ARZCBs have been provided. This review will enlighten the future research approaching boosted performance of ARZCBs through the development of efficient bifunctional cathode catalysts.

Graphite-N reinforced sludge biochar electrode: A experimental and DFT theoretical analysis of efficient evolution and in-situ utilization of H2O2.

Rational reuse of municipal sludge to produce electro-Fenton electrode can not only save resources, but also produce superior peroxide and degradation pollutants simultaneously. Herein, a novel electro-Fenton electrode derived from sludge biochar loaded on Ni foam (SBC@Ni) was constructed via high temperature pyrolysis and chemical coating for efficient H2O2 evolution and pollutant degradation. Systematic experiments and density functional theory calculations (DFT calculation) explained that the production of graphite C and graphite N during high-temperature pyrolysis of municipal sludge can greatly enhance the oxygen reduction reaction of SBC@Ni electrode and promote the evolution of H2O2. And the hybrid heterojunctions, such as FeP, also played a key role in electrocatalytic processes. Notably, the electrode still exhibited excellent performance after 1000 linear scans and 12 h of continuous current stimulation, which demonstrated the excellent stability of the electrode. Moreover, SBC@Ni electrode can not only effectively oxidize 4-chlorophenol through the electro-Fenton effect, but also fully mineralize organic matter, indicating promising environmental application. The free radical quenching experiment also revealed that the ·OH is the main active species for 4-CP degradation in SBC@Ni electro-Fenton system.

Measurements of Oxygen Evolution in Photosynthesis.

This chapter compares two different techniques for monitoring photosynthetic O2 production; the wide-spread Clark-type O2 electrode and the more sophisticated membrane inlet mass spectrometry (MIMS) technique. We describe how a simple membrane inlet for MIMS can be made out of a commercial Clark-type cell and outline the advantages and drawbacks of the two techniques to guide researchers in deciding which method to use. Protocols and examples are given for measuring O2 evolution rates and for determining the number of chlorophyll molecules per active photosystem II reaction center.

Few-Layer Meets Crystalline Structure: Collaborative Efforts for Improving Photocatalytic H2O2 Generation over Carbon Nitride.

Although the conversion of O2 and H2O to H2O2 over graphite carbon nitride (g-C3N4) has been realized by means of the photocatalytic process, the catalytic activity of pristine g-C3N4 is still restricted by the rapid charge recombination and inadequate exposure of the active site. In this work, we propose a straightforward strategy to solve these limitations by decreasing the thickness and improving the crystallinity of g-C3N4, resulting in the preparation of few-layered crystalline carbon nitride (FL-CCN). Benefiting from the minimal thickness and highly ordered in-plane triangular cavities within the structure, FL-CCN processes an extended π-conjugated system with a reduced charge transfer resistance and expanded specific surface area. These features accelerate the efficiency of photogenerated charge separation in FL-CCN and contribute to explore of its surface active sites. Consequently, FL-CCN exhibits a significantly improved H2O2 evolution rate (63.95 µmol g-1 h-1), which is 7.8 times higher than that of pristine g-C3N4 (8.15 µmol g-1 h-1), during the photocatalytic conversion of O2 and H2O. This systematic investigation offers valuable insights into the mechanism of photocatalytic H2O2 generation and the development of efficient catalysts.

Effects of n-butanol production on metabolism and the photosystem in Synecococcus elongatus PCC 7942 based on metabolic flux and target proteome analyses.

Although n-butanol (BuOH) is an ideal fuel because of its superior physical properties, it has toxicity to microbes. Previously, a Synechococcus elongatus PCC 7942 derivative strain that produces BuOH from CO2 was developed by introducing six heterologous genes (BUOH-SE strain). To identify the bottleneck in BuOH production, the effects of BuOH production and its toxicity on central metabolism and the photosystem were investigated. Parental (WT) and BUOH-SE strains were cultured under autotrophic conditions. Consistent with the results of a previous study, BuOH production was observed only in the BUOH-SE strain. Isotopically non-stationary 13C-metabolic flux analysis revealed that the CO2 fixation rate was much larger than the BuOH production rate in the BUOH-SE strain (1.70 vs 0.03 mmol gDCW-1 h-1), implying that the carbon flow for BuOH biosynthesis was less affected by the entire flux distribution. No large difference was observed in the flux of metabolism between the WT and BUOH-SE strains. Contrastingly, in the photosystem, the chlorophyll content and maximum O2 evolution rate per dry cell weight of the BUOH-SE strain were decreased to 81% and 43% of the WT strain, respectively. Target proteome analysis revealed that the amounts of some proteins related to antennae (ApcA, ApcD, ApcE, and CpcC), photosystem II (PsbB, PsbU, and Psb28-2), and cytochrome b6f complex (PetB and PetC) in photosystems decreased in the BUOH-SE strain. The activation of photosynthesis would be a novel approach for further enhancing BuOH production in S. elongatus PCC 7942.

G-C3N4 sheet nanoarchitectonics with island-like crystalline/amorphous homojunctions towards efficient H2 and H2O2 evolution.

Photocatalystic evolution of H2O2 from water and oxygen has attracted significant attention because of environmentally friendly. The absorption in visible and hydrophilic feature of graphitic carbon nitride (g-C3N4) make it a good candidate. In this paper, a rapid post-treatment at high temperature was developed to obtain g-C3N4 nanosheets with abundant crystalline/amorphous interfaces to form homojunctions, which optimized uniplanar carrier mobility dynamics. The conversion from bulk to two-dimensional g-C3N4 resulted from the breakage of interplanar hydrogen bonds and interlayer Van der Waals force. The unique morphology not only rendered photocatalyst with larger specific surface area but also inhibited the robust volume recombination of charge carriers. The accelerated charge carriers flow at the interface, interplane and interlayer together ameliorated the separation and transfer of electrons and holes. A new-emerged n→π* transition ameliorated the poor light utilization efficiency. Beyond the increased photocatalytic H2 evolution property (779.2 µmol g-1 h-1), optimized sample displayed a H2O2 evolution activity as high as 4877.1 µM g-1 h-1 under visible light illumination, which was ∼5.8 times of that of bulk g-C3N4. Detailed photocatalytic mechanism investigation manifested that the two-step single-electron oxygen reduction process occupied the dominant status in H2O2 evolution. This work proposed a novel strategy for obtaining g-C3N4 homojunctions as a promising bi-functional metal-free catalyst to be applied in clean energy production field.

Oxygen-modified graphitic carbon nitride with nitrogen-defect for metal-free visible light photocatalytic H2O2 evolution.

Photocatalytic oxygen reduction is regarded as the cleanest approach for the production of hydrogen peroxide (H2O2). Herein, oxygen-modified graphite carbon nitride (g-C3N4) with nitrogen-defect (namely g-C3N4-ND4-OM3) was synthesized by a feasible method. Owing to the existence of nitrogen vacancy and oxygen-containing functional group, the absorption bands derived from n â†’ π* and π â†’ π* electronic transitions were enhanced, thereby enlarging the visible light response range of catalysts. Interestingly, nitrogen-defect can capture electron and effectively suppress the recombination of photoinduced electrons and holes. More importantly, the introduction of oxygen-containing functional groups can improve the hydrophilicity of g-C3N4, which was beneficial for the adsorption of dissolved oxygen. The electrostatic potential distributions of g-C3N4-based photocatalyst structural unit were also changed after introducing nitrogen vacancy and oxygen-containing functional group, and the electron-donating ability of g-C3N4 was improved. As a result, the evolution rate of H2O2 catalyzed by g-C3N4-ND4-OM3 was as high as 146.96 µmol/g/L under visible light irradiation. The photocatalytic H2O2 generation was completed through the direct 2-e- oxygen reduction. In short, current work will share novel insights into photocatalytic H2O2 generation over g-C3N4-based catalyst.

Covalent Organic Frameworks for Energy Conversion in Photocatalysis.

Intensifying energy crises and severe environmental issues have led to the discovery of renewable energy sources, sustainable energy conversion, and storage technologies. Photocatalysis is a green technology that converts eco-friendly solar energy into high-energy chemicals. Covalent organic frameworks (COFs) are porous materials constructed by covalent bonds that show promising potential for converting solar energy into chemicals owing to their pre-designable structures, high crystallinity, and porosity. Herein, we highlight recent progress in the synthesis of COF-based photocatalysts and their applications in water splitting, CO2 reduction, and H2 O2 production. The challenges and future opportunities for the rational design of COFs for advanced photocatalysts are discussed. This Review is expected to promote further development of COFs toward photocatalysis.

Action of 2,6-Dichloro-1,4-benzoquinone on the O2-Evolving Activity of Photosystem II in Chlamydomonas reinhardtii Cells with and without Cell Wall: Inhibitory Effect of Its Oxidized Form.

Chlamydomonas reinhardtii is a widely used object in studies on green algae concerning both photosynthesis aspects and possible biotechnological approaches. The measurement of the maximum O2 evolution by photosystem II (PSII) in living algal cells in the presence of artificial acceptors is one of the commonly used methods for determining the photosynthetic apparatus state or its change as compared to a control, parent strain, etc., because PSII is the most sensitive component of the thylakoid membrane. The present study shows the need to use low concentrations of 2,6-dichloro-1,4-benzoquinone (DCBQ) paired with potassium ferricyanide (FeCy) for achieving the maximum O2 evolution rate, while a DCBQ concentration above certain threshold results in strong suppression of O2 evolution. The required DCBQ concentration depends on the presence of the cell wall and should be exactly ~0.1 mM or in the range of 0.2-0.4 mM for cells with and without a cell wall, respectively. The inhibition effect is caused, probably, by a higher content of DCBQ in the oxidized form inside cells; this depends on the presence of the cell wall, which influences the efficiency of DCBQ diffusion into and out of the cell, where it is maintained by FeCy in the oxidized state. The possible mechanism of DCBQ inhibition action is discussed.

Engineered Cobalt Single-Atoms@BiFeO3 Heteronanostructures for Highly Efficient Solar Water Oxidation.

Efficient charge-carrier separation and their utilization are the key factors in overcoming sluggish four-electron reaction kinetics involved in photocatalytic oxygen evolution. Here, a novel study demonstrates the significance of Na2 S2 O8 as a sacrificial agent in comparison to AgNO3 . Resultantly, BiFeO3 (BFO) and titanium doped-oxygen deficient BiFeO3 (Ti-BFO-R) nanostructures achieve ≈64 and 44.5 times higher O2 evolution in the presence of Na2 S2 O8 compared to AgNO3 as a sacrificial agent, respectively. Furthermore, the presence of Co single atoms (Co-SAs) deposited via immersion method on BFO and Ti-BFO-R nanostructures led to achieving outstanding O2 evolution at a rate of 16.11 and 23.89 mmol g-1 h-1 , respectively, which is 153 and 227.5 times higher compared to BFO (in the presence of AgNO3 ), the highest O2 evolution observed for BFO-based materials to date. The successful deposition of Co-SAs is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC HAADF-STEM) and X-ray absorption near-edge structure (XANES). The charge transfer investigations confirm the significance of Co-SAs on BFO-based photocatalysts for improved charge-carrier separation, transport, and utilization. This novel study validates the excellent role of Na2 S2 O8 as a sacrificial agent and Co-SAs as a cocatalyst for BFO-based nanostructures for efficient O2 evolution.

Rational modification of hydroxy-functionalized covalent organic frameworks for enhanced photocatalytic hydrogen peroxide evolution.

Covalent organic frameworks (COFs), a class of flexibly tunable crystalline materials, have fascinating potential in photocatalytic hydrogen peroxide (H2O2) evolution under visible light irradiation. However, achieving efficient catalytic activity by tuning the composition of COFs and the linkages of building blocks is still a challenge. Herein, four imine-linked COFs with different numbers of hydroxy-functionalized are constructed to unveil the latent structure-activity relationship between the reversibility of bonding in supramolecular chemistry and the photocatalytic H2O2 performance. As the optimized material, TAPT-HTA-COF (1H-COF) containing single hydroxy group in aldehyde node exhibits a highest ordered structure and conjugation degree along and across the plane in the extended frameworks originating from the flexibly reversible iminol-to-ketoenamine tautomerism than others, which broadens the visible light absorption and accelerates the dissociation of photogenerated carriers in 1H-COF. These merits ensure that 1H-COF has the highest H2O2 yield (44.5 µmol L-1) and O2 two-electron reduction pathway among the four COFs under visible light irradiation (λ > 420 nm, 10 vol% isopropanol aqueous solution). At the same time, the long-range ordered framework of 1H-COF is well preserved during the photocatalytic H2O2 evolution process assisted by the proton-induced tautomerization. This work facilitates the design and development of COF-based photocatalysts in the evolution of H2O2.

Cobalt-based co-ordination complex-derived nanostructure for efficient oxygen evolution reaction in acidic and alkaline medium.

Electrochemical water splitting is one of the most important method for energy conversion and storage. For this, the design and development of a low-cost robust electrocatalyst are highly desirable. In this study, Cobalt-based electrocatalyst for Oxygen Evolution Reaction was synthesized by thermal treatment of Cobalt-dehydroacetic acid (Co-DHA). The as-synthesized Co nanostructures and Co-DHA crystals were characterized with powder X-ray diffraction, X-ray photoelectron spectroscopy thermo-gravimetric analysis, and field emission scanning electron microscopy. The electrochemical O2 evolution study shows the overpotential (at 10 mV/cm-2) correspond to 294 mV vs reference hydrogen electrode (RHE) for K-300 (Co3O4@300), whereas K-500 (Co3O4@500) shows 170 mV vs RHE values in 1 M KOH solution, respectively. Similar trends have been observed for electrochemical O2 evolution studies in 0.5 M H2SO4, where K-300 and K-500 shows the overpotential (at 10mV/cm-2) of 234 mV vs RHE, and 199 mV vs RHE, respectively. The outcomes show better catalytic efficiency of K-500 as compared to K-300.

Spatially Controlled CO2 Conversion Kinetics in Natural Leaves for Motion Generation.

Living systems that can spontaneously exhibit directional motion belong to diverse classes such as bacteria, sperm and plankton. They have fascinated scientists in recent years to design completely artificial or biohybrid mobile objects. Natural ingredients, like parts of plants, have been used to elaborate miniaturized dynamic objects, which can move when they are combined with other, non-natural, building blocks. Herein, we report that the precise structural tailoring of natural plant leaves allows generating a spatially predefined and confined release of oxygen gas, due to the conversion of carbon dioxide. This constitutes the driving force for generating motion, which is solely due to the respiration of leaves by photosynthesis. The rate of gas evolution can be fine-tuned by changing the light intensity and the leaf size, allowing ultimately to control the motility of objects with dimensions ranging from the millimeter to the micrometer scale.

Construction of BiVO4/NiCo2O4 nanosheet Z-scheme heterojunction for highly boost solar water oxidation.

The sluggish water oxidation process is a severe obstacle for solar-driven water splitting. Therefore, it is imperative to develop a suitable photocatalyst with reduced energy barrier for strong oxidation. In this study, a Z-scheme BiVO4/NiCo2O4 (BVO/NCO) heterojunction system was designed by decorating ultrathin nickel-cobalt (NiCo2O4) spinel nanosheets on BiVO4 as an efficient photocatalyst for water oxidation. The unique structure of the system significantly reduced the energy barrier and improved the oxidation ability of BiVO4 to efficiently enhance the separation and transfer of the photogenerated carriers. Thus, the photocatalyst delivered an excellent O2 evolution performance of 1640.9 µmol∙g-1∙h-1 and showed 124% improved efficiency as compared to pristine BiVO4 and a quantum efficiency of 5.39% at 400 nm for O2 evolution. Additionally, the theoretical calculations revealed that the formation of *OOH was the rate-determining step for water oxidation. The decoration with NiCo2O4 significantly reduced the energy barrier between *O and *OOH, which eventually improved the photocatalytic performance of BVO/NCO. The results hold great promise for the potential application of spinel-based materials in efficient photocatalytic O2 evolution and offer fundamental insights into the design of efficient water oxidation heterojunctions.

Involvement of Carbonic Anhydrase CAH3 in the Structural and Functional Stabilization of the Water-Oxidizing Complex of Photosystem II from Chlamydomonas reinhardtii.

The involvement of carbonic anhydrases (CA) and CA activity in the functioning of photosystem II (PSII) has been studied for a long time and has been shown in many works. However, so far only for CAH3 from Chlamydomonas reinhardtii there is evidence for its association with the donor side of PSII, where the CA activity of CAH3 can influence the functioning of the water-oxidizing complex (WOC). Our results suggest that CAH3 is also involved in the organization of the native structure of WOC independently of its CA activity. It was shown that in PSII preparations from wild type (WT) the high O2-evolving activity of WOC was observed up to 100 mM NaCl in the medium and practically did not decrease with increasing incubation time with NaCl. At the same time, the WOC function in PSII preparations from CAH3-deficient mutant cia3 is significantly inhibited already at NaCl concentrations above 35 mM, reaching 50% at 100 mM NaCl and increased incubation time. It is suggested that the absence of CAH3 in PSII from cia3 causes disruption of the native structure of WOC, allowing more pronounced conformational changes of its proteins and, consequently, suppression of the WOC active center function, when the ionic strength of the medium is increased. The results of Western blot analysis indicate a more difficult removal of PsbP protein from PSII of cia3 at higher NaCl concentrations, apparently due to the changes in the intermolecular interactions between proteins of WOC in the absence of CAH3. At the same time, the values of the maximum quantum yield of PSII did not practically differ between preparations from WT and cia3, indicating no effect of CAH3 on the photoinduced electron transfer in the reaction center of PSII. The obtained results indicate the involvement of the CAH3 protein in the native organization of the WOC and, as a consequence, in the stabilization of its functional state in PSII from C. reinhardtii.

pH-induced hydrothermal synthesis of Bi2WO6 nanoplates with controlled crystal facets for switching bifunctional photocatalytic water oxidation/reduction activity.

Bifunctional photocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have attracted growing interest to understand the mechanisms governing different evolution reactions, and the bifunctional activity of a single type of crystalline photocatalyst has gained especial attention. We herein report the high photocatalytic OER and HER activities of Bi2WO6 nanoplates (BWO NPs) which are synthesized by a simple hydrothermal method, and the switchable OER and HER performances controlled by the pH value of the precursor solvent. In the pH range from 4 to 9, the thickness of BWO NPs along the [001] direction exhibits interesting dependence on the pH value, which decreases as the pH value increases. Correspondingly, the BWO NPs obtained at the pH value of 7 (BWO-7) show the highest photocatalytic OER activity, while the BWO NPs synthesized at the pH value of 9 (BWO-9) exhibit the highest photoactivity towards HER. The electronic band structure analysis indicates that the highest photocatalytic OER activity is related to the band alignment of the valence band maximum of Bi2WO6, which determines the efficient separation of photogenerated electrons and holes as well as the fast charge transfer kinetics. The crystal facet evolution resulting from thickness reduction promotes the exposure of {001} facets for HER and decreases the exposure of {100} and {010} facets for OER. This work provides new insights into the combined effects of crystal facets and electronic band structures on photocatalysis.

Suppressing Water Dissociation via Control of Intrinsic Oxygen Defects for Awakening Solar H2 O-to-H2 O2 Generation.

BiVO4 theoretically has a thermodynamic activity trend toward highly selective water oxidative H2 O2 formation, but it is more inclined to generate O2 in practical. The influence of intrinsic oxygen vacancy (Ovac ), especially, on surface reactivity, has never been considered as a possible activity loss mechanism in the synthetic BiVO4 . In this work, it is theoretically and experimentally demonstrated that the intrinsic surface Ovac is responsible for lower H2 O2 evolution activity via promoting water dissociation to form intermediate. Through an annealing process under a V2 O5 rich atmosphere, the surface Ovac can be eliminated that awakens the photoelectrochemical (PEC) water oxidative H2 O2 activity in a NaHCO3 electrolyte, which achieves an average of 58.4%, and increases by up to 4.28 times of the one annealed in air. This work offers a general understanding of catalytic activity loss and may be extended to other photo or electrocatalysts for catalytic selectivity regulation.

NIR-Driven Intracellular Photocatalytic O2 Evolution on Z-Scheme Ni3S2/Cu1.8S@HA for Hypoxic Tumor Therapy.

Hypoxia in a tumor microenvironment (TME) has inhibited the photodynamic therapy (PDT) efficacy. Here, Ni3S2/Cu1.8S nanoheterostructures were synthesized as a new photosensitizer, which also realizes the intracellular photocatalytic O2 evolution to relieve hypoxia in TME and enhance PDT as well. With the narrow band gap (below 1.5 eV), the near infrared (NIR) (808 nm) can stimulate their separation of the electron-hole. The novel Z-scheme nanoheterostructures, testified by experimental data and density functional theory (DFT) calculation, possess a higher redox ability, endowing the photoexited holes with sufficient potential to oxide H2O into O2, directly. Meanwhile, the photostimulated electrons can capture the dissolved O2 to form a toxic reactive oxygen species (ROS). Moreover, Ni3S2/Cu1.8S nanocomposites also possess the catalase-/peroxidase-like activity to convert the endogenous H2O2 into ·OH and O2, which not only cause chemodynamic therapy (CDT) but also alleviate hypoxia to assist the PDT as well. In addition, owing to the narrow band gap, they possess a high NIR harvest and great photothermal conversion efficiency (49.5%). It is noted that the nanocomposites also exhibit novel biodegradation and can be metabolized and eliminated via feces and urine within 2 weeks. The present single electrons in Ni/Cu ions induce the magnetic resonance imaging (MRI) ability for Ni3S2/Cu1.8S. To make sure that the cancer cells were specifically targeted, hyaluronic acid (HA) was grafted outside and Ni3S2/Cu1.8S@HA integrated photodynamic therapy (PDT), chemodynamic therapy (CDT), and photothermal therapy (PTT) to exhibit the great anticancer efficiency for hypoxic tumor elimination.

Cell size influences inorganic carbon acquisition in artificially selected phytoplankton.

Cell size influences the rate at which phytoplankton assimilate dissolved inorganic carbon (DIC), but it is unclear whether volume-specific carbon uptake should be greater in smaller or larger cells. On the one hand, Fick's Law predicts smaller cells to have a superior diffusive CO2 supply. On the other, larger cells may have greater scope to invest metabolic energy to upregulate active transport per unit area through CO2 -concentrating mechanisms (CCMs). Previous studies have focused on among-species comparisons, which complicates disentangling the role of cell size from other covarying traits. In this study, we investigated the DIC assimilation of the green alga Dunaliella tertiolecta after using artificial selection to evolve a 9.3-fold difference in cell volume. We compared CO2 affinity, external carbonic anhydrase (CAext ), isotopic signatures (δ13 C) and growth among size-selected lineages. Evolving cells to larger sizes led to an upregulation of CCMs that improved the DIC uptake of this species, with higher CO2 affinity, higher CAext and higher δ13 C. Larger cells also achieved faster growth and higher maximum biovolume densities. We showed that evolutionary shifts in cell size can alter the efficiency of DIC uptake systems to influence the fitness of a phytoplankton species.