The adaptive mechanisms of the marine diatom Thalassiosira weissflogii to long-term high CO2 and warming.

While it is known that increased dissolved CO2 concentrations and rising sea surface temperature (ocean warming) can act interactively on marine phytoplankton, the ultimate molecular mechanisms underlying this interaction on a long-term evolutionary scale are relatively unexplored. Here, we performed transcriptomics and quantitative metabolomics analyses, along with a physiological trait analysis, on the marine diatom Thalassiosira weissflogii adapted for approximately 3.5 years to warming and/or high CO2 conditions. We show that long-term warming has more pronounced impacts than elevated CO2 on gene expression, resulting in a greater number of differentially expressed genes (DEGs). The largest number of DEGs was observed in populations adapted to warming + high CO2, indicating a potential synergistic interaction between these factors. We further identified the metabolic pathways in which the DEGs function and the metabolites with significantly changed abundances. We found that ribosome biosynthesis-related pathways were upregulated to meet the increased material and energy demands after warming or warming in combination with high CO2. This resulted in the upregulation of energy metabolism pathways such as glycolysis, photorespiration, the tricarboxylic acid cycle, and the oxidative pentose phosphate pathway, as well as the associated metabolites. These metabolic changes help compensate for reduced photochemical efficiency and photosynthesis. Our study emphasizes that the upregulation of ribosome biosynthesis plays an essential role in facilitating the adaptation of phytoplankton to global ocean changes and elucidates the interactive effects of warming and high CO2 on the adaptation of marine phytoplankton in the context of global change.

Zirconium-Catalyzed Synthesis of 6-(Trifluoromethyl)-2H-pyran-2-ones via C-C Bond Cleavage.

A strategy for the annulation reaction of alkynones with ethyl 4,4,4-trifluoro-3-oxobutanoate through C-C bond cleavage is described. The zirconium-catalyzed transformation provides access to a wide range of structurally diverse 6-(trifluoromethyl)-2H-pyran-2-ones in moderate to good yields, utilizing Na2CO3 as a base. Further transformations into trifluoromethylated arene derivatives have been demonstrated as well. Furthermore, plausible reaction pathways are proposed by conducting various control experiments and isolating a ß-diketone intermediate (X-ray) containing an intramolecular hydrogen bond.

Copper Loading-Controlled Selective Synthesis of 2,5-Bis(trifluoromethyl) and Monotrifluoromethyl-Substituted Oxazoles.

A general domino annulation reaction of sulfonylmethyl isocyanide with trifluoroacetic anhydride in the presence of copper chloride as an additive is developed. The reaction affords 2,5-bis(trifluoromethyl)oxazoles in modest to good yields under mild conditions. A wide variety of sulfonylmethyl isocyanide and perfluorocarboxylic anhydride substrates are amenable to this transformation. Under a higher copper salt loading conditions, the reaction led to the formation of monotrifluoromethyl-substituted oxazole product.

DNA methylation and gene transcription act cooperatively in driving the adaptation of a marine diatom to global change.

Genetic changes together with epigenetic modifications such as DNA methylation have been demonstrated to regulate many biological processes and thereby govern the response of organisms to environmental changes. However, how DNA methylation might act cooperatively with gene transcription and thereby mediate the long-term adaptive responses of marine microalgae to global change is virtually unknown. Here we performed a transcriptomic analysis, and a whole-genome bisulfite sequencing, along with phenotypic analysis of a model marine diatom Phaeodactylum tricornutum adapted for 2 years to high CO2 and/or warming conditions. Our results show that the methylated islands (peaks of methylation) mCHH were positively correlated with expression of genes in the subregion of the gene body when the populations were grown under high CO2 or its combination with warming for ~2 years. We further identified the differentially expressed genes (DEGs), and hence the metabolic pathways in which they function, at the transcriptomics level in differentially methylated regions (DMRs). Although DEGs in DMRs contributed only 18-24% of the total DEGs, we found that those DEGs acted cooperatively with DNA methylation and then regulated key processes such as central carbon metabolism, amino acid metabolism, ribosome biogenesis, terpenoid backbone biosynthesis, and degradation of misfolded proteins. Taken together, by integrating transcriptomic, epigenetic, and phenotypic analysis, our study provides evidence for DNA methylation acting cooperatively with gene transcription to contribute to the adaptation of microalgae to global changes.

Multi-trait analysis reveals large interspecific differences for phytoplankton in response to thermal change.

Understanding the responses of multiple traits in phytoplankton, and identifying interspecific variabilities to thermal changes is crucial for predicting the impacts of ocean warming on phytoplankton distributions and community structures in future scenarios. Here, we applied a trait-based approach by examining the patterns in multi-traits variations (eight traits) and interspecific variabilities in five phytoplankton species (two diatoms, three dinoflagellates) in response to a wide range of ecologically relevant temperatures (14-30 °C). Our results show large inter-traits and interspecific variabilities of thermal reaction norms in all of the tested traits. We also found that the interspecific variability exceeded the variations induced by thermal changes. Constrained variations and trade-offs between traits both revealed substantial interspecific differences and shifted as the temperature changed. Our study helps to understand the species-specific response patterns of multiple traits to ocean warming and to investigate the implications of these responses in the context of global change.

Long-term adaptation to elevated temperature but not CO2 alleviates the negative effects of ultraviolet-B radiation in a marine diatom.

Multifaceted changes in marine environments as a result of anthropogenic activities are likely to have a compounding impact on the physiology of marine phytoplankton. Most studies on the combined effects of rising pCO2, sea surface temperature, and UVB radiation on marine phytoplankton were only conducted in the short-term, which does not allow to test the adaptive capacity of phytoplankton and associated potential trade-offs. Here, we investigated populations of the diatom Phaeodactylum tricornutum that were long-term (∼3.5 years, ∼3000 generations) adapted to elevated CO2 and/or elevated temperatures, and their physiological responses to short-term (∼2 weeks) exposure of two levels of ultraviolet-B (UVB) radiation. Our results showed that while elevated UVB radiation showed predominantly negative effects on the physiological performance of P. tricornutum regardless of adaptation regimes. Elevated temperature alleviated these effects on most of the measured physiological parameters (e.g., photosynthesis). We also found that elevated CO2 can modulate these antagonistic interactions, and conclude that long-term adaptation to sea surface warming and rising CO2 may alter this diatom's sensitivity to elevated UVB radiation in the environment. Our study provides new insights into marine phytoplankton's long-term responses to the interplay of multiple environmental changes driven by climate change.

Response mechanism of harmful algae Phaeocystis globosa to ocean warming and acidification.

Simultaneous ocean warming and acidification will alter marine ecosystem structure and directly affect marine organisms. The alga Phaeocystis globosa commonly causes harmful algal blooms in coastal areas of eastern China. P. globosa often outcompetes other species due to its heterotypic life cycle, primarily including colonies and various types of solitary cells. However, little is known about the adaptive response of P. globosa to ocean warming and acidification. This study aimed to reveal the global molecular regulatory networks implicated in the response of P. globosa to simultaneous warming and acidification. After exposure to warming and acidification, the phosphatidylinositol (PI) and mitogen-activated protein kinase (MAPK) signaling pathways of P. globosa were activated to regulate other molecular pathways in the cell, while the light harvesting complex (LHC) genes were downregulated to decrease photosynthesis. Exposure to warming and acidification also altered the intracellular energy flow, with more energy allocated to the TCA cycle rather than to the biosynthesis of fatty acids and hemolytic substances. The upregulation of genes associated with glycosaminoglycan (GAG) degradation prevented the accumulation of polysaccharides, which led to a reduction in colony formation. Finally, the upregulation of the Mre11 and Rad50 genes in response to warming and acidification implied an increase in meiosis, which may be used by P. globosa to increase the number of solitary cells. The increase in genetic diversity through sexual reproduction may be a strategy of P. globosa that supports rapid response to complex environments. Thus, the life cycle of P. globosa underwent a transition from colonies to solitary cells in response to warming and acidification, suggesting that this species may be able to rapidly adapt to future climate changes through life cycle transitions.

Inhibitory effects of Ipomoea cairica extracts on the harmful algae Phaeocystis globosa.

Ipomoea cairica (L.) Sweet is an invasive plant that cause serious invasion and damage in South China. Phaeocystis globosa is a common harmful algal bloom species on the southeast coast of China. Both species cause great environmental disturbances and serious economic damage to the localregion. This study explored the potential inhibitory effects of I. cairica leaf extracts on P. globosa. The results showed that solitary cells growth was inhibited at extract concentrations higher than 0.25 % (v/v). Although the colony diameter did not change, and the colony number increased rapidly in the first 36 h, we found that cells in the colonies had been damaged using scanning electron microscope and SYTOX-Green staining at 48 h. In addition, the rapid light-response curve of cells treated with extracts decreased, along with down-regulation of photosynthesis-related genes (psbA, psbD, and rbcL), suggesting damage to the photosynthetic system. Finally, the activities of antioxidant enzymes including superoxide dismutase, peroxidase, and catalase increased with increasing treatment time, indicating that cells activate antioxidant enzyme defense systems to alleviate the production of reactive oxygen species (ROS). Increased ROS levels disrupt cell membranes, alter cellular ultrastructures, and ultimately lead to cell death. This study not only achieved the reuse of invasive plant resources, but also demonstrated that I. cairica leaf extract has potential value as an algaecide.

Adaptation of a marine diatom to ocean acidification increases its sensitivity to toxic metal exposure.

Most previous studies investigating the interplay of ocean acidification (OA) and heavy metal on marine phytoplankton were only conducted in short-term, which may provide conservative estimates of the adaptive capacity of them. Here, we examined the physiological responses of long-term (~900 generations) OA-adapted and non-adapted populations of the diatom Phaeodactylum tricornutum to different concentrations of the two heavy metals Cd and Cu. Our results showed that long-term OA selected populations exhibited significantly lower growth and reduced photosynthetic activity than ambient CO2 selected populations at relatively high heavy metal levels. Those findings suggest that the adaptations to high CO2 results in an increased sensitivity of the marine diatom to toxic metal exposure. This study provides evidence for the costs and the cascading consequences associated with the adaptation of phytoplankton to elevated CO2 conditions, and improves our understanding of the complex interactions of future OA and heavy metal pollution in marine waters.

Increased genetic diversity loss and genetic differentiation in a model marine diatom adapted to ocean warming compared to high CO2.

Although high CO2 and warming could act interactively on marine phytoplankton, little is known about the molecular basis for this interaction on an evolutionary scale. Here we explored the adaptation to high CO2 in combination with warming in a model marine diatom Phaeodactylum tricornutum. Whole-genome re-sequencing identifies, in comparison to populations grown under control conditions, a larger genetic diversity loss and a higher genetic differentiation in the populations adapted for 2 years to warming than in those adapted to high CO2. However, this diversity loss was less under high CO2 combined with warming, suggesting that the evolution driven by warming was constrained by high CO2. By integrating genomics, transcriptomics, and physiological data, we found that the underlying molecular basis for this constraint is associated with the expression of genes involved in some key metabolic pathways or biological processes, such as the glyoxylate pathway, amino acid and fatty acid metabolism, and diel variability. Our results shed new light on the evolutionary responses of marine phytoplankton to multiple environmental changes in the context of global change and provide new insights into the molecular basis underpinning interactions among those multiple drivers.

Additive impacts of ocean acidification and ambient ultraviolet radiation threaten calcifying marine primary producers.

Ocean acidification (OA) represents a threat to marine organisms and ecosystems. However, OA rarely exists in isolation but occurs concomitantly with other stressors such as ultraviolet radiation (UVR), whose effects have been neglected in oceanographical observations. Here, we perform a quantitative meta-analysis based on 373 published experimental assessments from 26 studies to examine the combined effects of OA and UVR on marine primary producers. The results reveal predominantly additive stressor interactions (69-84% depending on the UV waveband), with synergistic and antagonistic interactions being rare but significantly different between micro- and macro-algae. In microalgae, variations in interaction type frequencies are related to cell volume, with antagonistic interactions accounting for a higher proportion in larger sized species. Despite additive interactions being most frequent, the small proportion of antagonistic interactions appears to have a stronger power, leading to neutral effects of OA in combination with UVR. High levels of UVR at near in situ conditions in combination with OA showed additive inhibition of calcification, but not when UVR was low. The results also reveal that the magnitude of responses is strongly dependent on experimental duration, with the negative effects of OA on calcification and pigmentation being buffered and amplified by increasing durations, respectively. Tropical primary producers were more vulnerable to OA or UVR alone compared to conspecifics from other climatic regions. Our analysis highlights that further multi-stressor long-term adaptation experiments with marine organisms of different cell volumes (especially microalgae) from different climatic regions are needed to fully disclose future impacts of OA and UVR.

A reduction in metabolism explains the tradeoffs associated with the long-term adaptation of phytoplankton to high CO2 concentrations.

Phytoplankton are responsible for nearly half of global primary productivity and play crucial roles in the Earth's biogeochemical cycles. However, the long-term adaptive responses of phytoplankton to rising CO2 remains unknown. Here we examine the physiological and proteomics responses of a marine diatom, Phaeodactylum tricornutum, following long-term (c. 900 generations) selection to high CO2 conditions. Our results show that this diatom responds to long-term high CO2 selection by downregulating proteins involved in energy production (Calvin cycle, tricarboxylic acid cycle, glycolysis, oxidative pentose phosphate pathway), with a subsequent decrease in photosynthesis and respiration. Nearly similar extents of downregulation of photosynthesis and respiration allow the high CO2 -adapted populations to allocate the same fraction of carbon to growth, thereby maintaining their fitness during the long-term high CO2 selection. These results indicate an important role of metabolism reduction under high CO2 and shed new light on the adaptive mechanisms of phytoplankton in response to climate change.

Lipid Remodeling Reveals the Adaptations of a Marine Diatom to Ocean Acidification.

Ocean acidification is recognized as a major anthropogenic perturbation of the modern ocean. While extensive studies have been carried out to explore the short-term physiological responses of phytoplankton to ocean acidification, little is known about their lipidomic responses after a long-term ocean acidification adaptation. Here we perform the lipidomic analysis of a marine diatom Phaeodactylum tricornutum following long-term (∼400 days) selection to ocean acidification conditions. We identified a total of 476 lipid metabolites in long-term high CO2 (i.e., ocean acidification condition) and low CO2 (i.e., ambient condition) selected P. tricornutum cells. Our results further show that long-term high CO2 selection triggered substantial changes in lipid metabolites by down- and up-regulating 33 and 42 lipid metabolites. While monogalactosyldiacylglycerol (MGDG) was significantly down-regulated in the long-term high CO2 selected conditions, the majority (∼80%) of phosphatidylglycerol (PG) was up-regulated. The tightly coupled regulations (positively or negatively correlated) of significantly regulated lipid metabolites suggest that the lipid remodeling is an organismal adaptation strategy of marine diatoms to ongoing ocean acidification. Since the composition and content of lipids are crucial for marine food quality, and these changes can be transferred to high trophic levels, our results highlight the importance of determining the long-term adaptation of lipids in marine producers in predicting the ecological consequences of climate change.

Adaptation of a marine diatom to ocean acidification and warming reveals constraints and trade-offs.

Ocean acidification and warming are recognized as two major anthropogenic perturbations of the modern ocean. However, little is known about the adaptive response of phytoplankton to them. Here we examine the adaptation of a marine diatom Thalassiosira weissflogii to ocean acidification in combination with ocean warming. Our results show that ocean warming have a greater effect than acidification on the growth of T. weissflogii over the long-term selection experiment (~380 generations), as well as many temperature response traits (e.g., optimum temperatures for photosynthesis, maximal net photosynthetic oxygen evolution rates, activation energy) in thermal reaction norm. These results suggest that ocean warming is the main driver for the evolution of the marine diatom T. weissflogii, rather than oceanacidification. However, the evolution resulting from warming can be constrained by ocean acidification, where ocean warming did not impose any effects at high CO2 level. Furthermore, adaptations to ocean warming alone or to the combination of ocean acidification and warming come with trade-offs by inhibiting photochemical performances. The constrains and trade-offs associated with the adaptation to ocean acidification and warming demonstrated in this study, should be considered for parameterizing evolutionary responses in eco-evolutionary models of phytoplankton dynamics in a future ocean.

Mn-Fe3O4 nanoparticles anchored on the urushiol functionalized 3D-graphene for the electrochemical detection of 4-nitrophenol.

Preparation of highly active and cost-effective electrode materials is of great interest in electrochemical detection. In this study, a simple urushiol-templated solvothermal method combined with calcination was proposed to fabricate N-doped three-dimensional graphene (3D-G) with Mn-doped Fe3O4 nanoparticles loaded on the surface (Mn-Fe3O4/3D-G). Because of the large active surface area, porous channel and high loading ratio of Mn-Fe3O4 nanoparticles, as-prepared Mn-Fe3O4/3D-G sensor showed high activity on the determination of 4-nitrophenol (4-NP), which are much improved from the control un-modified samples. The wide linear concentration range (5-100 µM), low detection limit (19 nM) and satisfactory recovery of 4-NP in various water samples (98.38-100.41%) indicated that the Mn-Fe3O4/3D-G electrode can be potentially used for real-world applications. This study gives a simple but meaningful strategy for constructing transition metal oxide/graphene composite materials with high electrocatalytic activity.

A thermoreversible crosslinking hot-melt adhesive: reversibility and performance.

The need to improve the environmental friendliness and achieve the recycling of resins is an ongoing process for hot-melt adhesive technology. In this work, a new type of thermoreversible crosslinking hot-melt adhesive-based Diels Alder (DA) reaction was prepared. The critical idea was to efficiently initiate the esterification to yield furoic acid (FA)-grafted poly(vinyl alcohol) (PVA-g-FA), and then PVA-g-FA was mixed with N,N'-(4,4'-methylenediphenyl)dimaleimide (MDI) to finally obtain the thermoreversible crosslinking adhesive (PVA-g-FA/MDI). The experimental results indicated that the reversibility of the DA reaction between the furan rings and the maleimide groups allowed PVA-g-FA/MDI to be dynamically crosslinked. It was able to crosslink at a temperature of 80 °C and decrosslink at 120 °C. Moreover, the performances of hot-melt adhesive were investigated. The PVA-g-FA/MDI had a better peeling strength (43.33 N mm-1), bond strength (11.84 MPa), and thermal conductivity (0.263 W m-1 K-1) than PVA resins. The light-transmittance and haze value were 52.8% and 12.24‰, respectively. The PVA-g-FA/MDI resin could be reused more than two times.

Light alters the responses of two marine diatoms to increased warming.

In this study, we examined the effects of increased temperature (15, 20 and 25 °C) and different light levels (50, 200 µmol photons m-2 s-1) on two widely distributed diatoms, namely Phaeodactylum tricornutum and Thalassiosira weissflogii. Results showed that increasing light level counteracted the negative effects of high temperature on photosynthesis in both species, suggesting an antagonistic interaction between light and temperature. Contrary to the above results, light limitation diminished the temperature-sensitivity of carbonic anhydrase activity in two diatoms. We also observed species-specific responses of biomass, where increased temperature significantly decreased the biomass of P. tricornutum at both low and high light levels but showed no effects on T. weissflogii. Our study demonstrated that light can alter the physiological responses of diatoms to temperature but also revealed interspecific variations. We predict that in the future ocean with shallower upper mixed layer, T. weissflogii may be more competitive than P. tricornutum.

A photo-reversible crosslinking resin for additive manufacturing: reversibility and performance.

Improving the adhesion between layers and achieving the recycling of resins are challenges in additive manufacturing (AM) technology. In this work, a new type of photo-reversible crosslinking resin based on polyvinyl alcohol (PVA) and coumarin (HMC) was prepared via grafting reaction. The critical idea was to create a coumarin based photo-reversible crosslinking resin by carefully tailoring the photo-crosslinking time and temperature, so that the resin could be extruded through the nozzle and then maintain the proper shape during UV-curing. Photo-reversible crosslinking of AM resin was realized without the use of monomers, photo-initiators or propagating. A reasonable irradiation time with 354 nm (crosslink) or 254 nm UV light (cleavage) of 10 min was critical for photo-reversible crosslinking of PVA-g-HMC at 120 °C. An important result of this work was that the developed photo-reversible crosslinked resin could be reused and the printed resin exhibits excellent adhesion properties, thermal conductivity and oxygen barrier performance.

Responses of carbonic anhydrases and Rubisco to abrupt CO2 changes of seawater in two marine diatoms.

Diatoms are experiencing striking fluctuations in seawater carbonate chemistry in the natural marine environment, especially in coastal seawaters. Here, we show that the diatoms Thalassiosira weissflogii and Phaeodactylum tricornutum, which utilize different carbon acquisition mechanisms, respond differently to short-term changes in seawater carbonate chemistry. Our results showed that T. weissflogii showed significantly higher photosynthetic oxygen evolution rates than that of P. tricornutum at low levels of CO2 or HCO3-. This suggests that T. weissflogii had higher affinities for CO2 or HCO3- when their concentrations were not sufficient to support saturated growth and photosynthesis. While the activity of Rubisco in P. tricornutum positively correlated with carbonic anhydrases (CA), we observed negative relationship between Rubisco and CA activity in the diatom T. weissflogii. These contrasting physiological responses of diatoms with varied carbon acquisition mechanisms indicate different abilities to cope up with abrupt changes in seawater carbonate chemistry. We propose that the ability to respond to varying carbonate chemistry may act as one determinant of the diatom distributions and phytoplankton community structures.

Effective adsorption of nickel (II) with Ulva lactuca dried biomass: isotherms, kinetics and mechanisms.

This study aimed to evaluate the Ni2+ ions adsorption capability of Ulva lactuca. The isotherms, kinetics and mechanisms for the adsorption of Ni2+ from aqueous solution by Ulva lactuca were also investigated. Influencing factors including initial pH, initial Ni2+ concentration, biomass, contact time were examined. The results indicate that the maximum Ni2+ adsorption capacity of 38.28 mg/g was obtained at pH 5, initial Ni2+ concentration 250 mg/L, biomass dosage 0.5 g/L and contact time 30 min. The adsorption can be well fitted with Langmuir isotherm, and the kinetics were well described by the pseudo-second-order model. The parameters of thermodynamics verified that Ni2+ adsorption on Ulva lactuca was a spontaneous and endothermic process. Analyses of FT-IR, SEM-EDS and XPS indicate that carboxyl and hydroxyl groups on the surface of biomass are involved in Ni2+ adsorption. The dried biomass of Ulva lactuca can be a cost-effective and eco-friendly adsorbent for the removal of Ni2+ from wastewater.