Phytoplankton-derived zwitterionic gonyol and dimethylsulfonioacetate interfere with microbial dimethylsulfoniopropionate sulfur cycling.

The marine sulfur cycle is substantially fueled by the phytoplankton osmolyte dimethylsulfoniopropionate (DMSP). This metabolite can be metabolized by bacteria, which results in the emission of the volatile sulfur species methanethiol (MeSH) and the climate-cooling dimethylsulfide (DMS). It is generally accepted that bacteria contribute significantly to DMSP turnover. We show that the other low molecular weight zwitterionic dimethylsulfonio compounds dimethylsulfonioacetate (DMSA) and gonyol are also widely distributed in phytoplankton and can serve as alternative substrates for volatile production. DMSA was found in 11 of the 16 surveyed phytoplankton species, and gonyol was detected in all haptophytes and dinoflagellates. These prevalent zwitterions are also metabolized by marine bacteria. The patterns of bacterial MeSH and DMS release were dependent on the zwitterions present. Certain bacteria metabolize DMSA and gonyol and release MeSH, in others gonyol inhibited DMS-producing enzymes. If added in addition to DMSP, gonyol entirely inhibited the formation of volatiles in Ruegeria pomeroyi. In contrast, no substantial effect of this compound was observed in the DMSP metabolism of Halomonas sp. We argue that the production of DMSA and gonyol and their inhibitory properties on the release of volatiles from DMSP has the potential to modulate planktonic sulfur cycling between species.

The metabolite dimethylsulfoxonium propionate extends the marine organosulfur cycle.

Algae produce massive amounts of dimethylsulfoniopropionate (DMSP), which fuel the organosulfur cycle1,2. On a global scale, several petagrams of this sulfur species are produced annually, thereby driving fundamental processes and the marine food web1. An important DMSP transformation product is dimethylsulfide, which can be either emitted to the atmosphere3,4 or oxidized to dimethylsulfoxide (DMSO) and other products5. Here we report the discovery of a structurally unusual metabolite, dimethylsulfoxonium propionate (DMSOP), that is synthesized by several DMSP-producing microalgae and marine bacteria. As with DMSP, DMSOP is a low-molecular-weight zwitterionic metabolite that carries both a positively and a negatively charged functional group. Isotope labelling studies demonstrate that DMSOP is produced from DMSP, and is readily metabolized to DMSO by marine bacteria. DMSOP was found in near nanomolar amounts in field samples and in algal culture media, and thus represents-to our knowledge-a previously undescribed biogenic source for DMSO in the marine environment. The estimated annual oceanic production of oxidized sulfur from this pathway is in the teragram range, similar to the calculated dimethylsulfide flux to the atmosphere3. This sulfoxonium metabolite is therefore a key metabolite of a previously undescribed pathway in the marine sulfur cycle. These findings highlight the importance of DMSOP in the marine organosulfur cycle.

Automated Quantification of Early Bone Alterations and Pathological Bone Turnover in Experimental Arthritis by in vivo PET/CT Imaging.

The assessment of bone damage is required to evaluate disease severity and treatment efficacy both in arthritis patients and in experimental arthritis models. Today there is still a lack of in vivo methods that enable the quantification of arthritic processes at an early stage of the disease. We performed longitudinal in vivo imaging with [18F]-fluoride PET/CT before and after experimental arthritis onset for diseased and control DBA/1 mice and assessed arthritis progression by clinical scoring, tracer uptake studies and bone volume as well as surface roughness measurements. Arthritic animals showed significantly increased tracer uptake in the paws compared to non-diseased controls. Automated CT image analysis revealed increased bone surface roughness already in the earliest stage of the disease. Moreover, we observed clear differences between endosteal and periosteal sites of cortical bone regarding surface roughness. This study shows that in vivo PET/CT imaging is a favorable method to study arthritic processes, enabling the quantification of different aspects of the disease like pathological bone turnover and bone alteration. Especially the evaluation of bone surface roughness is sensitive to early pathological changes and can be applied to study the dynamics of bone erosion at different sites of the bones in an automated fashion.

Synchronized regulation of different zwitterionic metabolites in the osmoadaption of phytoplankton.

The ability to adapt to different seawater salinities is essential for cosmopolitan marine phytoplankton living in very diverse habitats. In this study, we examined the role of small zwitterionic metabolites in the osmoadaption of two common microalgae species Emiliania huxleyi and Prorocentrum minimum. By cultivation of the algae under salinities between 16‰ and 38‰ and subsequent analysis of dimethylsulfoniopropionate (DMSP), glycine betaine (GBT), gonyol, homarine, trigonelline, dimethylsulfonioacetate, trimethylammonium propionate, and trimethylammonium butyrate using HPLC-MS, we could reveal two fundamentally different osmoadaption mechanisms. While E. huxleyi responded with cell size reduction and a nearly constant ratio between the major metabolites DMSP, GBT and homarine to increasing salinity, osmolyte composition of P. minimum changed dramatically. In this alga DMSP concentration remained nearly constant at 18.6 mM between 20‰ and 32‰ but the amount of GBT and dimethylsulfonioacetate increased from 4% to 30% of total investigated osmolytes. Direct quantification of zwitterionic metabolites via LC-MS is a powerful tool to unravel the complex osmoadaption and regulation mechanisms of marine phytoplankton.

Investigations of the uptake of dimethylsulfoniopropionate by phytoplankton.

No change here: Analysis with doubly labeled [(13)C(2)D(6)]DMSP and LC/MS revealed that dissolved DMSP is taken up and stored intracellularly by diverse phytoplankton species without transformation. This is even true for species that produce no quantifiable amounts of DMSP themselves.