Non-structural carbohydrate pools in a tropical forest

The pool size of mobile, i.e. non-structural carbohydrates (NSC) in trees reflects the balance between net photosynthetic carbon uptake (source) and irreversible investments in structures or loss of carbon (sink). The seasonal variation of NSC concentration should reflect the sink/source relationship, provided all tissues from root to crown tops are considered. Using the Smithsonian canopy crane in Panama we studied NSC concentrations in a semi-deciduous tropical forest over 22months. In the 9 most intensively studied species (out of the 17 investigated), we found higher NSC concentrations (starch, glucose, fructose, sucrose) across all species and organs in the dry season than in the wet season (NSC 7.2% vs 5.8% of dry matter in leaves, 8.8/6.0 in branches, 9.7/8.5 in stems, 8.3/6.4 in coarse and 3.9/2.2 in fine roots). Since this increase was due to starch only, we attribute this to drought-constrained growth (photosynthesis less affected by drought than sink activity). Species-specific phenological rhythms (leafing or fruiting) did not overturn these seasonal trends. Most of the stem volume (diameter at breast height around 40cm) stores NSC. We present the first whole forest estimate of NSC pool size, assuming a 200tha−1 forest biomass: 8% of this i.e. ca. 16tha−1 is NSC, with ca. 13tha−1 in stems and branches, ca. 0.5 and 2.8tha−1 in leaves and roots. Starch alone (ca. 10.5tha−1) accounts for far more C than would be needed to replace the total leaf canopy without additional photosynthesis. NSC never passed through a period of significant depletion. Leaf flushing did not draw heavily upon NSC pools. Overall, the data imply a high carbon supply status of this forest and that growth during the dry season is not carbon limited. Rather, water shortage seems to limit carbon investment (new tissue formation) directly, leaving little leeway for a direct CO2 fertilization effect

Multiband emission from single β-NaYF4(Yb,Er) nanoparticles at high excitation power densities and comparison to ensemble studies

Ensemble and single particle studies of the excitation power density (P)-dependent upconversion luminescence (UCL) of core and core-shell β-NaYF4:Yb,Er upconversion nanoparticles (UCNPs) doped with 20% Yb3+ and 1% or 3% Er3+ performed over a P regime of 6 orders of magnitude reveal an increasing contribution of the emission from high energy Er3+ levels at P > 1 kW/cm2. This changes the overall emission color from initially green over yellow to white. While initially the green and with increasing P the red emission dominate in ensemble measurements at P < 1 kW/cm2, the increasing population of higher Er3+ energy levels by multiphotonic processes at higher P in single particle studies results in a multitude of emission bands in the ultraviolet/visible/near infrared (UV/vis/NIR) accompanied by a decreased contribution of the red luminescence. Based upon a thorough analysis of the P-dependence of UCL, the emission bands activated at high P were grouped and assigned to 2–3, 3–4, and 4 photonic processes involving energy transfer (ET), excited-state absorption (ESA), cross-relaxation (CR), back energy transfer (BET), and non-radiative relaxation processes (nRP). This underlines the P-tunability of UCNP brightness and color and highlights the potential of P-dependent measurements for mechanistic studies required to manifest the population pathways of the different Er3+ levels.Peer Reviewe

Efficient Luminescent Solar Concentrators Based on Environmentally Friendly Cd‐Free Ternary AIS/ZnS Quantum Dots

Luminescent solar concentrators (LSC) allow to obtain renewable energy from building integrated photovoltaic systems. As promising efficient and long-term stable LSC fluorophores semiconductor nanocrystals like quantum dots (QDs) with size and composition tunable optoelectronic properties have recently emerged. The most popular II/VI or IV/VI semiconductor QDs contain, however, potentially hazardous cadmium or lead ions, which is a bottleneck for commercial applications. A simple aqueous based, microwave-assisted synthesis for environmentally friendly and highly emissive AgInS2/ZnS QDs is developed using 3-mercaptopropionic acid (MPA) and glutathione (GSH) and their incorporation into polylaurylmethacrylate (PLMA) polymer slabs integrable in LSC devices (10.4 × 10.4 × 0.2 cm3, G = 12.98). With this simple approach, optical power efficiencies (OPE) of 3.8% and 3.6% and optical quantum efficiencies (OQE) of 24.1% and 27.4% are obtained, which are among the highest values yet reported.German Research CouncilEuropean Union's Horizon 2020Marie Sklodowska‐CurieDeutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659Peer Reviewe

Absolute photoluminescence quantum yields of IR26 and IR-emissive Cd₁₋ₓHgₓTe and PbS quantum dots: method- and material-inherent challenges

Bright emitters with photoluminescence in the spectral region of 800–1600 nm are increasingly important as optical reporters for molecular imaging, sensing, and telecommunication and as active components in electrooptical and photovoltaic devices. Their rational design is directly linked to suitable methods for the characterization of their signal-relevant properties, especially their photoluminescence quantum yield (Φf ). Aiming at the development of bright semiconductor nanocrystals with emission >1000 nm, we designed a new NIR/IR integrating sphere setup for the wavelength region of 600–1600 nm. We assessed the performance of this setup by acquiring the corrected emission spectra and Φf of the organic dyes |trybe, IR140, and IR26 and several infrared (IR)-emissive Cd₁₋ₓHgₓTe and PbS semiconductor nanocrystals and comparing them to data obtained with two independently calibrated fluorescence instruments absolutely or relative to previously evaluated reference dyes. Our results highlight special challenges of photoluminescence studies in the IR ranging from solvent absorption to the lack of spectral and intensity standards together with quantum dot-specific challenges like photobrightening and photodarkening and the size-dependent air stability and photostability of differently sized oleate-capped PbS colloids. These effects can be representative of lead chalcogenides. Moreover, we redetermined the Φf of IR26, the most frequently used IR reference dye, to 1.1 × 10⁻³ in 1,2-dichloroethane DCE with a thorough sample reabsorption and solvent absorption correction. Our results indicate the need for a critical reevaluation of Φf values of IR-emissive nanomaterials and offer guidelines for improved Φf measurements

Particle-size-dependent upconversion luminescence of NaYF4: Yb, Er nanoparticles in organic solvents and water at different excitation power densities

A systematic study of the luminescence properties of monodisperse beta-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12-43 nm is presented utilizing steady-state and time-resolved fluorometry. Special emphasis was dedicated to the absolute quantification of size- and environment-induced quenching of upconversion luminescence (UCL) by high-energy O-H and C-H vibrations from solvent and ligand molecules at different excitation power densities (P). In this context, the still-debated population pathways of the F-4(9/2) energy level of Er3+ were examined. Our results highlight the potential of particle size and P value for color tuning based on the pronounced near-infrared emission of 12 nm UCNPs, which outweighs the red Er3+ emission under "strongly quenched" conditions and accounts for over 50% of total UCL in water. Because current rate equation models do not include such emissions, the suitability of these models for accurately simulating all (de)population pathways of small UCNPs must be critically assessed. Furthermore, we postulate population pathways for the F-4(9/2) energy level of Er3+, which correlate with the size-, environment-, and P-dependent quenching states of the higher Er3+ energy levels

Yb,Nd,Er-doped upconversion nanoparticles: 980 nm versus 808 nm excitation

Yb,Nd,Er-doped upconversion nanoparticles (UCNPs) have attracted considerable interest as luminescent reporters for bioimaging, sensing, energy conversion/shaping, and anticounterfeiting due to their capability to convert multiple near-infrared (NIR) photons into shorter wavelength ultraviolet, visible or NIR luminescence by successive absorption of two or more NIR photons. This enables optical measurements in complex media with very little background and high penetration depths for bioimaging. The use of Nd3+ as substitute for the commonly employed sensitizer Yb3+ or in combination with Yb3+ shifts the excitation wavelength from about 980 nm, where the absorption of water can weaken upconversion luminescence, to about 800 nm, and laser-induced local overheating effects in cells, tissue, and live animal studies can be minimized. To systematically investigate the potential of Nd3+ doping, we assessed the performance of a set of similarly sized Yb3+,Nd3+,Er3+-doped core- and core-shell UCNPs of different particle architecture in water at broadly varied excitation power densities (P) with steady state and time-resolved fluorometry for excitation at 980 nm and 808 nm. As a measure for UCNPs performance, the P-dependent upconversion quantum yield (phi(UC)) and its saturation behavior were used as well as particle brightness (B-UC). Based upon spectroscopic measurements at both excitation wavelengths in water and in a lipid phantom and B-UC-based calculations of signal size at different penetration depths, conditions under which excitation at 808 nm is advantageous are derived and parameters for the further optimization of triple-doped UCNPs are given

Novel exported fusion enzymes with chorismate mutase and cyclohexadienyl dehydratase activity: Shikimate pathway enzymes teamed up in no man's land

Chorismate mutase (CM) and cyclohexadienyl dehydratase (CDT) catalyze two subsequent reactions in the intracellular biosynthesis of L-phenylalanine (Phe). Here, we report the discovery of novel and extremely rare bifunctional fusion enzymes, consisting of fused CM and CDT domains, which are exported from the cytoplasm. Such enzymes were found in only nine bacterial species belonging to non-pathogenic γ- or β-Proteobacteria. In γ-proteobacterial fusion enzymes, the CM domain is N-terminal to the CDT domain, whereas the order is inverted in β-Proteobacteria. The CM domains share 15% to 20% sequence identity with the AroQγ class CM holotype of Mycobacterium tuberculosis (∗MtCM), and the CDT domains 40% to 60% identity with the exported monofunctional enzyme of Pseudomonas aeruginosa (PheC). In vitro kinetics revealed a Kₘ <7 μM, much lower than for ∗MtCM, whereas kinetic parameters are similar for CDT domains and PheC. There is no feedback inhibition of CM or CDT by the pathway's end product Phe, and no catalytic benefit of the domain fusion compared with engineered single-domain constructs. The fusion enzymes of Aequoribacter fuscus, Janthinobacterium sp. HH01, and Duganella sacchari were crystallized and their structures refined to 1.6, 1.7, and 2.4 Å resolution, respectively. Neither the crystal structures nor the size-exclusion chromatography show evidence for substrate channeling or higher oligomeric structure that could account for the cooperation of CM and CDT active sites. The genetic neighborhood with genes encoding transporter and substrate binding proteins suggests that these exported bifunctional fusion enzymes may participate in signaling systems rather than in the biosynthesis of Phe.ISSN:0021-9258ISSN:1083-351

Through enhanced tree dynamics carbon dioxide enrichment may cause tropical forests to lose carbon.

The fixation and storage of C by tropical forests, which contain close to half of the globe's biomass C, may be affected by elevated atmospheric CO2 concentration. Classical theoretical approaches assume a uniform stimulation of photosynthesis and growth across taxa. Direct assessments of the C balance either by flux studies or by repeated forest inventories also suggest a current net uptake, although magnitudes sometimes exceed those missing required to balance the global C cycle. Reasons for such discrepancies may lie in the nature of forest dynamics and in differential responses of taxa or plant functional types. In this contribution I argue that CO2 enrichment may cause forests to become more dynamic and that faster tree turnover may in fact convert a stimulatory effect of elevated CO2 on photosynthesis and growth into a long-term net biomass C loss by favouring shorter-lived trees of lower wood density. At the least, this is a scenario that deserves inclusion into long-term projections of the C relations of tropical forests. Species and plant functional type specific responses ('biodiversity effects') and forest dynamics need to be accounted for in projections of future C storage and cycling in tropical forests