Polyglycerols (sometimes also called “polyglycidols”) represent a class of highly biocompatible and multihydroxy-functional polymers that may be considered as a multifunctional analogue of ...poly(ethylene glycol) (PEG). Various architectures based on a polyglycerol scaffold are feasible depending on the monomer employed. While polymerization of glycidol leads to hyperbranched polyglycerols, the precisely defined linear analogue is obtained by using suitably protected glycidol as a monomer, followed by removal of the protective group in a postpolymerization step. This review summarizes the properties and synthetic approaches toward linear polyglycerols (linPG), which are at present mainly based on the application of ethoxyethyl glycidyl ether (EEGE) as an acetal-protected glycidol derivative. Particular emphasis is placed on the manifold functionalization strategies including, e.g., the synthesis of end-functional linPGs or multiheterofunctional modifications at the polyether backbone. Potential applications like bioconjugation and utilization as a component in degradable biomaterials or for diagnostics, in which polyglycerol acts as a promising PEG substitute are discussed. In the last section, the important role of linear polyglycerol as a macroinitiator or as a highly hydrophilic segment in block co- or terpolymers is highlighted.
Efficient polarization of organic molecules is of extraordinary relevance when performing nuclear magnetic resonance (NMR) and imaging. Commercially available routes to dynamical nuclear polarization ...(DNP) work at extremely low temperatures, relying on the solidification of organic samples and thus bringing the molecules out of their ambient thermal conditions. In this work, we investigate polarization transfer from optically pumped nitrogen vacancy centers in diamond to external molecules at room temperature. This polarization transfer is described by both an extensive analytical analysis and numerical simulations based on spin bath bosonization and is supported by experimental data in excellent agreement. These results set the route to hyperpolarization of diffusive molecules in different scenarios and consequently, due to an increased signal, to high-resolution NMR.
The enantioselective synthesis of cyclopropylzinc reagents has been achieved via a copper-catalyzed carbozincation of 3,3-disubstituted cyclopropenes with diorganozinc reagents. The obtained ...organozinc compounds can be easily functionalized with a broad range of electrophiles, including palladium-catalyzed cross-couplings, affording highly substituted cyclopropanes. The operationally simple procedure using very low quantities of a commercially available and inexpensive copper catalyst provides a new tool for the synthesis of highly enantioenriched cyclopropanes as single diastereoisomers.
Summary
Phosphate‐solubilising microorganisms (PSM) are often reported to have positive effects on crop productivity through enhanced phosphorus (P) nutrition. Our aim was to evaluate the validity of ...this concept. Most studies that report ‘positive effects’ of PSM on plant growth have been conducted under controlled conditions, whereas field experiments more frequently fail to demonstrate a positive response. Many studies have indicated that the mechanisms seen in vitro do not translate into improved crop P nutrition in complex soil–plant systems. Furthermore, associated mechanisms are often not rigorously assessed. We suggest that PSM do not mobilise sufficient P to change the crops’ nutritional environment under field conditions. The current concept, in which PSM solubilise P ‘for the plant’ should thus be revised. Although PSM have the capacity to solubilise P to meet their own needs, it is the turnover of the microbial biomass that subsequently provides P to plants over a longer time. Therefore, the existing concept of PSM function is unlikely to deliver a reliable strategy for increasing crop P nutrition. A further mechanistic understanding is needed to determine how P mobilisation by PSM as a component of the whole soil community can be manipulated to become more effective for plant P nutrition.
Following an idea by Joyner et al. Europhys. Lett. 107, 50004 (2014), a microwave graph with an antiunitary symmetry T obeying T^{2}=-1 is realized. The Kramers doublets expected for such systems are ...clearly identified and can be lifted by a perturbation which breaks the antiunitary symmetry. The observed spectral level spacings distribution of the Kramers doublets is in agreement with the predictions from the Gaussian symplectic ensemble expected for chaotic systems with such a symmetry.
The highly diastereo‐ and enantioselective formation of polysubstituted cyclopropanes was easily achieved through the asymmetric copper‐catalyzed carbomagnesiation reaction of nonfunctionalized ...cyclopropene derivatives. The carbometalated species generated in situ readily undergo C−C and C−X bond‐forming reactions with various electrophiles with complete retention of configuration.
Magnesiated: Diastereo‐ and enantiomerically enriched cyclopropylmagnesium halides were synthesized through the copper‐catalyzed addition of Grignard reagents across cyclopropenes. The carbometalated species generated in situ readily undergo C−C and C−X bond‐forming reactions with various electrophiles with complete retention of configuration.
Remote sensing enables the quantification of tropical deforestation with high spatial resolution. This in-depth mapping has led to substantial advances in the analysis of continent-wide fragmentation ...of tropical forests. Here we identified approximately 130 million forest fragments in three continents that show surprisingly similar power-law size and perimeter distributions as well as fractal dimensions. Power-law distributions have been observed in many natural phenomena such as wildfires, landslides and earthquakes. The principles of percolation theory provide one explanation for the observed patterns, and suggest that forest fragmentation is close to the critical point of percolation; simulation modelling also supports this hypothesis. The observed patterns emerge not only from random deforestation, which can be described by percolation theory, but also from a wide range of deforestation and forest-recovery regimes. Our models predict that additional forest loss will result in a large increase in the total number of forest fragments-at maximum by a factor of 33 over 50 years-as well as a decrease in their size, and that these consequences could be partly mitigated by reforestation and forest protection.
Cytotoxic T lymphocytes (CTLs) kill infected and cancerous cells. We detected transfer of cytotoxic multiprotein complexes, called supramolecular attack particles (SMAPs), from CTLs to target cells. ...SMAPs were rapidly released from CTLs and were autonomously cytotoxic. Mass spectrometry, immunochemical analysis, and CRISPR editing identified a carboxyl-terminal fragment of thrombospondin-1 as an unexpected SMAP component that contributed to target killing. Direct stochastic optical reconstruction microscopy resolved a cytotoxic core surrounded by a thrombospondin-1 shell of ~120 nanometer diameter. Cryo-soft x-ray tomography analysis revealed that SMAPs had a carbon-dense shell and were stored in multicore granules. We propose that SMAPs are autonomous extracellular killing entities that deliver cytotoxic cargo targeted by the specificity of shell components.
Context. Complex organic molecules are detected in many sources in the warm inner regions of envelopes surrounding deeply embedded protostars. Exactly how these species form remains an open question. ...Aims. This study aims to constrain the formation of complex organic molecules through comparisons of their abundances towards the Class 0 protostellar binary IRAS 16293–2422. Methods. We utilised observations from the ALMA Protostellar Interferometric Line Survey of IRAS 16293–2422. The species identification and the rotational temperature and column density estimation were derived by fitting the extracted spectra towards IRAS 16293–2422 A and IRAS 16293–2422 B with synthetic spectra. The majority of the work in this paper pertains to the analysis of IRAS 16293–2422 A for a comparison with the results from the other binary component, which have already been published. Results. We detect 15 different complex species, as well as 16 isotopologues towards the most luminous companion protostar IRAS 16293–2422 A. Tentative detections of an additional 11 isotopologues are reported. We also searched for and report on the first detections of methoxymethanol (CH 3 OCH 2 OH) and trans-ethyl methyl ether (t-C 2 H 5 OCH 3 ) towards IRAS 16293–2422 B and the follow-up detection of deuterated isotopologues of acetaldehyde (CH 2 DCHO and CH 3 CDO). Twenty-four lines of doubly-deuterated methanol (CHD 2 OH) are also identified. Conclusions. The comparison between the two protostars of the binary system shows significant differences in abundance for some of the species, which are partially correlated to their spatial distribution. The spatial distribution is consistent with the sublimation temperature of the species; those with higher expected sublimation temperatures are located in the most compact region of the hot corino towards IRAS 16293–2422 A. This spatial differentiation is not resolved in IRAS 16293–2422 B and will require observations at a higher angular resolution. In parallel, the list of identified CHD 2 OH lines shows the need of accurate spectroscopic data including their line strength.
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