Leaf Age-Dependent Photosystem II Photochemistry and Oxidative Stress Responses to Drought Stress in Arabidopsis thaliana Are Modulated by Flavonoid Accumulation

We investigated flavonoid accumulation and lipid peroxidation in young leaves (YL) and mature leaves (ML) of Arabidopsis thaliana plants, whose watering stopped 24 h before sampling, characterized as onset of drought stress (OnDS), six days before sampling, characterized as mild drought stress (MiDS), and ten days before sampling, characterized as moderate drought stress (MoDS). The response to drought stress (DS) of photosystem II (PSII) photochemistry, in both leaf types, was evaluated by estimating the allocation of absorbed light to photochemistry (Φ_PSII), to heat dissipation by regulated non-photochemical energy loss (Φ_NPQ) and to non-regulated energy dissipated in PSII (Φ_NO). Young leaves were better protected at MoDS than ML leaves, by having higher concentration of flavonoids that promote acclimation of YL PSII photochemistry to MoDS, showing lower lipid peroxidation and excitation pressure (1 − q_p). Young leaves at MoDS possessed lower 1 − q_p values and lower excess excitation energy (EXC), not only compared to MoDS ML, but even to MiDS YL. They also possessed a higher capacity to maintain low Φ_NO, suggesting a lower singlet oxygen (¹O₂) generation. Our results highlight that leaves of different developmental stage may display different responses to DS, due to differential accumulation of metabolites, and imply that PSII photochemistry in Arabidopsis thaliana may not show a dose dependent DS response.     

Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6‐Diisopropyl‐N‐(trimethylsilyl)anilino Ligand

Bulky amido ligands are precious in s‐block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n‐butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe₃)(Dipp)]^? (Dipp=2,6‐iPr₂‐C₆H₃). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s‐block metal amides. Solvation by N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (PMDETA) or N,N,N′,N′‐tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi‐solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe₃)(Dipp)}₂(μ‐nBu)]_∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies.     

The diagnostic accuracy of MRI for the detection of partial- and full-thickness rotator cuff tears in adults

This study assessed the diagnostic test accuracy of magnetic resonance imaging (MRI) in the detection of partial- and full-thickness rotator cuff tears in the adult population. A systematic review was conducted of the following electronic databases: Cochrane Central Register of Controlled Trials, Medline, Embase, CINAHL, AMED, ISI Web of Science, Current Controlled Trials, National Technical Information Service, the National Institute for Health Research Portfolio, the UK National Research Register Archive and WHO International Clinical Trials Registry Platform database and reference lists of articles. All studies assessing the sensitivity and/or specificity of MRI for adult patients with suspected rotator cuff tear where surgical procedures were the reference standard were included in the study. A meta-analysis was performed to calculate pooled sensitivity, specificity, likelihood and diagnostic odds ratio values, and summary receiver operating characteristic plots were constructed. Forty-four studies were included. These included 2751 shoulders in 2710 patients. For partial-thickness rotator cuff tears, the pooled sensitivity and specificity values were 0.80 [95% confidence interval (CI): 0.79-0.84] and 0.95 (95% CI: 0.94-0.97), respectively. For full-thickness tears, the sensitivity and specificity values were 0.91 (95% CI: 0.86-0.94) and 0.97 (95% CI: 0.96-0.98), respectively. While there was no substantial difference in diagnostic test accuracy between MRIs reviewed by general radiologists and those reviewed by musculoskeletal radiologists, higher-field-strength (3.0 T) MRI systems provided the greatest diagnostic test accuracy.     

Global alignment of molecular sequences via ancestral state reconstruction

We consider the trace reconstruction problem on a tree (TRPT): a binary sequence is broadcast through a tree channel where we allow substitutions, deletions, and insertions; we seek to reconstruct the original sequence from the sequences received at the leaves. The TRPT is motivated by the multiple sequence alignment problem in computational biology. We give a simple recursive procedure giving strong reconstruction guarantees at low mutation rates. To our knowledge, this is the first rigorous trace reconstruction result on a tree in the presence of indels.     

A Preparation Method for Well‐Defined Crystallites of Mgcl2‐Supported Ziegler‐Natta Catalysts and their Observation by AFM and SEM

A method for the preparation of well‐defined crystallites of MgCl₂‐supported Ziegler‐Natta catalysts on Si wafers has been developed. This has been achieved by the spin‐coating of a MgCl₂ solution onto a flat Si wafer, followed by controlled crystal growth to give well‐defined MgCl₂ · nEtOH crystallites. The growth of the crystallites on the flat silica facilitates their characterization using electron and scanning probe microscopy. The relative proportions of 120° and 90° edge angles indicate the preference for the formation of a particular crystallite face for the MgCl₂. Polyethylene has been identified to be formed on the lateral faces of the crystallite.

     

Strain-Enhanced Metallic Intermixing in Shape-Controlled Multilayered Core–Shell Nanostructures: Toward Shaped Intermetallics

Controlling the surface composition of shaped bimetallic nanoparticles could offer precise tunability of geometric and electronic surface structure for new nanocatalysts. To achieve this goal, a platform for studying the intermixing process in a shaped nanoparticle was designed, using multilayered Pd-Ni-Pt core–shell nanocubes as precursors. Under mild conditions, the intermixing between Ni and Pt could be tuned by changing layer thickness and number, triggering intermixing while preserving nanoparticle shape. Intermixing of the two metals is monitored using transmission electron microscopy. The surface structure evolution is characterized using electrochemical methanol oxidation. DFT calculations suggest that the low-temperature mixing is enhanced by shorter diffusion lengths and strain introduced by the layered structure. The platform and insights presented are an advance toward the realization of shape-controlled multimetallic nanoparticles tailored to each potential application.     

Ultraviolet photoelectron spectroscopic study of MS σ bonding energy and of spiroconjugation effects in group IVA thiospiranes

He(I) and He(II) ultraviolet photoelectron spectra of tetrathiometallaspiranes

(M = C, Si, Ge, Sn) yield data for quantitative characterization of several structural effects. Spiroconjugation of the lone pair orbitals of the sulfur atoms is indicated by the splitting patterns of the n_s ionization bands in the low IE region (8–9_eV); quantitative evaluation confirms that there is a marked decrease of the spiroconjugation effects with increasing size of M. Energy values are assigned by UP spectral analysis to MS σ bond orbitals which show a small variation with M between ca. 10 and 11 eV, consistent with the small electronegativity variation, and to CS bond orbitals in the spirane rings, fairly constant around 13.5 eV. Ionizations of the quasi-valence 4d orbitals in the Sn derivative are identified at 34.38 and 35.42 eV, and suggest, by comparison with other known Sn compounds, a considerably high overall electronegativity of the ligands in the present compound.     

Doping Platinum with Germanium: An Effective Way to Mitigate the CO Poisoning

The vulnerability towards CO poisoning is a major drawback affecting the efficiency and long-term performance of platinum catalysts in fuel cells. In the present work, by a combination of density functional theory calculations and mass spectrometry experiments, we test and explain the promotional effect of Ge on Pt catalysts with higher resistance to deactivation via CO poisoning. A thorough exploration of the configurational space of gas-phase Pt_n⁺ and GePt_n−1⁺ (n=5–9) clusters using global minima search techniques and the subsequent electronic structure analysis reveals that germanium doping reduces the binding strength between Pt and CO by hindering the 2π-back-donation. Importantly, the clusters remain catalytically active towards H₂ dissociation. The ability of Ge to weaken the Pt−CO interaction was confirmed by mass spectrometry experiments. Ge can be a promising alloying agent to tune the selectivity and improve the durability of Pt particles, thus opening the way to novel catalytic alternatives for fuel cells.     

Modulating Magnetic and Photoluminescence Properties in 2-Aminonicotinate-Based Bifunctional Coordination Polymers by Merging 3d Metal Ions

Herein, the synthesis and study of bifunctional coordination polymers (CPs) with both magnetic and photoluminescence properties, derived from a heterometallic environment, are reported. As a starting point, three isostructural monometallic CPs with the formula [M(μ-2ani)₂]_n (M^II=Mn ( 1_Mn ), Co ( 3_Co ) and Ni ( 4_Ni ); 2ani=2-aminonicotinate), crystallise as chiral 2D-layered structures stacked by means of supramolecular interactions. These compounds show high thermal stability in the solid state (above 350 °C), despite which, in aqueous solution, compound 1_Mn is shown to partially transform into a novel 1D chain CP with the formula [Mn(2ani)₂(μ-H₂O)₂]_n ( 2_Mn ). A study of the direct current (dc) magnetic properties of 1_Mn , 3_Co and 4_Ni reveals a spin-canted structure derived from antisymmetric antiferromagnetic weak exchanges along the chiral network (as confirmed by DFT calculations) and magnetic anisotropy of the ions, in such a way that long-range ordering is observed with variable magnitude for the spin carriers. Moreover, compounds 3_Co and 4_Ni show no frequency-dependent alternating current (ac) susceptibility curves under zero dc field; this is characteristic behaviour of a glassy state that may be partially supressed for 3_Co by applying an external dc field. To overcome long-range magnetic ordering, Co^II ions are diluted in a diamagnetic Zn^II-based matrix, which enables single-molecule magnet behaviour. Interestingly, this strategy allows a bifunctional Co_xZn_1−x2ani material, which is imbued with a strong photoluminescent emitting capacity, as characterised by an intense blue light followed by a green afterglow, to be obtained.     

On the lack of dispersion for a class of magnetic Dirac flows

We show that global Strichartz estimates for magnetic Dirac operators generally fail, if the potentials do not decay fast enough at infinity. In order to prove this, we construct some explicit examples of homogeneous magnetic potentials with less than Coulomb decay, that is, with homogeneity-degree more than ?1, such that the magnetic field points to a fixed direction, which does not depend on ${x \in \mathbb{R}^{3}}$ .