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Single crystals of Nb2PdxSe5 have been grown covering a broad range of palladium stoichiometries from x = 0.68–0.95 (Pd2 occupancies of 0.36 and 0.90, respectively). Miscibility gaps in the Pd stoi...

The synthesis of a large family of heterobimetallic lanthanide copper sulfates was realized via stoichiometric hydrothermal reactions among Ln2O3, CuO, and H2SO4, giving rise to four distinct phases, namely Ln2Cu(SO4)2(OH)4 (Ln = Sm-Ho) (LnCuSO4-1), Ln4Cu(SO4)2(OH)10 (Ln = Tm-Lu) (LnCuSO4-2), LnCu(SO4)(OH)3 (Ln = Nd-Gd, except Pm) (LnCuSO4-3), and LnCu(SO4)(OH)3 (Ln = Dy-Lu) (LnCuSO4-4), with completely different topologies. The passage from LnCuSO4-1 and LnCuSO4-3 to LnCuSO4-2 and LnCuSO4-4 across the 4f series, respectively, can be ascribed to the effect of lanthanide contraction, which progressively induces shrinking of the Ln-O distance, reduction in the Ln coordination number, and eventually structural transitions. The incorporation of identical 3d-4f metal ions into different spin-lattices, in conjunction with substitution of diverse Ln3+ cations within the same spin-lattice, gives rise to tunable magnetic properties varying from ferromagnetic ordering in GdCuSO4-3 and HoCuSO4-4 to antiferromagnetic ordering in YbCuSO4-4, and to paramagnetic correlations found in GdCuSO4-1 and YbCuSO4-2.

Curium is unique in the actinide series because its half-filled 5f 7 shell has lower energy than other 5f n configurations, rendering it both redox-inactive and resistant to forming chemical bonds that engage the 5f shell1–3. This is even more pronounced in gadolinium, curium’s lanthanide analogue, owing to the contraction of the 4f orbitals with respect to the 5f orbitals4. However, at high pressures metallic curium undergoes a transition from localized to itinerant 5f electrons5. This transition is accompanied by a crystal structure dictated by the magnetic interactions between curium atoms5,6. Therefore, the question arises of whether the frontier metal orbitals in curium(iii)–ligand interactions can also be modified by applying pressure, and thus be induced to form metal–ligand bonds with a degree of covalency. Here we report experimental and computational evidence for changes in the relative roles of the 5f/6d orbitals in curium–sulfur bonds in [Cm(pydtc)4]− (pydtc, pyrrolidinedithiocarbamate) at high pressures (up to 11 gigapascals). We compare these results to the spectra of [Nd(pydtc)4]− and of a Cm(iii) mellitate that possesses only curium–oxygen bonds. Compared with the changes observed in the [Cm(pydtc)4]− spectra, we observe smaller changes in the f–f transitions in the [Nd(pydtc)4]− absorption spectrum and in the f–f emission spectrum of the Cm(iii) mellitate upon pressurization, which are related to the smaller perturbation of the nature of their bonds. These results reveal that the metal orbital contributions to the curium–sulfur bonds are considerably enhanced at high pressures and that the 5f orbital involvement doubles between 0 and 11 gigapascal. Our work implies that covalency in actinides is complex even when dealing with the same ion, but it could guide the selection of ligands to study the effect of pressure on actinide compounds. Enhanced covalency is achieved for a curium complex with curium–sulfur bonds by subjecting the compound to high pressures, indicating that pressure can be used to tune covalency in actinide compounds.

With the advent of lanthanide-based technologies, there is a clear need to advance the fundamental understanding of 4f-element chelation chemistry. Herein, we contribute to a growing body of lanthanide chelation chemistry and report the synthesis of bimetallic 4f-element complexes within an imine/hemiacetalate framework

Crystalline porous materials such as covalent organic frameworks (COFs) are advanced materials to tackle challenges of catalysis and separation in industrial processes. Their synthetic routes often require elevated temperatures, closed systems with high pressure, and long reaction times, hampering their industrial applications. Here we use a traditionally unperceived strategy to assemble highly crystalline COFs by electron beam irradiation with controlled received dosage, contrasting sharply with the previous observation that radiation damages the crystallinity of solids. Such synthesis by electron beam irradiation can be achieved under ambient conditions within minutes, and the process is amendable for large-scale production. The intense and targeted energy input to the reactants leads to new reaction pathways that favor COF formation in nearly quantitative yield. This strategy is applicable not only to known COFs but also to new series of flexible COFs that are difficult to obtain using traditional methods.

β-[NH4][UF5] and [NH4][Pu3F13] have been prepared by mild hydrothermal reactions. Their single-crystal structures have been observed to offer unexpected similarities in topology. β-[NH4][UF5] (P21/...

The structural chemistry of elements relevant to the FLiBe molten salt reactor, Th, U, Np, and Zr, including Ce and Nd (as analogues for Pu and Am, respectively), have been examined using hydrothermal synthesis at 200 °C. These reactions serve to model the reaction of molten salts under hydrolysis conditions. The results show that U and Np formed

Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here, electrospray ionization was used to generate gas-phase complexes [ML3]3+, where M = La, Lu, or Am and L is EtBTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine. Collision-induced dissociation (CID) of [ML3]3+ in the presence of H2O yielded a protonated ligand [L(H)]+ and hydroxide [ML2(OH)]2+ or hydrate [ML(L-H)(H2O)]2+, where (L-H)- is a deprotonated ligand. Although solution affinities indicate stronger binding of BTPs toward Am3+ versus Ln3+, the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accordance with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL3]3+ versus [LaL3]3+ and for both product isomers, [ML2(OH)]2+ and [ML(L-H)(H2O)]2+. More facile removal of a ligand from [AmL3]3+ by CID does not necessarily contradict stronger Am3+-L binding, as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predicting the seemingly anomalous CID behavior, the computational results indicate greater participation of Am 5f versus La 4f orbitals in metal-ligand bonding.

Funding Acknowledgements Type of funding sources: Private company. Main funding source(s): Boston Scientific Introduction Low nadir temperatures and long thaw times with cryoballoon ablation are associated with successful pulmonary vein isolation (PVI). Recently, a system that maintains uniform pressure and size has been introduced to improve catheter stability during cryoballoon ablation. The present results examine the relationship between cryoballoon time to isolation (TTI) and other biophysical parameters; time to -40ºC (TT-40), nadir temperature, time to thaw (TT0), and first pass isolation success in patients with paroxysmal AF (PAF). Methods POLAR ICE, a prospective, non-randomized, multicenter (international) registry (NCT04250714), enrolled 400 patients across 19 centers, between Aug 2020 and May 2021. This study included any patients indicated for treatment of PAF with the POLARx cryoablation system. Cryodosing regimen was left to the operator and not specified by study protocol. Procedural characteristics, such as time to isolation (TTI), cryoablations per pulmonary vein, nadir temperature, and occlusion grade were recorded. PVI was confirmed via entrance block. Biophysical parameters for ablations longer than 120s were evaluated. Results Data on 389 PVI procedures (n=2303 ablations) were collected. Of those ablations, 1914 (83%) had a duration of at least 120s and were included in this analysis. Isolation was attempted using the CB alone. TTI was reported in 1335 ablations with the majority (64%) occurring within 60s. Biophysical parameters and single shot success rates were examined based on TTI. Ablations with TTI Conclusions These data suggest a correlation between cryoballoon biophysical parameters and single shot success. Good occlusion likely drives faster freeze and lower nadir temperatures, resulting in longer thaw times with this novel cryoballoon. Future research should examine the relationship between these parameters to drive optimization of cryoablation techniques and provide guidance toward improved workflow.

Funding Acknowledgements Type of funding sources: Private company. Main funding source(s): Boston Scientific Background/Introduction Pulmonary vein isolation (PVI) using a cryoballoon is well-established for the treatment of paroxysmal atrial fibrillation (PAF). Initial experience with a novel cryoballoon (CB) with a stable low balloon pressure (POLARx, Boston Scientific) has demonstrated acute procedural safety and efficacy in de novo PVI procedures in patients with paroxysmal AF. However, to date, there is limited multicenter data on real world acute outcomes and procedural characteristics with this novel cryoballoon. Purpose The purpose of POLAR ICE was to provide real-world data on the acute and chronic outcomes of cryoballoon ablation with POLARx for the treatment of PAF. Here we report on the initial acute outcomes up to 3 months including procedural efficacy, safety, and biophysical parameters. Methods POLAR ICE, a prospective, non-randomized, multicenter (international) registry (NCT04250714), enrolled 400 patients across 19 centers, between Aug 2020 and May 2021. This study included any patients indicated for treatment of PAF with the POLARx cryoablation system. The study protocol did not mandate any specific cryodosing regimen, this was left to the operator. Procedural characteristics, such as time to isolation (TTI), cryoablations per pulmonary vein, balloon nadir temperature, and occlusion grade were recorded. PVI was confirmed with entrance block testing. Results Complete PVI was achieved in 96.1% of PVs (1437/1496). Procedure and fluoroscopy times were 69.0±25.2 min and 15.8±10.0 min, respectively. Left atrial dwell time was 47.3±18.8 min. The cryoablation characteristics by vein are shown in the Table 1. An average of 4.9±1.8 ablations were performed per patient (1.3±0.7 per vein). Grade 3 or 4 occlusion was achieved in 98.1% of PVs reported. Electrical isolation was achieved with an average TTI of 50±33.8s and in 81.4% of PVs isolation required only a single cryoablation. Nadir temperatures across all pulmonary veins averaged -56.3± 6.5C. Time to -40C was 32.9±11s and Time to Thaw (0C) was 19.5±6.7s across all veins. PVI was performed on atypical anatomies (12 LCPV, 7 RMPV, & 3 RCPV) in 19 pts. Serious adverse events included phrenic nerve palsy (0.5%), tamponade (0.5%), AV block (0.3%), stroke (0.3%), and transient ischemic attack (0.3%). Conclusions Real world usage data on the novel CB suggests that this device is safe and effective, with a PV isolation success rate of 96.2% and 81.4% of PVs isolated with a single cryoablation. These data are in keeping with reports on other cryoballon systems and have markedly shorter procedure times than have been previously reported on this cryoballon.

Microglia utilize their phagocytic activity to prune redundant synapses and refine neural circuits during precise developmental periods. However, the neuronal signals that control this phagocytic clockwork remain largely undefined. Here, we show that neuronal signal-regulatory protein alpha (SIRPα) is a permissive cue for microglial phagocytosis in the developing murine retina. Removal of neuronal, but not microglial, SIRPα reduced microglial phagocytosis, increased synpase numbers, and impaired circuit function. Conversely, prolonging neuronal SIRPα expression extended developmental microglial phagocytosis. These outcomes depended on the interaction of presynaptic SIRPα with postsynaptic CD47. Global CD47 deficiency modestly increased microglial phagocytosis, while CD47 overexpression reduced it. This effect was rescued by coexpression of neuronal SIRPα or codeletion of neuronal SIRPα and CD47. These data indicate that neuronal SIRPα regulates microglial phagocytosis by limiting microglial SIRPα access to neuronal CD47. This discovery may aid our understanding of synapse loss in neurological diseases.

A berkelium mellitate is added to a small family of structurally characterized Bk compounds. The 5f → 5f transitions on average blue shift and the compound changes colour with applied pressure unlike other actinide mellitates.

Californium (Cf) is currently the heaviest element accessible above microgram quantities. Cf isotopes impose severe experimental challenges due to their scarcity and radiological hazards. Consequently, chemical secrets ranging from the accessibility of 5f/6d valence orbitals to engage in bonding, the role of spin–orbit coupling in electronic structure, and reactivity patterns compared to other f elements, remain locked. Organometallic molecules were foundational in elucidating periodicity and bonding trends across the periodic table1–3, with a twenty-first-century renaissance of organometallic thorium (Th) through plutonium (Pu) chemistry4–12, and to a smaller extent americium (Am)13, transforming chemical understanding. Yet, analogous curium (Cm) to Cf chemistry has lain dormant since the 1970s. Here, we revive air-/moisture-sensitive Cf chemistry through the synthesis and characterization of [Cf(C5Me4H)2Cl2K(OEt2)]n from two milligrams of 249Cf. This bent metallocene motif, not previously structurally authenticated beyond uranium (U)14,15, contains the first crystallographically characterized Cf–C bond. Analysis suggests the Cf–C bond is largely ionic with a small covalent contribution. Lowered Cf 5f orbital energy versus dysprosium (Dy) 4f in the colourless, isoelectronic and isostructural [Dy(C5Me4H)2Cl2K(OEt2)]n results in an orange Cf compound, contrasting with the light-green colour typically associated with Cf compounds16–22.

The interplay of bond strength and covalency are examined in AnO2Cl2(OPcy3)2(An = Pu, U) complexes. The synthesis oftrans-PuO2Cl2(OPcy3)2,1-Pu, has been carried out and confirmed by single crystal X-ray diffraction along with UV-vis-NIR, and31P NMR spectroscopies. Theoretical analysis finds that despite a higher calculated covalency for the Pu-Cl interaction, the Pu-OPcy3interaction is stronger due to the accumulation of electron density in the interatomic region. The coordination of equatorial ligands slightly decreases the strength of the Pu Oylinteractions relative to the free gas phase (PuO2)2+ion.

Three samarium(II) crown ether complexes, [Sm(15-crown-5)2]I2 (1), [Sm(15-crown-5)2]I2·CH3CN (2), and [Sm(benzo-15-crown-5)2]I2 (3), have been prepared via the reaction of SmI2 with the corresponding crown ether in either THF or acetonitrile in good to moderate yields. The compounds have been characterized by single crystal X-ray diffraction and a variety of spectroscopic techniques. In all cases, the Sm(II) centers are sandwiched between two crown ether molecules and are bound by the five etheric oxygen atoms from each crown ether to yield 10-coordinate environments. Despite the higher symmetry crystal class of 1 (R3c), the samarium center resides on a general position, whereas in 2 and 3 (both in P21/c) the metal centers lie upon inversion centers. Moreover, the complexes in 2 and 3 are approximated well by D5d symmetry. The molecule in 1, however, is distorted from idealized D5d symmetry, and the crown ethers are more puckered than observed in 2 and 3. All three complexes luminesce in the NIR at low temperatures. However, the nature of the luminescence differs between the three compounds. 1 exhibits broadband photoluminescence at 20 °C but at low temperatures transitions to narrow peaks. 2 only exhibits nonradiative decay at 20 °C and at low temperatures retains a mixture of broadband and fine transitions. Finally, 3 displays broadband luminescence regardless of temperature. Spin-orbit (SO) CASSCF calculations reveal that the outer-sphere iodide anions influence whether broadband luminescence from 5d → 4f or fine 4f → 4f transitions occur through the alteration of symmetry around the metal centers and the nature of the excited states as a function of temperature.

Using a redox-active dioxophenoxazine ligand, DOPO (DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazine-9-olate), a family of actinide (U, Th, Np, and Pu) and Hf tris(ligand) coordination compounds was synthesized. The full characterization of these species using 1H NMR spectroscopy, electronic absorption spectroscopy, SQUID magnetometry, and X-ray crystallography showed that these compounds are analogous and exist in the form M(DOPOq)2(DOPOsq), where two ligands are of the oxidized quinone form (DOPOq) and the third is of the reduced semiquinone (DOPOsq) form. The electronic structures of these complexes were further investigated using CASSCF calculations, which revealed electronic structures consistent with metals in the +4 formal oxidation state and one unpaired electron localized on one ligand in each complex. Furthermore, f orbitals of the early actinides show a sizable bonding overlap with the ligand 2p orbitals. Notably, this is the first example of a plutonium-ligand radical species and a rare example of magnetic data being recorded for a homogeneous plutonium coordination complex.

An

The aqueous reaction of mellitic acid (H6mell) with 242PuBr3·nH2O forms two plutonium mellitates, 242Pu2(mell)(H2O)9·H2O (Pu-1α) and 242Pu2(mell)(H2O)8·2H2O (Pu-1β). These compounds are compared to the isomorphous lanthanide mellitates with similar ionic radii via bond length analysis. Both plutonium compounds form three-dimensional metal-organic frameworks, with Pu-1α having two unique metal centers and Pu-1β having one. All plutonium metal centers exhibit nine-coordinate geometries. Our results show metal-oxygen bond lengths for plutonium significantly shorter than those of the previously reported lanthanum and herein reported cerium analogues, consistent with the nine-coordinate ionic radii. Clear Laporte-forbidden 5f → 5f transitions are observed in the ultraviolet-visible-near-infrared spectra and are assigned to trivalent plutonium. However, there is a distinct color difference between the two plutonium compounds.

The interaction of Np(V) with borate was investigated in 0.1–5.0 M NaCl and 0.25–4.5 M MgCl2 solutions with 7.2 ≤ pHm ≤ 10.0 (pHm = –log[H+]) and 0.004 M ≤ [B]tot ≤ 0.16 M. Experiments were performed under an Ar-atmosphere at T = (22 ± 2) °C using a combination of under- and oversaturation solubility experiments, NIR spectroscopy, and extensive solid phase characterization. A bathochromic shift (≈5 nm) in the Np(V) band at λ = 980 nm indicates the formation of weak Np(V)–borate complexes under mildly alkaline pHm-conditions. The identification of an isosbestic point supports the formation of a single Np(V)–borate species in dilute MgCl2 systems, whereas a more complex aqueous speciation (eventually involving the formation of several Np(V)–borate species) is observed in concentrated MgCl2 solutions. The solubility of freshly prepared NpO2OH(am) remained largely unaltered in NaCl and MgCl2 solutions with [B]tot = 0.04 M within the timeframe of this study (t ≤ 300 days). At [B]tot = 0.16 M, a kinetically hindered but very significant drop in the solubility of Np(V) (3–4 log10-units, compared to borate-free systems) was observed in NaCl and dilute MgCl2 solutions with pHm ≤ 9. The drop in the solubility was accompanied by a clear change in the colour of the solid phase (from green to white-greyish). XRD and TEM analyses showed that the amorphous NpO2OH(am) “starting material” transformed into crystalline solid phases with similar XRD patterns in NaCl and MgCl2 systems. XPS, SEM–EDS and EXAFS further indicated that borate and Na/Mg participate stoichiometrically in the formation of such solid phases. Additional undersaturation solubility experiments using the newly formed Na–Np(V)–borate(cr) and Mg–Np(V)–borate(cr) compounds further confirmed the low solubility ([Np(V)]aq ≈ 10−6–10−7 M) of such solid phases in mildly alkaline pHm-conditions. The formation of these solid phases represents a previously unreported retention mechanism for the highly mobile Np(V) under boundary conditions (pHm, [B]tot, ionic strength) of relevance to certain repository concepts for nuclear waste disposal.

Single crystalline bulk assemblies of metal halide clusters show great potential as highly efficient light emitters with tunable photophysical properties. However, synthetic control of the geometry...

Limb-girdle muscular dystrophies (LGMD) are a genetically heterogeneous category of autosomal inherited muscle diseases. Many genes causing LGMD have been identified, and clinical trials are beginning for treatment of some genetic subtypes. However, even with the gene-level mechanisms known, it is still difficult to get a robust and generalizable prevalence estimation for each subtype due to the limited amount of epidemiology data and the low incidence of LGMDs. Taking advantage of recently published exome and genome sequencing data from the general population, we used a Bayesian method to develop a robust disease prevalence estimator. This method was applied to nine recessive LGMD subtypes. The estimated disease prevalence calculated by this method was largely comparable with published estimates from epidemiological studies; however, it highlighted instances of possible underdiagnosis for LGMD2B and 2L. The increasing size of aggregated population variant databases will allow for robust and reproducible prevalence estimates of recessive disease, which is critical for the strategic design and prioritization of clinical trials.

In several areas of the central nervous system (CNS) neurons are regionally organized into groups or layers that carry out specific activities. In this form of patterning, neurons of distinct types localize their cell bodies to just one or a few of the layers within a structure. However, little is known about whether diverse neuron types within a lamina share molecular features that coordinate their organization. To begin to identify such candidates, we used the laminated murine retina to screen 92 lacZ reporter lines available through the Knockout Mouse Project. Thirty-two of these displayed reporter expression in restricted subsets of inner retina neurons. We then identified the spatiotemporal expression patterns of these genes at key developmental stages. This uncovered several that were heavily enriched in development but reduced in adulthood, including the transcriptional regulator Hmga1. An additional set of genes displayed maturation associated laminar enrichment. Among these, we identified Bbox1 as a novel gene that specifically labels all neurons in the ganglion cell layer but is largely excluded from otherwise molecularly similar neurons in the inner retina. Finally, we established Dbn1 as a new marker enriched in amacrines and Fmnl3 as a marker for subsets of αRGCs. Together, these data provide a spatiotemporal map for laminae-specific molecules and suggest that diverse neuron types within a lamina share coordinating molecular features that may inform their fate or function.

The reaction of 242PuO2 with HF and LiF under hydrothermal conditions results in the formation of Li4PuF8 and LiPuF5. These compounds were structurally characterized using single-crystal X-ray diffraction, and UV-vis-near-IR absorption spectroscopy was employed to confirm the oxidation state of the plutonium in the compounds as 4+. The structure of Li4PuF8 consists of [PuF8]4- anions that adopt a bicapped trigonal-prismatic geometry with approximate C2v symmetry. These molecules are bridged by Li+ cations. In contrast, LiPuF5 forms a dense three-dimensional network constructed from [PuF9]5- units that are bridged by F- anions. The Pu4+ cations are found within tricapped trigonal prisms. Extensive theoretical analysis of the electronic and bonding interactions is included with a comparison between the results derived from complete-active-space self-consistent-field at different levels of theory, quantum theory of atoms in molecules, interacting quantum atom, natural localized molecular orbital, and Wiberg bond order analyses. Covalent interactions in these compounds are examined, and intramolecular trends in covalent and electrostatic interactions are discussed.

We report the small-scale synthesis, isolated yield, single-crystal X-ray structure, 1H NMR solution spectroscopy /solid-state UV/Vis-nIR spectroscopy, and density functional theory (DFT)/ab initio wave function theory calculations on an Am3+ organometallic complex, [Am(C5Me4H)3] (1). This constitutes the first quantitative data on Am−C bonding in a molecular species.

The merging of small-scale syntheses and rapid crystallization methods have provided access to crystalline samples of berkelium (Z=97) and californium (Z=98) coordination complexes and compounds that can be interrogated with a suite of spectroscopic tools and structural elucidation approaches that have come online over the last 20 years. The combination of this experimental data with relativistic theoretical methods that capture the effects of spin-orbit coupling and scalar relativistic effects have allowed us to understand the electronic structure of berkelium and californium compounds at a level of detail that was not previously possible. The harbinger of this new era of post-curium chemistry was the synthesis and characterization of [Cf{B6 O8 (OH)5 }]. This compound possesses a structure type that is distinct from earlier actinide borates, a reduction in coordination number for californium, contracted Cf-O bond lengths, a substantially reduced magnetic moment with respect to the calculated free-ion moment and, most importantly, vibronically coupled broadband photoluminescence. Ligand-field analysis also showed that the splitting of the ground state was larger than typically found in the f-block elements, and when taken together places its overall electronic structure as a hybrid of d- and f-block components. The discovery of the unusual properties of this compound has led to the development of large families of 4f and 5f coordination complexes, in an effort to uncover the underlying origin of the electronic structure oddities, and whether there really is a sharp onset of these changes at californium. This in turn pushed the development of far more challenging berkelium chemistry (from a radiologic standpoint) because the half-life of the isotopes decreases from 351 years for 249 Cf to 330 days for 249 Bk. This short review details some of the chemistry that has been reported over the last 15 years, and its consequences for understanding the periodic table.

The precise organization of fine scale molecular architecture is critical for the nervous system and other biological functions and would benefit from nanoscopic imaging methods with improved accessibility, throughput, and native tissue compatibility. Here, we report RAIN-STORM, a rapid and scalable imaging approach that enables three-dimensional nanoscale target visualization for multiple subcellular and intracellular targets within tissue at depth. RAIN-STORM utilizes conventional tissue samples, readily available reagents in optimized formulas, requires no specialized sample handling, and is suitable for commercial instrumentation. To illustrate RAIN-STORM’s ability for quantitative high-resolution nanoscopic tissue imaging, we utilized the well-organized but structurally complex retina. We show that RAIN-STORM is rapid and versatile, enabling 3D nanoscopic imaging of over 20 distinct targets to reveal known and novel nanoscale features of synapses, neurons, glia, and vascular. Further, imaging parameters are compatible with a wide range of tissue sources and molecular targets across a spectrum of biological structures. Finally, we show that this method can be applied to clinically derived samples and reveal the nanoscale distribution of molecular targets within human samples. RAIN-STORM thus enables rapid 3D imaging for a range of molecules, paving the way for high throughput studies of nanoscopic molecular features in intact tissue from diverse sources.

The synthesis, characterization, and theoretical analysis of meridional americium tribromide tris(tricyclohexylphosphine oxide), mer-AmBr3(OPcy3)3, has been achieved and is compared with its early lanthanide (La to Nd) analogs. The data show that homo trans ligands display significantly shorter bonds than the cis or hetero trans ligands. This is particularly pronounced in the americium compound. DFT along with multiconfigurational CASSCF calculations show that the contraction of the bonds relates qualitatively with overall covalency, i.e. americium shows the most covalent interactions compared to lanthanides. However, the involvement of the 5p and 6p shells in bonding follows a different order, namely cerium > neodymium ∼ americium. This study provides further insight into the mechanisms by which ITI operates in low-valent f-block complexes., Structural, spectroscopic and theoretical analyses of mer-MBr3(OPcy3)3 (M = Am, Nd, Pr, Ce, La) reveal significant amounts of metal based p-orbital contribution.

Homeostatic control of blood glucose requires different physiological responses in the fasting and post-prandial states. We reasoned that glucose measurements under non-standardised conditions (random glucose; RG) may capture diverse glucoregulatory processes more effectively than previous genome-wide association studies (GWAS) of fasting glycaemia or after standardised glucose loads. Through GWAS meta-analysis of RG in 493,036 individuals without diabetes of diverse ethnicities we identified 128 associated loci represented by 162 distinct signals, including 14 with sex-dimorphic effects, 9 discovered through trans-ethnic analysis, and 70 novel signals for glycaemic traits. Novel RG loci were particularly enriched in expression in the ileum and colon, indicating a prominent role for the gastrointestinal tract in the control of blood glucose. Functional studies and molecular dynamics simulations of coding variants of GLP1R, a well-established type 2 diabetes treatment target, provided a genetic framework for optimal selection of GLP-1R agonist therapy. We also provided new evidence from Mendelian randomisation that lung function is modulated by blood glucose and that pulmonary dysfunction is a diabetes complication. Thus, our approach based on RG GWAS provided wide-ranging insights into the biology of glucose regulation, diabetes complications and the potential for treatment stratification.

Early in the COVID-19 pandemic, people living in cities were much more likely than rural residents to become infected with and die from the virus. Beginning in the summer of 2020, however, the proportional increase in virus spread became much greater in rural areas. By March 2021, per capita cases and deaths were greater in nonmetro than in metro areas. Multi-variate regression analysis found that political views were the most important variable explaining per capita COVID-19 cases, while measures of disadvantage were the best predictors of COVID-19 deaths. Counties with high proportions of Trump voters had higher per capita cases, and in nonmetro areas, these counties had higher death rates. Overall, the best predictor of COVID-19 death rates is low levels of educational attainment, high poverty rates, and high minority populations.

Fine-scale molecular architecture is critical for nervous system and other biological functions. Methods to visualize these nanoscale structures would benefit from enhanced accessibility, throughput, and tissue compatibility. Here, we report RAIN-STORM, a rapid and scalable nanoscopic imaging optimization approach that improves three-dimensional visualization for subcellular targets in tissue at depth. RAIN-STORM uses conventional tissue samples and readily available reagents and is suitable for commercial instrumentation. To illustrate the efficacy of RAIN-STORM, we utilized the retina. We show that RAIN-STORM imaging is versatile and provide 3D nanoscopic data for over 20 synapse, neuron, glia, and vasculature targets. Sample preparation is also rapid, with a 1-day turnaround from tissue to image, and parameters are suitable for multiple tissue sources. Finally, we show that this method can be applied to clinical samples to reveal nanoscale features of human cells and synapses. RAIN-STORM thus paves the way for high-throughput studies of nanoscopic targets in tissue.

International audience; The aim of this review was to update the recommendations for optimal pain management after open and laparoscopic or robotic prostatectomy. Optimal pain management is known to influence postoperative recovery, but patients undergoing open radical prostatectomy typically experience moderate dynamic pain in the immediate postoperative day. Robot-assisted and laparoscopic surgery may be associated with decreased pain levels as opposed to open surgery. We performed a systematic review using Preferred Reporting Items for Systematic Reviews and Meta-Analysis (PRISMA) with PROcedure SPECific Postoperative Pain ManagemenT (PROSPECT) methodology. Randomised controlled trials (RCTs) published in the English language, from January 2015 until March 2020, assessing postoperative pain, using analgesic, anaesthetic and surgical interventions, were identified from MEDLINE, EMBASE and Cochrane Databases. Of the 1797 studies identified, 35 RCTs and 3 meta-analyses met our inclusion criteria. NSAIDs and COX-2 selective inhibitors proved to lower postoperative pain scores. Continuous intravenous lidocaine reduced postoperative pain scores during open surgery. Local wound infiltration showed positive results in open surgery. Bilateral transversus abdominis plane (TAP) block was performed at the end of surgery and lowered pain scores in robot-assisted procedures, but results were conflicting for open procedures. Basic analgesia for prostatic surgery should include paracetamol and NSAIDs or COX-2 selective inhibitors. TAP block should be recommended as the first-choice regional analgesic technique for laparoscopic/robotic radical prostatectomy. Intravenous lidocaine should be considered for open surgeries.

A pair of neptunium Schiff base coordination complexes, NpVIO2L(MeOH) and NpIVL2 {H2L = N,N′-bis[(4,4′-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized and analyzed by severa...

A facile synthesis of an americium complex with a sulfur-donor ligand has been developed, allowing characterization of americium bonding from multiple perspectives via several techniques. Reaction of

Questions: Buffel grass (Cenchrus ciliaris L.) is a drought-adapted invasive plant that has become a serious environmental weed in many arid and semi-arid systems. This paper examined whether eradication of buffel grass infestations: (i) increases frequency, richness and diversity of native vegetation and seed bank pools; and (ii) improves availability of seed resources for granivores. Location: Alluvial ironwood/corkwood woodlands in arid central Australia. Methods: We assessed differences in floristic and seed bank composition between buffel-infested sites and sites where buffel grass had been eradicated ca. 12 years previously. Plant species frequency data from nested-quadrat sampling were amalgamated into plant functional groups to examine their relationship to buffel treatment. A seed flotation method was employed to: (i) assess seed bank composition of functional groups at eradicated vs. infested sites; and (ii) test whether the mass of seeds available for granivores was higher at buffel-free sites. Results: Buffel-eradicated sites supported richer and more diverse vegetation and seed banks across all functional groups except perennial grasses. The effect was strongest for perennial forbs, annual/short-lived forbs, and annual/short-lived grasses. The overall mass of seeds of non-buffel grass species was ca. 10-fold higher at buffel-removed sites. Numbers of seeds of species in the 0.001–0.009 9 g and 0.000 1–0.000 99 g size classes, both of which contain species with seeds consumed by granivores, were ca. 20- and 14-fold higher respectively at buffel-removed sites. Conclusions: Buffel grass removal at localised scales provides islands of habitat with improved opportunities for native plant re-establishment and abundant foraging resources for granivores. Future research must disentangle the relative importance of dispersal vs. residual seed banks for community restoration after buffel grass invasion. Extended delays in eradication could allow seed bank reserves to deteriorate to a state that no longer permits regeneration.

An approach to obtaining substantial amounts of data from a hazardous starting material that can only be obtained and handled in small quantities is demonstrated by the investigation of a single small-scale reaction of cyclooctatetraene, C8H8, with a solution obtained from the reduction of Cp'3Pu (Cp' = C5H4SiMe3) with potassium graphite. This one reaction coupled with oxidation of a product has provided single-crystal X-ray structural data on three organoplutonium compounds as well as information on redox chemistry thereby demonstrating an efficient route to new reactivity and structural information on this highly radioactive element. The crystal structures were obtained from the reduction of C8H8 by a putative Pu(II) complex, (Cp'3PuII)1-, generated in situ, to form the Pu(III) cyclooctatetraenide complex, [K(crypt)][(C8H8)2PuIII], 1-Pu, and the tetra(cyclopentadienyl) Pu(III) complex, [K(crypt)][Cp'4PuIII], 2-Pu. Oxidation of the sample of 1-Pu with Ag(I) afforded a third organoplutonium complex that has been structurally characterized for the first time, (C8H8)2PuIV, 3-Pu. Complexes 1-Pu and 3-Pu contain Pu sandwiched between parallel (C8H8)2- rings. The (Cp'4PuIII)- anion in 2-Pu features three η5-Cp' rings and one η1-Cp' ring, which is a rare example of a formal Pu-C η1-bond. In addition, this study addresses the challenge of small-scale synthesis imparted by radiological and material availability of transuranium isotopes, in particular that of pure metal samples. A route to an anhydrous Pu(III) starting material from the more readily available PuIVO2 was developed to facilitate reproducible syntheses and allow complete spectroscopic analysis of 1-Pu and 2-Pu. PuIVO2 was converted to PuIIIBr3(DME)2 (DME = CH3OCH2CH2OCH3) and subsequently PuIIIBr3(THF)x, which was used to independently synthesize 1-Pu, 2-Pu, and 3-Pu.