Solvent attenuation of dispersion interactions quantified in polar and nonpolar media using rigid CH-π balances.

Solvent attenuation of dispersion interactions was quantified using a new class of rigid intramolecular CH-π molecular balances. These balances incorporate small, two-carbon CH donors that minimize solvophobic effects and isolate the dispersion component. Folding energies (Δ ) were measured across eight solvents: cyclohexane, toluene, chloroform, ethyl acetate, acetone, acetonitrile, DMSO, and methanol.

Wild pigs impact reproductive season movements and space use of wild turkeys.

Background: Impacts of invasive species on the movements and space use of native fauna have potential implications during the reproductive period. Over the last three decades, native wild turkeys () have experienced a notable decline in productivity while invasive wild pigs () have expanded populations throughout the southeastern United States. Camera studies have shown that the presence of wild pigs can negatively impact detection of wild turkeys in areas of overlapping use.

A Mixed-Anion Design Approach for High-Efficiency X-ray Scintillators: A Study of KLn(SO)F (Ln = Eu, Gd, Tb, Dy, Ho, and Tm).

High-quality single crystals of mixed anion rare earth sulfate fluorides KLn(SO)F (Ln = Eu, Gd, Tb, Dy, Ho, and Tm), monoclinic space group 2/, were obtained using an HF-free mild hydrothermal synthesis. Thermal, magnetic, and optical properties of these materials were investigated after determining their crystal structures and their chemical compositions using a combination of single-crystal and powder X-ray diffraction. Notably, the photoluminescence and radioluminescence behavior of KEuSOF and KTbSOF were studied for the first time, featuring the intense green radioluminescence of KTbSOF, which is comparable to the integrated intensity of the commercial bismuth germanium oxide (BiGeO) scintillator, while KEuSOF scintillates in red with an integrated intensity of 49% of BiGeO.

Non-spectator behavior of a neutral phosphine ligand driven by a redox-active boron cluster.

A new concept of ligand ambiphilicity that relies on the redox behavior of the indirectly coordinated boron cluster scaffold instead of the direct involvement of a single center in a ligand is introduced. A copper(i) complex of a carboranyl-based triphosphine, [ P--{CB}-P--{CB}- P]CuPF, in acetonitrile solution coordinates an exogenous X anion (X = Cl or N ) at the phosphorus center of the ligand and not at the cationic metal site to form [ P(X)--{CB}-P--{CB}- P]Cu(CHCN). This first example of a nontraditional ligation behavior for a trigonal phosphine is imparted by an internal two-electron event at the boron cluster, which renders a non-constrained electron-donating phosphine group into an electrophilic coordination site.

Stimuli-responsive photoswitch-actinide binding: a match made in MOFs.

The fundamentals of switchable actinide-ligand binding modes are central for designing new platforms for addressing challenges associated with, for example, isolation of pure radiological daughters for nuclear medicine or methods for efficient nuclear stockpile recycling. This study is the first to report actinide binding modes controlled by an external stimulus photochromic moieties, realized through probing thermodynamics and kinetics aspects, including changes in photoswitch isomerization constants upon metal coordination and enthalpies associated with the synergistic actinide-switch photochromic processes. A comprehensive analysis of the presented concept was executed through evaluation of data acquired through a multivariate strategy involving isothermal titration calorimetry, crystallography, spectroscopy, and theoretical modeling on the example of actinide-containing compounds based on thorium(iv)-, and uranium(iv, vi), as well as transuranic elements such as plutonium(iv) in solution and within a metal-organic framework (MOF) matrix for the first time.

Investigation of Americium-Containing Phosphates, Silicates, Borates, Molybdates, and Fluorides Synthesized via High-Temperature Flux Crystal Growth.

The crystal chemistry of americium-containing extended structures was investigated, and several classes of americium-containing solid-state oxide materials were obtained in single-crystal form via high-temperature flux crystal growth. This enabled the structural characterization of rare examples of ternary, quaternary, and penternary americium-containing silicates KAm (SiO) and CsAmSiO, phosphates NaAm (PO) and KAm (PO), borates BaAm(BO) and AmBO, borate halides CaAm(BO)Cl, molybdates LiAmMoO, and fluorides CsAmF. Using these crystallographic data, the ionic radii of Am with coordination numbers of six (0.

Impacts of Wild Pigs on Space Use and Movements of Wild Turkeys During Autumn and Winter.

Wild pigs () affect native flora and fauna in the areas they invade, including ground-nesting birds. While results from camera-based studies have suggested that wild pigs could spatiotemporally impact resource selection of wild turkeys (), there has yet to be published a foundational mechanism proposed to support such impact. Additionally, while the autumn and winter seasons serve as an important period for improving body condition for spring breeders like wild turkeys, there exists a knowledge gap in the literature with respect to potential impacts of wild pigs on wild turkeys during this non-breeding period.

A low-temperature, one-step synthesis for monazite can transform monazite into a readily usable advanced nuclear waste form.

It has been demonstrated that monazite-type materials are excellent candidates for nuclear waste forms, and hence, their facile synthesis is of great importance for the needed sequestration of existing nuclear waste. The synthesis of monazite, LaPO, requires inconveniently high temperatures near 1000°C and generally involves the conversion of the presynthesized rhabdophane, LaPO•nHO, to the LaPO monazite phase. During this structure transformation, the rhabdophane converts irreversibly to the thermodynamically stable monoclinic monazite structure.

Embracing complexities in agricultural water management through nexus planning.

A major challenge for agricultural water management (AWM) in the 21st century is to feed a growing population in the face of increasing intersectoral resource competition, evolving diets, degradation, pandemics, geopolitical conflicts and climate change. This has to be achieved within the planetary boundaries and without compromising the livelihood and environmental (ecosystem) objectives linked to water, including provisioning, supporting and regulating services. This paper uses a systems and nexus lens to unravel the centrality and complexities in AWM, with particular emphasis on the interconnected dimensions and objectives of AWM, as well as its practices and technologies.

Kinetic Control and Trapping in the Supramolecular Polymerization of m-Terphenyl Bis-Urea Macrocycles.

Herein, we examine pathway complexity in the supramolecular polymerization of a novel m-terphenyl bis-urea macrocycle. Designed to induce kinetically metastable states, the macrocycle's concentration-dependent aggregation was studied via H NMR and IR spectroscopy in THF and CHCl₃. Temperature-dependent UV-Vis spectroscopy in water/THF revealed a cooperative nucleation-growth mechanism, indicated by a shift in λmax to longer wavelengths upon cooling.

Ionothermal Synthesis of AmBOCl: A Chiral Cubic Americium Borate Cluster.

Ionic liquids were used as low temperature solvents for the synthesis of new lanthanide and transuranic-element (TRU) borate cluster structures. Ionothermal synthesis with the ionic liquid [BMIm]Cl (1-butyl-3-methylimidazolium chloride) yielded the La, Nd, and Am containing phases LaBOCl, NdBOCl, and AmBOCl. The structures of the La, Nd, and Am borate clusters were determined by single crystal X-ray diffraction (SCXRD) and found to be cubic, in the chiral space group 23.

Synthesis, Optical, and Magnetic Properties of the Mixed Chalcogenide Semiconductor Series Eu(II)SiSeS, Prepared via the Flux-Assisted Boron Chalcogen Mixture Method.

We report a detailed structural study of a series of five new quaternary Eu(II)-containing mixed chalcogenide phases, EuSiSeS, EuSiSeS, EuSiSeS, EuSiSeS, and EuSiSe, synthesized using the flux-assisted boron chalcogen mixture (BCM) method. High-quality crystals were grown, and their crystal structures were determined by single-crystal X-ray diffraction. All members of the EuSiSeS series crystallize in the monoclinic crystal system with space group 2/, except EuSiSe, which crystallizes in the 2 space group.

Accessing bimetallic complexes through a variable bridging ligand strategy.

In this contribution we are introducing a Variable Bridging Ligand (VBL) strategy for the preparation of heterometallic complexes. One synthetic challenge associated with other methods described in the existing literature stems from the fact that if there is a need to change the donor groups on a metalloligand, both the initial ligand and the resulting metalloligand must be synthesized all over again. To circumvent this problem, we reasoned that if a metal complex would have one labile ligand that can be easily replaced by various bridging polytopic species, several metalloligands can thus be generated starting from the same starting material.

Sensitivity of Mild Hydrothermal Synthesis to the Reaction Conditions: Targeting Mixed-Metal Hexagonal Tungsten Bronze Fluorides MMF to Investigate Their Magnetic Behavior.

The synthesis of five quaternary hexagonal tungsten bronze (HTB) fluorides, MMF, ( = Cs and Rb; M = Co, Ni, and Zn; and = V) via a mild hydrothermal route is reported. The crystal structures and compositions were determined using a combination of single-crystal X-ray diffraction, Rietveld refinement of powder X-ray diffraction data, and inductively coupled plasma optical emission spectroscopy analysis. This study highlights the sensitivity of the mild hydrothermal method on the reaction temperature, solvent system, and quantity of starting reagents that directly influence the selective synthesis of kinetically stabilized fluoride materials, including hydrated fluorides, β-pyrochlores, and HTB.

Inhalation of SP-101 Followed by Inhaled Doxorubicin Results in Robust and Durable Transgene Expression in the Airways of Wild-Type and Cystic Fibrosis Ferrets.

Cystic fibrosis (CF) is a serious genetic disease caused by mutations in the CF transmembrane conductance regulator (CFTR) gene. Approved small molecule therapies benefit the majority of people with CF (pwCF), but unfortunately not all. Gene addition offers a mutation agnostic treatment option for all pwCF.

SP-101, A Novel Adeno-Associated Virus Gene Therapy for the Treatment of Cystic Fibrosis, Mediates Functional Correction of Primary Human Airway Epithelia From Donors with Cystic Fibrosis.

Cystic fibrosis (CF) is caused by mutations in the gene encoding the CF transmembrane conductance regulator (CFTR) protein. Although CF affects multiple organs, lung disease is the main cause of morbidity and mortality, and gene therapy is expected to provide a mutation-agnostic option for treatment. SP-101 is a recombinant adeno-associated virus (AAV) gene therapy vector carrying a human minigene, , and is being investigated as an inhalation treatment for people with CF.

Flux Synthesis of Alkaline-Earth Lanthanide Borates as Potential Nuclear Waste Forms.

Neodymium is typically considered the best surrogate for trivalent americium and can be used to identify Am containing materials that are likely to form. We have explored the alkaline-earth lanthanide borate phase space using alkaline-earth halide/carbonate fluxes. This resulted in the synthesis of new compounds AELn(BO)X (AE = Ca, Sr; Ln = Pr, Nd, Eu, Tb; X = Cl, Br) and AELn(BO) (AE = Sr, Ba; Ln = Pr, Nd) as well as the synthesis of two compounds of BaLn(BO)(BO) (Ln = Eu, Tb) crystallizing in a new structure type.

Redox-Active Carboranyl Diphosphine as an Electron and Proton Transfer Agent.

In this work, we report the first example of the PCET reactivity for a boron cluster compound, the zwitterionic -carboranyl diphosphonium derivative 7-P(H)Bu-10-P(H)Pr--CBH. This main-group reagent efficiently transfers two electrons and two protons to quinones to yield hydroquinones and regenerate a neutral -carboranyl diphosphine, 1-PBu-2-PPr--CBH. As we have previously reported the conversion of this -carboranyl diphosphine into the zwitterionic derivative upon reaction with main group hydrides, the transformation reported herein represents a complete synthetic cycle for the metal-free reduction of quinones, with the redox-active carboranyl diphosphine scaffold acting as a mediator.

Friends or Foes: Fundamental Principles of Th-Organic Scaffold Chemistry Using Zr-Analogs as a Guide.

The fundamental interest in actinide chemistry, particularly for the development of thorium-based materials, is experiencing a renaissance owing to the recent and rapidly growing attention to fuel cycle reactors, radiological daughters for nuclear medicine, and efficient nuclear stockpile development. Herein, we uncover fundamental principles of thorium chemistry on the example of Th-based extended structures such as metal-organic frameworks in comparison with the discrete systems and zirconium extended analogs, demonstrating remarkable over two-and-half-year chemical stability of Th-based frameworks as a function of metal node connectivity, amount of defects, and conformational linker rigidity through comprehensive spectroscopic and crystallographic analysis as well as theoretical modeling. Despite exceptional chemical stability, we report the first example of studies focusing on the reactivity of the most chemically stable Th-based frameworks in comparison with the discrete Th-based systems such as metal-organic complexes and a cage, contrasting multicycle recyclability and selectivity (>97%) of the extended structures in comparison with the molecular compounds.

Durable transgene expression and efficient re-administration after rAAV2.5T-mediated fCFTRΔR gene delivery to adult ferret lungs.

The dosing interval for effective recombinant adeno-associated virus (rAAV)-mediated gene therapy of cystic fibrosis lung disease remains unknown. Here, we assessed the durability of rAAV2.5T-fCFTRΔR-mediated transgene expression and neutralizing antibody (NAb) responses in lungs of adult wild-type ferrets.

Does type of bone graft matter? A retrospective review of the use of biological bone grafts in patients undergoing elective 1-3 level spinal interbody fusion.

Objective: There is a lack of strong evidence for use of expensive bone substitutes. This study compares perioperative data and patient reported quality-of-life outcomes across the varied types of bone graft extenders. The study analyzes the existing Quality and Outcomes Database and evaluates patient reported outcomes for 1-3 level lumbar fusion procedures comparing across different types of biologics bone graft.

Synthesis and cluster structure distortions of biscarborane dithiol, thioether, and disulfide.

The synthesis and structural characterization of the first sulfur-containing derivatives of the C,C-biscarborane {-CB} cluster - thiol, thioether, and disulfide - are reported. The biscarboranyl dithiol (1-HS-CBH) exhibits an exceedingly long intracluster carbon-carbon bond length of 1.858(3) Å, which is attributed to the extensive interaction between the lone pairs of the thiol groups and the unoccupied molecular orbital of the carborane cluster.

Breaking the photoswitch speed limit.

The forthcoming generation of materials, including artificial muscles, recyclable and healable systems, photochromic heterogeneous catalysts, or tailorable supercapacitors, relies on the fundamental concept of rapid switching between two or more discrete forms in the solid state. Herein, we report a breakthrough in the "speed limit" of photochromic molecules on the example of sterically-demanding spiropyran derivatives through their integration within solvent-free confined space, allowing for engineering of the photoresponsive moiety environment and tailoring their photoisomerization rates. The presented conceptual approach realized through construction of the spiropyran environment results in ~1000 times switching enhancement even in the solid state compared to its behavior in solution, setting a record in the field of photochromic compounds.