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At least 145 records · Page 8

Mechanism of Ni-Catalyzed Photochemical Halogen Atom-Mediated C(sp 3 )–H Arylation

Within the context of Ni photoredox catalysis, halogen atom photoelimination from Ni has emerged as a fruitful strategy for enabling hydrogen atom transfer (HAT)-mediated C(sp 3 )–H functionalization. Despite the numerous synthetic transformations invoking this paradigm, a unified mechanistic hypothesis that is consistent with experimental findings on the catalytic systems and accounts for halogen radical formation and facile C(sp 2 )–C(sp 3 ) bond formation remains elusive. We employ kinetic analysis, organometallic synthesis, and computational investigations to decipher the mechanism of a prototypical Ni-catalyzed photochemical C(sp 3 )–H arylation reaction. Our findings revise the previous mechanistic proposals, first by examining the relevance of SET and EnT processes from Ni intermediates relevant to the HAT-based arylation reaction. Our investigation highlights the ability for blue light to promote efficient Ni–C(sp 2 ) bond homolysis from cationic Ni III and C(sp 2 )–C(sp 3 ) reductive elimination from bipyridine Ni II complexes. However interesting, the rates and selectivities of these processes do not account for the productive catalytic pathway. Instead, our studies support a mechanism that involves halogen atom evolution from in situ generated Ni II dihalide intermediates, radical capture by a Ni II (aryl)(halide) resting state, and key C–C bond formation from Ni III . Oxidative addition to Ni I , as opposed to Ni 0 , and rapid Ni III /Ni I comproportionation play key roles in this process. Furthermore, the findings presented herein offer fundamental insight into the reactivity of Ni in the broader context of catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cyclometalated Platinum Compounds from Competing C–H/C–X Bond Activation Pathways

X−C^N^N (X = Br, Cl) ligands were reacted with [Pt 2 Me 4 (μ- SMe 2 ) 2 ], 1, resulting in a six-coordinate cyclometalated platinum(IV) compound containing an anionic C^N^N ligand when X = Br and both a platinum(IV) and a platinum(II) product when X = Cl. The platinum(II) species was formed by C−H activation, followed by reductive elimination of methane. The platinum compounds were characterized by multinuclear NMR spectroscopy and single-crystal X-ray diffraction (SCXRD). Photophysical properties were explored by using UV/vis, emission, and transient absorption (TA) spectroscopies. DFT and TDDFT calculations were performed to examine the competition between C−H activation and C−X oxidative addition and compared to experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Test of the Gravitational Force Law on Cosmological Scales Using the Kinematic Sunyaev-Zeldovich Effect

The mean pairwise velocity of massive halos reflects the gravitational force law on cosmic scales. For this work, we combine cosmic microwave background intensity maps from the Atacama Cosmology Telescope and a galaxy catalog from the Sloan Digital Sky Survey to estimate the mean pairwise velocity using the kinematic Sunyaev-Zeldovich (kSZ) effect. On scales from 30 to 230 megaparsecs, we constrain the gravitational acceleration between pairs of halos at separation 𝑟 to be 𝑔 ∝ 1/𝑟 𝑛 with 𝑛 = 2.1 ± 0.3, which is consistent with Newtonian gravity in an expanding spacetime (i.e., the standard Λ⁢ CDM model). This constraint shows agreement with an inverse quadratic radial dependence over the large distances separating galaxy halos, as expected in standard cosmology. Upcoming surveys have the potential to rule out 𝑛 = 1 at 10⁢𝜎 significance. Our results establish the kSZ effect as a powerful tool for testing gravity on cosmological scales.

alternative gravity theories↗

Placing High-redshift Quasars in Perspective: A Catalog of Spectroscopic Properties from the Gemini Near Infrared Spectrograph–Distant Quasar Survey

Here, we present spectroscopic measurements for 226 sources from the Gemini Near Infrared Spectrograph–Distant Quasar Survey (GNIRS-DQS). Being the largest uniform, homogeneous survey of its kind, it represents a flux-limited sample ($m_i$ ≲ 19.0 mag, H ≲ 16.5 mag) of Sloan Digital Sky Survey (SDSS) quasars at 1.5 ≲ $\mathcal{z}$ ≲ 3.5 with a monochromatic luminosity ($\lambda {L}_{\lambda }$) at 5100 Å in the range of 10 44 –10 46 erg s –1 . A combination of the GNIRS and SDSS spectra covers principal quasar diagnostic features, chiefly the C IV λ1549, Mg ii λλ2798, 2803, Hβ λ4861, and [O III ] λλ4959, 5007 emission lines, in each source. The spectral inventory will be utilized primarily to develop prescriptions for obtaining more accurate and precise redshifts, black hole masses, and accretion rates for all quasars. Additionally, the measurements will facilitate an understanding of the dependence of rest-frame ultraviolet–optical spectral properties of quasars on redshift, luminosity, and Eddington ratio, and test whether the physical properties of the quasar central engine evolve over cosmic time.

79 ASTRONOMY AND ASTROPHYSICS↗

Testing Low-Loss Microstrip Materials with MKIDs for Microwave Applications

Future measurements of the millimeter-wavelength sky require a low-loss superconducting microstrip, typically made from niobium and silicon-nitride, coupling the antenna to detectors. Here, we propose a simple device for characterizing these low-loss microstrips at 150 GHz. In our device we illuminate an antenna with a thermal source and compare the measured power at 150 GHz transmitted down microstrips of different lengths. The power measurement is made using Microwave Kinetic Inductance Detectors (MKIDs) fabricated directly onto the microstrip dielectric, and comparing the measured response provides a direct measurement of the microstrip loss. Our proposed structure provides a simple device (4 layers and a DRIE etch) for characterizing the dielectric loss of various microstrip materials and substrates. We present initial results using these devices. We demonstrate that the millimeter wavelength loss of microstrip lines, a few tens of millimeters long, can be measured using a practical aluminum MKID with a black body source at a few tens of Kelvin.

47 OTHER INSTRUMENTATION↗

Iron, magnesium, and titanium isotopic fractionations between garnet, ilmenite, f ayalite, biotite, and tourmaline: Results from NRIXS, ab initio , and study of mineral separates from the Moosilauke metapelite

Interpreting isotopic signatures documented in natural rocks requires knowledge of equilibrium isotopic fractionation factors. Here, we determine equilibrium Fe isotope fractionation factors between several common rock-forming minerals using a comparative approach involving three independent methods: (i) isotopic analyses of natural minerals from a metapelite from Mt. Moosilauke, New Hampshire, for which equilibration temperature and pressure are well constrained to be near the aluminosilicate triple point (T ≃ 500 °C, P ≃ 4 kbar), (ii) Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements of Fe force constants of minerals, and (iii) Density Functional Theory (DFT) ab initio calculations of Fe force constants of minerals. The minerals studied for Fe isotopes include, in increasing order of their β-factors: garnet < ilmenite ≈ fayalite < biotite < tourmaline < muscovite ≈ plagioclase. Some of this ordering is affected by the presence of Fe 3+ in the minerals, which tends to form stiffer bonds and be associated with heavy Fe isotope enrichments relative to Fe 2+ . We are, however, able to assess the magnitude of the effect of the ratio Fe 3+ /ΣFe on equilibrium fractionation factors, notably on the ilmenite-hematite solid solution. Equilibrium Fe isotopic fractionation factors between garnet, ilmenite, biotite, tourmaline and fayalite are determined. We also report Mg and Ti isotopic compositions of selected Moosilauke minerals that allow us to better constrain the equilibrium fractionation factors for garnet-biotite-tourmaline (Mg isotopes) and biotite-ilmenite (Ti isotopes). We show how the newly determined equilibrium fractionation factors can be used to address diverse problems in Earth and planetary sciences, notably (i) Fe and Mg isotopic fractionation during anatexis, (ii) Fe isotopic fractionation in lunar ilmenite, and (iii) Ti isotopic fractionation during fluvial transport of minerals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cosolvent-tuned interactions in ionic liquids: A vibrational and quantum-chemical study of ethylene glycol ratio effects

Ionic liquids (ILs) are attractive media for CO 2 capture but remain limited by viscosity and cost. Blending ILs with ethylene glycol (EG) is a practical route to mitigate these constraints, yet the molecular origins of cosolvent effects and their dependence on composition are not well resolved. We combine Fourier-transform infrared (FT-IR) spectroscopy with quantum-chemical (DFT) analysis to elucidate how the IL:EG molar ratio modulates intermolecular interactions and electronic structure. Computed vibrational frequencies enable mode assignment and deconvolution of overlapping bands, revealing systematic, ratio-dependent shifts and broadenings in (i) EG O–H stretching, (ii) cation and EG C–H stretchings (imidazolium C2–H, C4–H, C5–H, methyl and ethyl groups, -CH2 of EG), (iii) anion signature modes (e.g., CN motifs), and (iv) EG C–O and C–C stretchings, consistent with the redistribution of hydrogen-bonding networks. Molecular electrostatic potential (MESP) maps quantify attenuation of extreme potential regions with increasing EG, indicating progressive screening of cation–anion electrostatic interactions. Quantum Theory of Atoms in Molecules (QTAIM) identifies emergent bond critical points between EG and the IL ions, while Reduced Density Gradient–Noncovalent Interaction (RDG–NCI) analysis differentiates strong directional hydrogen bonds from dispersive contacts across compositions. Together, these results show that EG fraction controls a switch from predominantly ion–ion to mixed ion–EG coordination, altering local polarity and polarizability that underlie the observed FT-IR trends. The framework provides composition–structure–spectrum relationships that can guide rational selection of IL:EG ratios to balance favorable molecular interactions with practical performance targets in scalable CO 2 capture systems.

DAC↗

Multi-parametric analysis for mixed integer linear programming: An application to transmission upgrade and congestion management

Upgrading the capacity of existing transmission lines is essential for meeting the growing energy demands, facilitating the integration of renewable energy, and ensuring the security of the transmission system. This study focuses on the selection of lines whose capacities and by how much should be expanded from the perspective of the Independent System Operators (ISOs) to minimize the total system cost. We employ advanced multi-parametric programming and an enhanced branch-and-bound algorithm to address complex mixed-integer linear programming (MILP) problems, considering multi-period time constraints and physical limitations of generators and transmission lines. To characterize the various decisions in transmission expansion, we model the increased capacity of existing lines as parameters within a specified range. This study first relaxes the binary variables to continuous variables and applies the Lagrange method and Karush-Kuhn-Tucker (KKT) conditions to obtain optimal solutions and identify critical regions associated with active and inactive constraints. Moreover, we extend the traditional branch-and-bound (B&B) method by determining the problem’s upper and lower bounds at each node of the B&B decision tree, helping to manage computational challenges in large-scale MILP problems. Here, we compare the difference between the upper and lower bounds to obtain an approximate optimal solution within the decision-makers’ tolerable error range. In addition, the first derivative of the objective function on the parameters of each line is used to inform the selection of lines for easing congestion and maximizing social welfare. Finally, the capacity upgrades are selected by weighing the reductions in system costs against the expense of upgrading line capacities. The findings are supported by numerical simulations and provide transmission-line planners with decision-making guidance.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Dual-Emitting Cyclometalated Platinum Compounds with Isocyanide Ligands

Cyclometalated platinum(II) compounds with both C^N chelating iminic ligands and isocyanide ligands were synthesized. Two sets of compounds from the reaction of two separate HC^N ligands (derived from thiophene or benzene) with [Pt2Me4(μ-SMe 2 ) 2 ] were obtained, resulting in square planar compounds with an anionic C^N ligand, a methyl ligand, and a dimethyl sulfide (dms) ligand completing the coordination sphere. Subsequently, the dms ligand was easily substituted by several isocyanide ligands (2-naphthyl, adamantyl, 2,6-dimethylphenyl, ptoluenesulfonylmethyl). The compounds were characterized by multinuclear NMR spectroscopy, IR spectroscopy, and singlecrystal X-ray diffraction (SCXRD). Their photophysical properties were explored using UV/vis, emission, and transient absorption (TA) spectroscopy. The emission spectra for the thiophene-derived compounds showed well-defined dual emission peaks, while the benzene-derived compounds’ bands appeared less resolved. DFT and TDDFT calculations were performed, and results were compared to the observed spectroscopic properties of the newly synthesized complexes.

Inorganic carbon compounds↗

Tale of Three Molecular Nitrides: Mononuclear Vanadium (V) and (IV) Nitrides As Well As a Mixed-Valence Trivanadium Nitride Having a V 3 N 4 Double-Diamond Core

Here, transmetallation of [VCl 3 (THF) 3 ] and [TlTp tBu,Me ] afforded [(Tp tBu,Me )VCl 2 ] (1, Tp tBu,Me = hydro-tris(3-tert-butyl-5-methylpyrazol-1-yl)borate), which was reduced with KC 8 to form a $C_{3v}$ symmetric V II complex, [(Tp tBu,Me )VCl] (2). Complex 1 has a high-spin ($\textit{S}$ = 1) ground state and displays rhombic high-frequency and -field electron paramagnetic resonance (HFEPR) spectra, while complex 2 has an $\textit{S}$ = 3/2 4 A 2 ground state observable by conventional EPR spectroscopy. Complex 1 reacts with NaN 3 to form the V V nitride-azide complex [(Tp tBu,Me )V≡N(N 3 )] (3). A likely V III azide intermediate en route to 3, [(Tp tBu,Me )VCl(N 3 )] (4), was isolated by reacting 1 with N 3 SiMe 3 . Complex 4 is thermally stable but reacts with NaN3 to form 3, implying a bis-azide intermediate, [(Tp tBu,Me )V(N 3 ) 2 ] (A), leading to 3. Reduction of 3 with KC 8 furnishes a trinuclear and mixed-valent nitride, [{(Tp tBu,Me )V} 2 ($μ_{4-}$VN 4 )] (5), conforming to a Robin–Day class I description. Complex 5 features a central vanadium ion supported only by bridging nitride ligands. Contrary to 1, complex 2 reacts with NaN 3 to produce an azide-bridged dimer, [{(Tp tBu,Me )V} 2 (1,3-$μ_2$-N 3 ) 2 ] (6), with two antiferromagnetically coupled high-spin V II ions. Complex 5 could be independently produced along with [($κ_2$-Tp tBu,Me ) 2 V] upon photolysis of 6 in arene solvents. The putative {V IV ≡N} intermediate, [(Tp tBu,Me )V≡N] (B), was intercepted by photolyzing 6 in a coordinating solvent, such as tetrahydrofuran (THF), yielding [(Tp tBu,Me )V≡N(THF)] (B-THF). In arene solvents, B-THF expels THF to afford 5 and [($κ_2$-Tp tBu,Me ) 2 V]. A more stable adduct (B-OPPh 3 ) was prepared by reacting B-THF with OPPh 3 . These adducts of B are the first neutral and mononuclear V IV nitride complexes to be isolated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

β decay of neutron-rich 76 Cu and the structure of 76 Zn

In this work, the β decay of 76 Cu to the levels of 76 Zn was studied at the Holifield Radioactive Ion Beam Facility (HRIBF) at Oak Ridge National Lab (ORNL). A purified 76 Cu beam was developed and data were recorded for the decay of the A=76 decay chain using four high-purity germanium (HPGe) clover detectors at the Low-energy Radioactive Ion Beam Spectroscopy Station (LeRIBSS). In this measurement, data on γ-ray emission following β decay, including βγ and γγ coincidences, were collected and γγ spectra were analyzed to identify the statistically significant coincidences. From this analysis, we propose a level scheme for 76 Zn which contains a total of 59 energy levels up to 6.0 MeV containing 105 γ rays. We have identified an additional 53 γ rays associated with this decay which could not be place in the decay scheme due to insufficient coincidence information or no energy match to identified levels. No γ rays from states in 75 Zn fed in the delayed-neutron branch were observed even though other γ rays in the A=75 decay chain were observed. Spin and parity assignments are proposed for some levels based on comparison to systematics and shell model calculations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

12.3% Efficient Lifted-Off and Reconstructed As-Doped CdTe Thin Film Solar Cell

CdTe:As devices grown by MOCVD in the superstrate configuration have been reconfigured to a substrate structure, by employing a cleaving and reconstruction technique. Indium and aluminium doped Zinc oxide (IZO and AZO) layers were used as the transparent front interface without a metal grid. A substrate efficiency of 12.3% was realized with AZO front contact, retaining 80% of the superstrate device efficiency and an impressive approximately 99% of the open-circuit voltage. The IZO-based substrate device on the other hand performed at approximately 69 % retained efficiency. The crucial role of front interfaces is highlighted by the two contacts used here. The results in this work show promise for the development of highly efficient substrate CdTe:As devices.

II-VI semiconductor materials↗

Molecular analysis and essentiality of Aro1 shikimate biosynthesis multi-enzyme in Candida albicans

In the human fungal pathogen Candida albicans, ARO1 encodes an essential multi-enzyme that catalyses consecutive steps in the shikimate pathway for biosynthesis of chorismate, a precursor to folate and the aromatic amino acids. We obtained the first molecular image of C. albicans Aro1 that reveals the architecture of all five enzymatic domains and their arrangement in the context of the full-length protein. Aro1 forms a flexible dimer allowing relative autonomy of enzymatic function of the individual domains. Our activity and in cellulo data suggest that only four of Aro1’s enzymatic domains are functional and essential for viability of C. albicans, whereas the 3-dehydroquinate dehydratase (DHQase) domain is inactive because of active site substitutions. We further demonstrate that in C. albicans, the type II DHQase Dqd1 can compensate for the inactive DHQase domain of Aro1, suggesting an unrecognized essential role for this enzyme in shikimate biosynthesis. In contrast, in Candida glabrata and Candida parapsilosis, which do not encode a Dqd1 homolog, Aro1 DHQase domains are enzymatically active, highlighting diversity across Candida species.

59 BASIC BIOLOGICAL SCIENCES↗

Combining Astrometry and Elemental Abundances: The Case of the Candidate Pre-Gaia Halo Moving Groups G03-37, G18-39, and G21-22

While most moving groups are young and nearby, a small number have been identified in the Galactic halo. Understanding the origin and evolution of these groups is an important piece of reconstructing the formation history of the halo. Here we report on our analysis of three putative halo moving groups: G03-37, G18-39, and G21-22. Based on Gaia EDR3 data, the stars associated with each group show some scatter in velocity (e.g., Toomre diagram) and integrals of motion (energy, angular momentum) spaces, counter to expectations of moving-group stars. We choose the best candidate of the three groups, G21-22, for follow-up chemical analysis based on high-resolution spectroscopy of six presumptive members. Using a new Python code that uses a Bayesian method to self-consistently propagate uncertainties from stellar atmosphere solutions in calculating individual abundances and spectral synthesis, we derive the abundances of α- (Mg, Si, Ca, Ti), Fe-peak (Cr, Sc, Mn, Fe, Ni), odd-Z (Na, Al, V), and neutron-capture (Ba, Eu) elements for each star. We find that the G21-22 stars are not chemically homogeneous. Based on the kinematic analysis for all three groups and the chemical analysis for G21-22, we conclude the three are not genuine moving groups. The case for G21-22 demonstrates the benefit of combining kinematic and chemical information in identifying conatal populations when either alone may be insufficient. Comparing the integrals of motion and velocities of the six G21-22 stars with those of known structures in the halo, we tentatively associate them with the Gaia-Enceladus accretion event.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Detecting rare neutral atomic-carbon absorbers with a deep neural network

ABSTRACT C i absorbers play an important role as indicators for exploring the presence of cold gas in the interstellar medium of galaxies. However, the current data base of C i absorbers is very limited due to their weak absorption feature and rarity. Here, we report results from a search of C i λλ1560, 1656 absorption lines using Mg ii absorbers as signposts with modified deep learning algorithms, which provides a very quick way to search for weak C i absorber candidates. A total of 107 C i absorbers were detected, which nearly doubles the size of previously known samples. In addition, we found 17 C i absorbers to be associated with 2175 Å dust absorbers (2DAs), i.e. about 16 per cent C i absorbers are associated with 2DAs. Comparing the average dust depletion patterns of C i absorbers with those of damped Lyman α absorbers (DLAs), Mg ii absorbers, Ca ii absorbers, and 2175 Å dust absorbers (2DAs) shows that C i absorbers generally have environments with more dust than DLAs, Mg ii, and Ca ii absorbers, but similar to dust in 2DAs. Similarity between the dust depletion pattern of C i absorbers to that of the warm disc in the Milky Way indicates that C i absorption clouds are possibly associated with disc components in distant galaxies. Therefore, C i absorbers are confirmed to be excellent probes to trace cold gas and dust in the Universe.

Ge, Jian↗

Molecular-Scale Characterization of Photoinduced Charge Separation in Mixed-Dimensional InSe–Organic van der Waals Heterostructures

Layered indium selenide (InSe) is an emerging two-dimensional semiconductor that has shown significant promise for high-performance transistors and photodetectors. The range of optoelectronic applications for InSe can potentially be broadened by forming mixed-dimensional van der Waals heterostructures with zero-dimensional molecular systems that are widely employed in organic electronics and photovoltaics. Here, we report the spatially resolved investigation of photoinduced charge separation between InSe and two molecules (C 70 and C 8 -BTBT) using scanning tunneling microscopy combined with laser illumination. We experimentally and computationally show that InSe forms type-II and type-I heterojunctions with C 70 and C 8 -BTBT, respectively, due to an interplay of charge transfer and dielectric screening at the interface. Laser-excited scanning tunneling spectroscopy reveals a ~0.25 eV decrease in the energy of the lowest unoccupied molecular orbital of C 70 with optical illumination. Furthermore, photoluminescence spectroscopy and Kelvin probe force microscopy indicate that electron transfer from InSe to C 70 in the type-II heterojunction induces a photovoltage that quantitatively matches the observed downshift in the tunneling spectra. In contrast, no significant changes are observed upon optical illumination in the type-I heterojunction formed between InSe and C 8 -BTBT. Density functional theory calculations further show that, despite the weak coupling between the molecular species and InSe, the band alignment of these mixed-dimensional heterostructures strongly differs from the one suggested by the ionization potential and electronic affinities of the isolated components. Self-energy-corrected density functional theory indicates that these effects are the result of the combination of charge redistribution at the interface and heterogeneous dielectric screening of the electron–electron interactions in the heterostructure. In addition to providing specific insight for mixed-dimensional InSe–organic van der Waals heterostructures, this work establishes a general experimental methodology for studying localized charge transfer at the molecular scale that is applicable to other photoactive nanoscale systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Coherence of Metal Absorbers toward Background Quasar Pairs

Abstract We investigate the spatial coherence of metal absorption lines in the circumgalactic medium using 4115 quasar pairs from Sloan Digital Sky Survey DR16. We identify 184 Mg ii (15 with dual detections) and 50 C iv (11 with dual detections) absorber pairs. The fraction of pairs with fractional equivalent width difference δW r ≤ 0.5 declines with projected separation: for Mg ii , it drops from ∼52% at 0–25 kpc to ∼7% at 100–200 kpc, while for C iv , it decreases from ∼100% to ∼21% over 0–200 kpc. In every separation bin, C iv absorbers with δW r ≤ 0.5 maintain a higher fraction than Mg ii absorbers. Similar results are obtained when the nondetections are treated as 2 σ W r upper limits in a survival analysis. The transverse autocorrelation function shows strong Mg ii clustering within 0–25 kpc, whereas the C iv excess remains relatively flat out to ∼100 kpc. These findings suggest that high-ionization C iv gas retains coherence over larger transverse scales than low-ionization Mg ii gas, in agreement with previous lensed quasar and high-resolution studies.

Li, Jing [Guangxi University] (ORCID:0009000148751↗