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The chemistry of linear uranyl(V/VI) dioxo cations, [Oyl–U–Oyl]+/2+, is dominated by coordination of uranium in the equatorial plane. Effects of this constraint were evaluated by experiment and theory for gas-phase mixed-valence UV/VI coordination dimers in which uranyl moieties are linked by alkyl dicarboxylates, [(UO2+)(UO22+)(OOC-(CH2)n-2-COO2–)2]– (n = 3–12). Faster O2-addition to dimers with short linkers n = 3 and 4, vs. n ≥ 5, suggests a structural difference. Computed structures with the shortest linkers have bridging dicarboxylates and nearly parallel, non-interacting uranyls. Longer linkers, n = 5–7, accommodate uranyl orientations with distinct UV–UVI end-on cation-cation interactions (CCIs), whereby Lewis base Oyl from UV coordinates to the acid UVI, denoted as UVOyl···UVI. The dimer structure for n = 8 has a UV–UVI side-on diamond-shape CCI, with UVOyl···UVI and UVIOyl···UV interactions. Addition of O2 to the n = 4 and 5 dimers yields [(UO22+)2(OOC-(CH2)n-2-COO2–)2(O2–)]–, with UV oxidized to UVI and O2 reduced to O2–. Whereas O2 can associate to and oxidize the exposed UV center for dimers with n = 3 and 4, the more crowded UV site in the CCI structures inhibits O2 addition. The results demonstrate rational structural control of uranyl-uranyl bonding and reactivity in small coordination complexes.

Compression is essential to high bandwidth applications such as scientific simulations and sensing applications to reduce resource burden such as storage, network transmission, and more recently I/O. Existing lossy compression methods attempt to minimize the Euclidean distance between original data and reconstructed data, which significantly limits either compression performance or reconstruction quality since original and reconstructed data sequences should be aligned. Substituting the Euclidean distance for a statistical similarity maximizes the compression performance while retaining essential data features. By implementing this methodology, IDEALEM has recently demonstrated compression ratios far exceeding 100:1, better than best-known compression methods, while preserving reconstruction quality. This work proposes an online algorithm for streaming data compression which takes account of generally concave trend of compression ratio curve, and optimizes key operation parameters. We demonstrate that the proposed algorithm successfully adapts one of the key parameters in IDEALEM to the optimal value and yields near maximum compression ratios for time series data.

In uranyl coordination complexes, UO2(L)n2+, uranium in the formally dipositive [O=U=O]2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν3. This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of the enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν3 red-shift. Here, ν3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν3 frequency From computed ν3 frequencies for bare UO2 cations and neutrals, it is inferred that the effective charge of uranyl in UO2(L)n2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlation between ν3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.

Gas-phase organoactinyl complexes possessing discrete An-C bonds (An = U, Np, Pu) were synthesized in a quadrupole ion trap by endothermic decarboxylation of [AnO2(O2C-R)3]- anion complexes in which a formally AnO22+ actinyl core is coordinated by three carboxylate ligands, with R = CH3 (methyl), CH3CC (1-propynyl), C6H5 (phenyl), C6F5 (pentafluorophenyl). Decarboxylation and competing ligand loss were studied computationally by density functional theory complementing experiment. Although decarboxylation was computed to be the energetically most favorable process in all cases, reduction from An(VI) to An(V) via neutral ligand loss was often prevalent, particularly for An = Np, Pu, presumably resulting from barriers associated with decarboxylation. Comparative hydrolysis rates of the An-C bonds were experimentally determined, and the chemical properties of these bonds were analyzed by the quantum theory of atoms in molecules. The measured hydrolysis rates differed by up to 3 orders of magnitude: the fastest was for [(CH3CC)UO2(O2C-CCCH3)2]- and the slowest for [(C6F5)PuO2(O2C-C6F5)2]-. There is a general correlation between hydrolysis exothermicity and hydrolysis rate. Prototypical hydrolysis reaction pathways computed for R = CH3 (An = U, Np) reveal a mechanism in which an outer-sphere water becomes inner-sphere concomitant with transfer of an H atom to yield an OH ligand and CH4, with a net energy release of 170 kJ mol-1 and a transition state barrier of 45 kJ mol-1 for An = U. Infrared multiphoton dissociation spectra of selected complexes were acquired to confirm the predicted structures by agreement between the computed and observed vibrational frequencies. The experiment and theory results provide an evaluation of the comparative propensities for formation of the organoactinyls as a function of actinide and carboxylate and an assessment of the nature and stability toward hydrolysis of the primarily ionic An-C bonds.

A non-oxido V(v) complex with glutaroimide-dioxime (H3L), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L)2]·2H2O, and the structure determined by X-ray diffraction. It is the first non-oxido V(v) complex that has been directly synthesized in and crystallized from aqueous solution. The distorted octahedral structure contains two fully deprotonated ligands (L3-) coordinating to V5+, each in a tridentate mode via the imide N (R V-N = 1.96 Å) and oxime O atoms (R V-O = 1.87-1.90 Å). Using 17O-labelled vanadate as the starting material, concurrent 17O/51V/1H/13C NMR, in conjunction with ESI-MS, unprecedentedly demonstrated the stepwise displacement of the oxido V[double bond, length as m-dash]O bonds by glutaroimide-dioxime and verified the existence of the "bare" V5+/glutaroimide-dioxime complex, [V(L)2]-, in aqueous solution. In addition, the crystal structure of an intermediate 1 : 1 V(v)/glutaroimide-dioxime complex, [VO2(HL)]-, in which the oxido bonds of vanadate are only partially displaced, corroborates the observations by NMR and ESI-MS. Results from this work provide important insights into the strong sorption of vanadium on poly(amidoxime) sorbents in the recovery of uranium from seawater. Also, because vanadium plays important roles in biological systems, the syntheses of the oxido and non-oxido V5+ complexes and the unprecedented demonstration of the displacement of the oxido V[double bond, length as m-dash]O bonds help with the on-going efforts to develop new vanadium compounds that could be of importance in biological applications.

A non-oxido V(v) complex with glutaroimide-dioxime (H3L), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L)2]·2H2O, and the structure determined by X-ray diffraction. It is the first non-oxido V(v) complex that has been directly synthesized in and crystallized from aqueous solution. The distorted octahedral structure contains two fully deprotonated ligands (L3-) coordinating to V5+, each in a tridentate mode via the imide N (RV-N = 1.96 Å) and oxime O atoms (RV-O = 1.87-1.90 Å). Using 17O-labelled vanadate as the starting material, concurrent 17O/51V/1H/13C NMR, in conjunction with ESI-MS, unprecedentedly demonstrated the stepwise displacement of the oxido V 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O bonds by glutaroimide-dioxime and verified the existence of the "bare" V5+/glutaroimide-dioxime complex, [V(L)2]-, in aqueous solution. In addition, the crystal structure of an intermediate 1 : 1 V(v)/glutaroimide-dioxime complex, [VO2(HL)]-, in which the oxido bonds of vanadate are only partially displaced, corroborates the observations by NMR and ESI-MS. Results from this work provide important insights into the strong sorption of vanadium on poly(amidoxime) sorbents in the recovery of uranium from seawater. Also, because vanadium plays important roles in biological systems, the syntheses of the oxido and non-oxido V5+ complexes and the unprecedented demonstration of the displacement of the oxido VO bonds help with the on-going efforts to develop new vanadium compounds that could be of importance in biological applications.

Gas-phase lanthanide-SO2 complexes, Ln(CH3SO2)3(SO2)-, were produced by collision induced dissociation (CID) of Ln(CH3SO2)4- precursors prepared by electrospray ionization. For all lanthanides except Eu, CID of Ln(CH3SO2)4- resulted in CH3 loss to form Ln(CH3SO2)3(SO2)-, which spontaneously react with O2 to form Ln(CH3SO2)3(O2)-. CID of Eu(CH3SO2)4- produced only Eu(CH3SO2)3-, with reduction from Eu(III) to Eu(II). For Ln = Yb and Sm, the Ln(CH3SO2)4- underwent neutral ligand loss to form Ln(CH3SO2)3-, which reacted with O2 to yield Ln(CH3SO2)3(O2)-, recovering the Ln(III) oxidation state. The CID results show parallels to condensed-phase Ln3+/Ln2+ redox chemistry. Density functional theory (DFT) calculations on Ln(CH3SO2)3(SO2)- for Ln = La, Yb and Lu reveal that SO2 acts as a bidentate oxygen bound ligand for doublet ground-state La(CH3SO2)3(SO2)- and Lu(CH3SO2)3(SO2)-, while the ground state for Yb(CH3SO2)3(SO2)- is an open-shell singlet with a monodentate SO2 ligand. Loss of CH3 is computed to be much more favorable than neutral ligand loss for La(CH3SO2)4- and Lu(CH3SO2)4-, whereas both channels are comparable in energy for Yb(CH3SO2)4-, in accord with the experiments. DFT results for fragmentation of Cu(CH3SO2)2- reveal that formation of the organometallic complex, Cu(CH3SO2)(CH3)-, is energetically most favorable, in agreement with contrasting fragmentation pathways of copper and lanthanide complexes.

Background: Several clinical trials have shown that vernakalant is effective in terminating recent onset atrial fibrillation (AF). The electrophysiological actions of vernakalant are not fully understood.Methods and Results: Here we report the results of a blinded study comparing the in vitro canine atrial electrophysiological effects of vernakalant, ranolazine, and dl-sotalol. Action potential durations (APD(50,75,90)), effective refractory period (ERP), post repolarization refractoriness (PRR), maximum rate of rise of the action potential (AP) upstroke (V(max)), diastolic threshold of excitation (DTE), conduction time (CT), and the shortest S(1)-S(1) permitting 1:1 activation (S(1)-S(1)) were measured using standard stimulation and microelectrode recording techniques in isolated normal, non-remodeled canine arterially perfused left atrial preparations. Vernakalant caused variable but slight prolongation of APD(90) (P=not significant), but significant prolongation of APD(50) at 30 μmol/L and rapid rates. In contrast, ranolazine and dl-sotalol produced consistent concentration- and reverse rate-dependent prolongation of APD(90). Vernakalant and ranolazine caused rate-dependent, whereas dl-sotalol caused reverse rate-dependent, prolongation of ERP. Significant rate-dependent PRR developed with vernakalant and ranolazine, but not with dl-sotalol. Other sodium channel-mediated parameters (ie, V(max), CT, DTE, and S(1)-S(1)) also were depressed significantly by vernakalant and ranolazine, but not by dl-sotalol. Only vernakalant elevated AP plateau voltage, consistent with blockade of ultrarapid delayed rectified potassium current and transient outward potassium current.Conclusions: In isolated canine left atria, the effects of vernakalant and ranolazine were characterized by use-dependent inhibition of sodium channel-mediated parameters, and those of dl-sotalol by reverse rate-dependent prolongation of APD(90) and ERP. This suggests that during the rapid activation rates of AF, the I(Na) blocking action of the mixed ion channel blocker vernakalant takes prominence. This mechanism may explain vernakalant's anti-AF efficacy. [ABSTRACT FROM AUTHOR]

BACKGROUND AND PURPOSE: Computerized 3-dimensional (3-D) motion measurement systems are used by those interested in human motion. The purposes of this study were (1) to determine the limits of accuracy in determining intersegmental angles during pendular motion at varying speeds and (2) to determine changes in accuracy introduced by autodigitization and digitization by experienced manual raters. METHODS: Angular speed of a T-shaped pendulum was systematically increased by releasing the pendulum from 4 angles (0 degrees [no movement], 45 degrees, 90 degrees, and 120 degrees). Twelve reference angles calculated from markers placed on the pendulum were estimated over 20 frames for 10 trials at each release position. RESULTS: Mean errors across trials and frames for intersegmental angles reconstructed by a 3-D motion measurement system were within +/- 1 degree across all release positions. An analysis of variance and a post hoc Tukey test revealed that the mean error for the autodigitized trials was larger than that for the manually digitized trials. For the autodigitized trials, the static trials (release position=0 degrees) produced less mean error than the trials with movement produced. The ICCs showed a high degree of consistency among all raters, ranging from .707 to .999. CONCLUSION AND DISCUSSION: Our findings support the conclusion that under carefully controlled conditions, a 3-D motion measurement system can produce clinically acceptable measurements of accuracy across a range of angular speeds. Furthermore, acceptable accuracy is possible regardless of the digitization method. [ABSTRACT FROM AUTHOR]

BACKGROUND AND PURPOSE: Three-dimensional computerized gait analysis continues to grow in use among physical therapists and other clinical specialists interested in quantitative data regarding human ambulation. This study documented the accuracy of reconstructed angular estimates under static and dynamic conditions using the Ariel Performance Analysis System. METHODS: Angular velocity was systematically increased by raising the release position of a T-shaped pendulum. Angular velocities were examined by releasing the pendulum from four angles (0 degree-static, 45 degrees, 90 degrees, and 120 degrees). Twelve reference angles were estimated over 20 autodigitized frames for 10 trials at each release position. Intraclass correlation coefficients (ICCs) and analysis-of-variance (ANOVA) procedures were used to test the hypothesis that the error of angular estimates grows with increasing angular velocity. RESULTS: Mean errors of the reconstructed angles were consistently within +/- 1.0 degree, regardless of angular velocity. An ANOVA revealed a statistically significant angular velocity effect, characterized by release position. The 90-degree release position produced the greatest error, followed by the 120-, 45-, and 0-degree release positions. The error was not significantly different between the 120- and 45-degree release positions. Intraclass correlation coefficients greater than .90 were found for all frame-to-frame angular velocities, except for the 90-degree release position. The angle estimates consistently underestimated the reference angles, regardless of release position. CONCLUSION AND DISCUSSION: The results suggest that clinically accurate angular estimates can be obtained across the range of angular velocities used in this study. [ABSTRACT FROM AUTHOR]

Dilanthanide complexes with one-electron delocalization are important targets for understanding the specific 4f/5d-bonding feature in lanthanide chemistry. Here, we report an isolable azide-bridged dicerium complex 3 [{(Trapen TMS )Ce} 2 (μ-N 3 )] • [Trapen = tris (2-aminobenzyl)amine; TMS = SiMe 3 ], which is synthesized by the reaction of tripodal ligand-supported (Trapen TMS )Ce IV Cl complex 2 with NaN 3 . The structure and bonding nature of 3 are fully characterized by X-ray crystal diffraction analysis, electron paramagnetic resonance (EPR), magnetic measurement, cyclic voltammetry, X-ray absorption spectroscopy, and quantum-theoretical studies. Complex 3 presents a trans-bent central Ce-N 3 -Ce unit with a single electron of two mixed-valent Ce atoms. The unique low-temperature (2 K) anisotropic EPR signals [ g = 1.135, 2.003, and 3.034] of 3 indicate that its spin density is distributed on the central Ce-N 3 -Ce unit with marked electron delocalization. Quantum chemical analyses show strong 4f/5d orbital mixing in the singly occupied molecular orbital of 3 , which allows for the unpaired electron to extend throughout the cerium-azide-cerium unit via a multicentered one-electron (Ce-N 3 -Ce) interaction. This work extends the family of mixed-valent dilanthanide complexes and provides a paradigm for understanding the bonding motif of ligand-bridged dilanthanide complexes.

We report the gas-phase preparation, isolation, and reactivity of a series of organolanthanides featuring the Ln-CH 3 bond. The complexes are formed by decarboxylating anionic lanthanide acetates to form trivalent [Ln III (CH 3 )(CH 3 CO 2 ) 3 ] - (Ln = La, Ce, Pr, Nd, Sm, Tb, Tm, Yb, Lu), divalent [Eu II (CH 3 )(CH 3 CO 2 ) 2 ] - , and the first examples of tetravalent organocerium complexes featuring Ce IV -C alkyl σ-bonds: [Ce IV (O)(CH 3 )(CH 3 CO 2 ) 2 ] - and [Ce IV (O)(CH 3 )(NO 3 ) 2 ] - . Attempts to isolate Pr IV -CH 3 and Tb IV -CH 3 were unsuccessful; however, fragmentation patterns reveal that the oxidation of Ln III to a Ln IV -oxo-acetate complex is more favorable for Ln = Pr than for Ln = Tb. The rate of Ln-CH 3 hydrolysis is a measure of bond stability, and it decreases from La III -CH 3 to Lu III -CH 3 , with increasing steric crowding for smaller Ln stabilizing the harder Ln-CH 3 bond against hydrolysis. [Eu II (CH 3 )(CH 3 CO 2 ) 2 ] - engages in a much faster hydrolysis versus Ln III -CH 3 . The surprising observation of similar hydrolysis rates for Ce IV -CH 3 and Ce III -CH 3 is discussed with respect to sterics, the oxo ligand, and bond covalency in σ-bonded organolanthanides.

Understanding the fundamental chemistry of soft N,S-donor ligands with actinides across the series is critical for separation science toward sustainable nuclear energy. This task is particularly challenging when the ligands are redox active. We herein report a series of actinyl complexes with a N,S-donor redox-active ligand that stabilizes different oxidation states across the actinide series. These complexes are isolated and characterized in the gas phase, along with high-level electronic structure studies. The redox-active N,S-donor ligand in the products, C 5 H 4 NS, acts as a monoanion in [U VI O 2 (C 5 H 4 NS - )] + but as a neutral radical with unpaired electrons localized on the sulfur atom in [Np V O 2 (C 5 H 4 NS • )] + and [Pu V O 2 (C 5 H 4 NS • )] + , resulting in different oxidation states for uranium and transuranic elements. This is rationalized by considering the relative energy levels of actinyl(VI) 5f orbitals and S 3p lone pair orbitals of the C 5 H 4 NS - ligand and the cooperativity between An-N and An-S bonds that provides additional stability for the transuranic elements.

Although synthesis, reactivity, and bonding of U(IV) and Th(IV) complexes have been extensively studied, direct comparison of fully analogous compounds is rare. Herein, we report corresponding complexes 1-U and 1-Th , in which U(IV) and Th(IV) are supported by the tetradentate pyridine-decorated dianionic ligand N 2 NN' (1,1,1-trimethyl- N -(2-(((pyridin-2-ylmethyl)(2-((trimethylsilyl)amino)benzyl)amino)methyl)phenyl)silanamine). Although 1-U and 1-Th are structurally very similar, they display disparate reactivities with TMS 3 SiK (tris(trimethylsilyl)silylpotassium). The reaction of (N 2 NN')UCl 2 ( 1-U ) and 1 equiv of TMS 3 SiK in THF unexpectedly formed [Cl(N 2 NN')U] 2 O ( 2-U ) featuring an unusual bent U-O-U moiety. In contrast, a salt elimination reaction between (N 2 NN')ThCl 2 ( 1-Th ) and 1 equiv of TMS 3 SiK led to thorium complex 2-Th , in which the pyridyl group has undergone a 1,4-addition nucleophilic attack. Complex 2-Th serves as a synthon for preparing dimetallic bis-azide complex 3-Th by reaction with NaN 3 . The complexes were characterized by X-ray crystal diffraction, solution NMR, FT-IR, and elemental analysis. Computations of the formation mechanism of 2-U from 1-U suggest reduced U(III) as a key intermediate for promoting the cleavage of the C-O bonds of THF. The inaccessible nature of Th(III) as an intermediate oxidation state explains the very different reactivity of 1-Th versus 1-U . Given that reactants 1-U and 1-Th and products 2-U and 2-Th all comprise tetravalent actinides, this is an unusual case of very disparate reactivity despite no net change in the oxidation state. Complexes 2-U and 3-Th provide a basis for the synthesis of other dinuclear actinide complexes with novel reactivity and properties.

2D lamellar membranes (2DLMs) are used for efficient desalination and nanofiltration. However, weak interactions between adjacent stacked nanosheets result in susceptibility to swelling that limits practical applicability. Inspired by the super adhesion of multi-point suction cups on octopus tentacles, a 2DLM is constructed from Ti 3 C 2 T x MXene supported by the macrocyclic "multi-point" molecule cucurbit[5]uril (CB5) and demonstrated for nanofiltration of methyl blue (MB) and enrichment of uranyl carbonate. Experimental results and density functional theory calculations indicate that CB5 rivets to the surface of the nanoflakes through strong stable interactions between its multiple binding sites and surface hydroxyl functional groups on MXene nanosheets. This novel 2DLM exhibits excellent nanofiltration performance (69 L m -2 h -1 bar -1 permeance with 93.6% rejection for MB) and can be recycled at least 30 times without significant degradation. The 2DLM exhibits excellent swelling resistance at high salinity, with a demonstration of selective enrichment of uranyl carbonate from artificial water and natural seawater. The results provide a new strategy for constructing highly stable 2DLMs with interlayer spacing controllable from sub-nano to nanometer scales, for size-selective sieving of molecules and ions, high-efficiency nanofiltration, and other applications., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Dinuclear perchlorate complexes of uranium, neptunium, and plutonium were characterized by reactivity and DFT, with results revealing structures containing pentavalent, hexavalent, and heptavalent actinyls, and actinyl-actinyl interactions (AAIs). Electrospray ionization produced native complexes [(AnO 2 ) 2 (ClO 4 ) 3 ] - for An:An = U:U, Np:Np, Pu:Pu, and Np:Pu, which are intuitively formulated as actinyl(V) perchlorates. However, DFT identified lower-energy structures [(AnO 2 )(AnO 3 )(ClO 4 ) 2 (ClO 3 )] - comprising a perchlorate fragmented to ClO 3 , actinyl(VI) cation An VI O 2 2+ , and neutral AnO 3 . For U:U and Np:Np, and Np in Np:Pu, the coordinated AnO 3 is calculated as actinyl(VI) with an equatorial oxo, [O yl ═An VI ═O yl ][═O eq ], whereas for Pu:Pu, it is plutonyl(V) oxyl, [O yl ═Pu V ═O yl ][-O eq • ]. The implied lower stability of Pu VI versus Np VI indicates weaker Pu═O eq versus Np═O eq bonding. Adsorption of O 2 by the U:U complex suggests oxidation of U V to U VI , corroborating the assignment of perchlorate [(An V O 2 ) 2 (ClO 4 ) 3 ] - . DFT predicts the O 2 adducts are [(An VI O 2 )(O 2 )(An VI O 2 )(ClO 4 ) 3 ] - with actinyls oxidized from +V to +VI by bridging peroxide, O 2 2- . In accordance with reactivity, O 2- addition is computed as substantially exothermic for U:U and least favorable for Pu:Pu. Collision-induced dissociation of native complexes eliminated ClO 2 to yield [(AnO 2 )(O) 2 (AnO 2 )(ClO 4 ) 2 ] - , in which fragmented O atoms bridge as oxyl O -• and oxo O 2- to yield uranyl(VI) and plutonyl(VI), or as oxos O 2- to yield neptunyl(VII), [O yl ═Np VII ═O yl ] 3+ .

Stressful environmental conditions can shape both an individual's phenotype and that of its offspring. However, little is known about transgenerational effects of chronic (as opposed to acute) stressors, nor whether these vary across the breeding lifespan of the parent. We exposed adult female (F0 generation) three-spined sticklebacks ( Gasterosteus aculeatus ) to chronic environmental stressors and compared their reproductive allocation with that of non-exposed controls across early, middle and late clutches produced within the single breeding season of this annual population. There was a seasonal trend (but no treatment difference) in F0 reproductive allocation, with increases in egg mass and fry size in late clutches. We then tested for transgenerational effects in the non-exposed F1 and F2 generations. Exposure of F0 females to stressors resulted in phenotypic change in their offspring and grandoffspring that were produced late in their breeding lifespan: F1 offspring produced from the late-season clutches of stressor-exposed F0 females had higher early life survival, and subsequently produced heavier eggs and F2 fry that were larger at hatching. Changed maternal allocation due to a combination of seasonal factors and environmental stressors can thus have a transgenerational effect by influencing the reproductive allocation of daughters, especially those born late in life.

Effectively adjusting and controlling the valence state of neptunium (Np) is essential in its separation during spent fuel reprocessing. Hydrazine and its derivatives as free-salts can selectively reduce Np(VI) to Np(V). Reduction mechanisms of Np(VI) with hydrazine and four derivatives have been explored using multiple theoretical methods in our previous works. Herein, we examine the reduction mechanism of Np(VI) with hydrazinopropionitrile (NCCH 2 N 2 H 3 ) which exhibits faster kinetics than most other hydrazine derivatives probably due to its σ-π hyperconjugation effect. Free radical ion pathways I, II and III involving the three types of hydrazine H atoms were found that correspond to the experimentally established mechanism of reduction of two Np(VI) via initial oxidation to [NCCH 2 N 2 H 3 ] + ˙, followed by conversion to NCCH 2 N 2 H (+2H 3 O + ) and ultimately to CH 3 CN + N 2 . Potential energy profiles suggest that the second redox stage is rate-determining for all three pathways. Pathway I with water-mediated proton transfer is energetically preferred for hydrazinopropionitrile. Analyses using the approaches of localized molecular orbitals (LMOs), quantum theory of atoms in molecules (QTAIM), and intrinsic reaction coordinate (IRC) elucidate the bonding evolution for the structures on the reaction pathways. The results of the spin density reveal that the reduction of the first Np(VI) ion is the outer-sphere electron transfer, while that of the second Np(VI) ion is the hydrogen transfer. This work offers new insights into the nature of reduction of Np(VI) by hydrazinopropionitrile via water-mediated proton transfer, and provides a basis for designing free-salt reductants for Np separations.

We report on the reactivity of gas-phase lanthanide-oxide nitrate complexes, [Ln(O)(NO 3 ) 3 ] - (denoted LnO 2+ ), produced via elimination of NO 2 • from trivalent [Ln III (NO 3 ) 4 ] - (Ln = Ce, Pr, Nd, Sm, Tb, Dy). These complexes feature a Ln III -O • oxyl, a Ln IV ═O oxo, or an intermediate Ln III/IV oxyl/oxo bond, depending on the accessibility of the tetravalent Ln IV state. Hydrogen atom abstraction reactivity of the LnO 2+ complexes to form unambiguously trivalent [Ln III (OH)(NO 3 ) 3 ] - reveals the nature of the oxide bond. The result of slower reactivity of PrO 2+ versus TbO 2+ is considered to indicate higher stability of the tetravalent praseodymium-oxo, Pr IV ═O, versus Tb IV ═O. This is the first report of Pr IV as more stable than Tb IV , which is discussed with respect to ionization potentials, standard electrode potentials, atomic promotion energies, and oxo bond covalency via 4f- and/or 5d-orbital participation.

Bond dissociation energies (BDEs) reported in the literature for lanthanide monofluorides and lanthanide monochlorides LnX, where X = F or Cl, exhibit substantial irregular variations across the Ln series. It is demonstrated here that correlations of these variations with reported experimentally based atomic energies to prepare the Ln constituent for bonding reveal the nature of the bonding. Whereas some molecular characteristics are well understood in the context of highly ionic bonding, with LnX considered to be (Ln + )(X - ), some significant variations in BDEs are not well rationalized simply by ionization to convert Ln to Ln + for bonding. Focusing here on lanthanide monofluorides LnF, a consideration of alternative Ln preparation schemes shows that a particularly good rationalization of BDEs is obtained by invoking the participation of a lanthanide 5d electron in bonding. This 5d participation could be in ionic (Ln + )(F - ) via π-donation from F - 2p to empty Ln + 5d orbitals or in covalent π-bonded Ln:F via polarization from Ln 5d to F 2p, with these ionic and polar covalent perspectives ultimately being equivalent. The inference of lanthanide 5d involvement suggests that the valence 4f and 6s electrons do not effectively participate in some key aspects of the bonding, presumably due to poor spatial overlap with F 2p orbitals. An extension to actinide monofluorides, AnF, assumes analogous ionic or polar covalent bonding involving a valence 6d electron and results in predictions for BDEs that include a general decrease from left to right across the series, except for a distinctive local minimum at AmF. Determining the BDE for AmF would serve to evaluate the predictions and the underlying assumption of 6d bonding. The BDE assessments/predictions for neutral monofluorides, LnF and AnF, are also applied to cationic LnF + and AnF + , and it is noted that the approach can be directly extended to f-element monochlorides, monobromides, and monoiodides.

Controlling the properties of heavy element complexes, such as those containing berkelium, is challenging because relativistic effects, spin-orbit and ligand-field splitting, and complex metal-ligand bonding, all dictate the final electronic states of the molecules. While the first two of these are currently beyond experimental control, covalent M‒L interactions could theoretically be boosted through the employment of chelators with large polarizabilities that substantially shift the electron density in the molecules. This theory is tested by ligating Bk III with 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine (terpy*), a ligand with a large dipole. The resultant complex, Bk(terpy*)(NO 3 ) 3 (H 2 O)·THF, is benchmarked with its closest electrochemical analog, Ce(terpy*)(NO 3 ) 3 (H 2 O)·THF. Here, we show that enhanced Bk‒N interactions with terpy* are observed as predicted. Unexpectedly, induced polarization by terpy* also creates a plane in the molecules wherein the M‒L bonds trans to terpy* are shorter than anticipated. Moreover, these molecules are highly anisotropic and rhombic EPR spectra for the Ce III complex are reported., (© 2021. The Author(s).)

Electrorefining process has been widely used to separate and purify metals, but it is limited by deposition potential of the metal itself. Here we report in-situ anodic precipitation (IAP), a modified electrorefining process, to purify aluminium from contaminants that are more reactive. During IAP, the target metals that are more cathodic than aluminium are oxidized at the anode and forced to precipitate out in a low oxidation state. This strategy is fundamentally based on different solubilities of target metal chlorides in the NaAlCl 4 molten salt rather than deposition potential of metals. The results suggest that IAP is able to efficiently and simply separate components of aluminum alloys with fast kinetics and high recovery yields, and it is also a valuable synthetic approach for metal chlorides in low oxidation states., (© 2021. The Author(s).)

Experiments were performed at the Lawrence Berkeley National Laboratory 88-Inch Cyclotron facility to investigate the electron-transfer reduction reaction of dipositive Lr ( Z = 103) with O 2 gas. Ions of 255 Lr were produced in the fusion-evaporation reaction 209 Bi( 48 Ca,2n) 255 Lr and were studied with a novel gas-phase ion chemistry technique. The produced 255 Lr 2+ ions were trapped and O 2 gas was introduced, such that the charge-exchange reaction to reduce 255 Lr 2+ to 255 Lr 1+ was observed and the reaction rate constant was determined to be k = 1.5(7) × 10 -10 cm 3 /mol/s. The observation that this reaction proceeds establishes the lower limit on the second ionization potential of Lr to be 13.3(3) eV. This gives further support that the actinide series terminates with Lr. Additionally, this result can be used to better interpret the situation concerning the placement of Lu and Lr on the periodic table within the current framework of the actinide hypothesis. The success of this experimental approach now identifies unique opportunities for future gas-phase reaction studies on actinide and super heavy elements.

The energetics of hydrolysis reactions for high oxidation states of oxo/hydroxo monomeric actinide species (Th IV O 2 , Pa IV O 2 , U IV O 2 , Pa V O 2 (OH), U V O 2 (OH), U VI O 3 , Np VI O 3 , Np VII O 3 (OH), and Pu VII O 3 (OH)) were calculated at the CCSD(T) level. The first step is the formation of a Lewis acid/base adduct with H 2 O (hydration), followed by a proton transfer to form a dihydroxide molecule (hydrolysis); this process is repeated until all oxo groups are hydrolyzed. The physisorption (hydration) for each H 2 O addition was predicted to be exothermic, ca. -20 kcal/mol. The hydrolysis products are preferred energetically over the hydration products for the +IV and +V oxidation states. The compounds with An VI are a turning point in terms of favoring hydration over hydrolysis. For An VII O 3 (OH), hydration products are preferred, and only two waters can bind; the complete hydrolysis process is now endothermic, and the oxidation state for the An in An(OH) 7 is +VI with two OH groups each having one-half an electron. The natural bond order charges and the reaction energies provide insights into the nature of the hydrolysis/hydration processes. The actinide charges and bond ionicity generally decrease across the period. The ionic character decreases as the oxidation state and coordination number increase so that covalency increases moving to the right in the actinide period.

Uranium trioxide, UO 3 , has a T-shaped structure with bent uranyl, UO 2 2+ , coordinated by an equatorial oxo, O 2- . The structure of cation UO 3 + is similar but with an equatorial oxyl, O •- . Neutral and cationic uranium trioxide coordinated by nitrates were characterized by collision induced dissociation (CID), infrared multiple-photon dissociation (IRMPD) spectroscopy, and density functional theory. CID of uranyl nitrate, [UO 2 (NO 3 ) 3 ] - (complex A1 ), eliminates NO 2 to produce nitrate-coordinated UO 3 + , [UO 2 (O • )(NO 3 ) 2 ] - ( B1 ), which ejects NO 3 to yield UO 3 in [UO 2 (O)(NO 3 )] - ( C1 ). Finally, C1 associates with H 2 O to afford uranyl hydroxide in [UO 2 (OH) 2 (NO 3 )] - ( D1 ). IRMPD of B1 , C1 , and D1 confirms uranyl equatorially coordinated by nitrate(s) along with the following ligands: ( B1 ) radical oxyl O •- ; ( C1 ) oxo O 2- ; and ( D1 ) two hydroxyls, OH - . As the nitrates are bidentate, the equatorial coordination is six in A1 , five in B1 , four in D1 , and three in C1 . Ligand congestion in low-coordinate C1 suggests orbital-directed bonding. Hydrolysis of the equatorial oxo in C1 epitomizes the inverse trans influence in UO 3 , which is uranyl with inert axial oxos and a reactive equatorial oxo. The uranyl ν 3 IR frequencies indicate the following donor ordering: O 2- [best donor] ≫ O •- > OH - > NO 3 - .

Despite that bond dissociation energies (BDEs) are among the most fundamental and relevant chemical properties they remain poorly characterized for most elementary lanthanide hydroxides and halides. Lanthanide ions Ln+ = Eu+, Tm+ and Yb+ are here shown to react with H2O to yield hydroxides LnOH+. Under low-energy conditions such reactions must be exothermic, which implies a lower limit of 499 kJ mol-1 for the Ln+-OH BDEs. This limit is significantly higher than previously reported for YbOH+ and is unexpectedly similar to the BDE for Yb+-F. To explain this apparent anomaly, it is considered feasible that the inefficient hydrolysis reactions observed here in a quadrupole ion trap mass spectrometer may actually be endothermic. More definitive and broad-based evaluations and comparisons require additional and more reliable BDEs and ionization energies for key lanthanide molecules, and/or energies for ligand-exchange reactions like LnF + OH ↔ LnOH + F. The hydroxide results motivated an assessment of currently available lanthanide monohalide BDEs. Among several intriguing relationships is the distinctively higher BDE for neutral LuF versus cationic LuF+, though quantifying this comparison awaits a more accurate value for the anomalously high ionization energy of LuF.

Herein we present a new viologen-based radical-containing metal-organic framework (RMOF) Gd-IHEP-7, which upon heating in air undergoes a single-crystal-to-single-crystal transformation to generate Gd-IHEP-8. Both RMOFs exhibit excellent air and water stability as a result of favorable radical-radical interactions, and their long-lifetime radicals result in wide spectral absorption in the range 200-2500 nm. Gd-IHEP-7 and Gd-IHEP-8 show excellent activity toward solar-driven nitrogen fixation, with ammonia production rates of 128 and 220 μmol h -1  g -1 , respectively. Experiments and theoretical calculations indicate that both RMOFs have similar nitrogen fixation pathways. The enhanced catalytic efficiency of Gd-IHEP-8 versus Gd-IHEP-7 is attributed to intermediates stabilized by enhanced hydrogen bonding., (© 2020 Wiley-VCH GmbH.)

Gas-phase reactions of pentavalent metal dioxide cations M V O 2 + with water were studied experimentally for M = V, Nb, Ta, Pr, Pa, U, Pu, and Am. Addition of two H 2 O can occur by adsorption to yield hydrate (H 2 O) 2 M V O 2 + or by hydrolysis to yield hydroxide M V (OH) 4 + . Displacement of H 2 O by acetone indicates hydrates for Pr V , U V , Pu V , and Am V , whereas nondisplacement indicates hydroxides for Nb V , Ta V , and Pa V . Computed potential energy profiles agree with the experimental results and furthermore indicate that acetone unexpectedly induces dehydrolysis and displaces two H 2 O from (H 2 O)VO(OH) 2 + to yield (acetone) 2 VO 2 + . Structures and energies for several M V , as well as for Th IV and U VI , indicate that hydrolysis is governed by the involvement of valence f versus d orbitals in bonding: linear f-element dioxides are more resistant to hydrolysis than bent d-element dioxides. Accordingly, for early actinides, hydrolysis of Th IV is characteristic of a 6d-block transition metal; hydration of U V and U VI is characteristic of 5f actinyls; and Pa V is intermediate between 6d and 5f. The praseodymium oxide cation Pr V O 2 + is assigned as an actinyl-like lanthanyl with properties governed by 4f bonding.

The separation of actinides has a vital place in nuclear fuel reprocessing, recovery of radionuclides, and remediation of environmental contamination. Here we propose a new paradigm of nanocluster-based actinide separation, namely, nanoextraction, that can achieve efficient sequestration of uranium in an unprecedented form of giant coordination nanocages using a cone-shaped macrocyclic pyrogallol[4]arene as the extractant. The U 24 -based hexameric pyrogallol[4]arene nanocages with distinctive [U 2 (PG) 2 ] binuclear units (PG = pyrogallol) that rapidly assembled in situ in monophasic solvent were identified by single-crystal X-ray diffraction, MALDI-TOF mass spectrometry, NMR spectroscopy, and small-angle X-ray and neutron scattering. Comprehensive biphasic extraction studies showed that this novel separation strategy has enticing advantages such as fast kinetics, high efficiency, and good selectivity over lanthanides, thereby demonstrating its potential for efficient separation of actinide ions.

The anions pertechnetate, TcO4-, and perrhenate, ReO4-, exhibit very similar chemical and physical properties. Revealing and understanding disparities between them enhances fundamental understanding of both. Electrospray ionization generated the gas-phase proton bound dimer (TcO4-)(H+)(ReO4-). Collision induced dissociation of the dimer yielded predominantly HTcO4 and ReO4-, which according to Cooks' kinetic method indicates that the proton affinity (PA) of TcO4- is greater than that of ReO4-. Density functional theory computations agree with the experimental observation, providing PA[TcO4-] = 300.1 kcal mol-1 and PA[ReO4-] = 297.2 kcal mol-1. Attempts to rationalize these relative PAs based on elementary molecular parameters such as atomic charges indicate that the entirety of bond formation and concomitant bond disruption needs to be considered to understand the energies associated with such protonation processes. Although in both the gas and solution phases, TcO4- is a stronger base than ReO4-, it is noted that the significance of even such qualitative accordance is tempered by the very different natures of the underlying phenomena.

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 [ML 3 ] 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 [ML 3 ] 3+ in the presence of H 2 O yielded a protonated ligand [L(H)] + and hydroxide [ML 2 (OH)] 2+ or hydrate [ML(L-H)(H 2 O)] 2+ , where (L-H) - is a deprotonated ligand. Although solution affinities indicate stronger binding of BTPs toward Am 3+ versus Ln 3+ , 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 [AmL 3 ] 3+ versus [LaL 3 ] 3+ and for both product isomers, [ML 2 (OH)] 2+ and [ML(L-H)(H 2 O)] 2+ . More facile removal of a ligand from [AmL 3 ] 3+ by CID does not necessarily contradict stronger Am 3+ -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.

The isolated gas-phase actinide dioxide dications, AnO 2 2+ , were evaluated by DFT and coupled cluster CCSD(T) calculations for 12 actinides, An = U-Lr. CASSCF calculations were used to define the orbitals for the CCSD(T) calculations. The characteristic linear [O═An═O] 2+ hexavalent actinyl(VI) was found to be the lowest energy structure for An = U, Np, and Pu, which also form stable actinyl(VI) species in solution and possibly for Am when spin-orbit effects are included. For Am, there is a divalent [An II (O 2 )] 2+ structure where the dioxygen is an end-on physisorbed η 1 - 3 O 2 2 kcal/mol above the actinyl when spin-orbit effects are included which lower the energy of the actinyl structure. For An = Cm, Bk, and Lr, the lowest energy structure is trivalent [An III (O 2 - )] 2+ where the dioxygen is a side-on superoxide, η 2 -O 2 - . For Cm, the actinyl is close in energy to the ground state when spin-orbit effects are included. For An = Cf, Es, Fm, Md, and No, the lowest energy structure is divalent [An II (O 2 )] 2+ where the dioxygen is an end-on physisorbed η 1 - 3 O 2 . The relative energies suggest that curyl(VI) and berkelyl(VI), like well-known americyl(VI), might be stabilized by coordinating ligands in condensed phases. The results further indicate that for californyl and beyond, the actinyl(VI) moieties will probably be elusive even using strong donor ligands. The prevalence of low oxidation states (OSs) An(II) and An(III) for transplutonium actinides reflects stabilization of the 5f orbitals and validates established trends, including the remarkably high stability of divalent No. Bond distances and other parameters suggest maximum bond covalency around plutonyl(VI), with a particularly substantial decrease in bond strength between americyl(VI) and curyl(VI).

Despite that two-dimensional transition metal carbides and carbonitrides (MXenes) are burgeoning candidates for remediation of environmental pollutants, the construction of robust functionalized MXene nanosheets with a high affinity for target heavy metal ions and radionuclides remains a challenge. Here we report the successful placement of amidoxime chelating groups on Ti 3 C 2 T x MXene surface by diazonium salt grafting. The introduction of amidoxime functional groups significantly enhances the selectivity of Ti 3 C 2 T x nanosheets for uranyl ions and also greatly improves their stability in aqueous solution, enabling efficient, rapid, and recyclable uranium extraction from aqueous solutions containing competitive metal ions. Benefiting from the excellent conductivity of MXenes, the amidoxime functionalized Ti 3 C 2 T x nanosheets show outstanding electrochemical performance such that when loaded on carbon cloth the application of an electric field increases the uranium adsorption capacity from 294 to 626 mg/g, outperforming all organic electrochemical sorption materials reported previously. The present work provides an effective strategy to functionalize MXene nanosheets with fundamental implications for the design of MXene-based selective electrosorption electrode materials.

Although metal-organic frameworks (MOFs) have been reported as important porous materials for the potential utility in metal ion separation, coordinating the functionality, structure, and component of MOFs remains a great challenge. Herein, a series of anionic rare earth MOFs (RE-MOFs) were synthesized via a solvothermal template reaction and for the first time explored for uranium(VI) capture from an acidic medium. The unusually high extraction capacity of UO 2 2+ (e.g., 538 mg U per g of Y-MOF) was achieved through ion-exchange with the concomitant release of Me 2 NH 2 + , during which the uranium(VI) extraction in the series of isostructural RE-MOFs was found to be highly sensitive to the ionic radii of the metal nodes. That is, the uranium(VI) adsorption capacities continuously increased as the ionic radii decreased. In-depth mechanism insight was obtained from molecular dynamics simulations, suggesting that both the accessible pore volume of the MOFs and hydrogen-bonding interactions contribute to the strong periodic tendency of uranium(VI) extraction.

Gas-phase coordination complexes of actinyl(v) cations, AnO 2 + , provide a basis to assess fundamental aspects of actinide chemistry. Electrospray ionization of solutions containing an actinyl cation and sulfonate anion CH 3 SO 2 - or C 6 H 5 SO 2 - generated complexes [(An V O 2 )(CH 3 SO 2 ) 2 ] - or [(An V O 2 )(C 6 H 5 SO 2 ) 2 ] - where An = Np or Pu. Collision induced dissociation resulted in C-S bond cleavage for methanesulfinate to yield [(An V O 2 )(CH 3 SO 2 )(SO 2 )] - , whereas hydrolytic ligand elimination occurred for benzenesulfinate to yield [(An V O 2 )(C 6 H 5 SO 2 )(OH)] - . These different fragmentation pathways are attributed to a stronger C 6 H 5 -SO 2 - versus CH 3 -SO 2 - bond, which was confirmed for both the bare and coordinating sulfinate anions by energies computed using a relativistic multireference perturbative approach (XMS-CASPT2 with spin-orbit coupling). The results demonstrate shutting off a ligand fragmentation channel by increasing the strength of a particular bond, here a sulfinate C-S bond. The [(An V O 2 )(CH 3 SO 2 )(SO 2 )] - complexes produced by CID spontaneously react with O 2 to eliminate SO 2 , yielding [(AnO 2 )(CH 3 SO 2 )(O 2 )] - , a process previously reported for An = U and found here for An = Np and Pu. Computations confirm that the O 2 /SO 2 displacement reactions should be exothermic or thermoneutral for all three An, as was experimentally established. The computations furthermore reveal that the products are superoxides [(An V O 2 )(CH 3 SO 2 )(O 2 )] - for An = Np and Pu, but peroxide [(U VI O 2 )(CH 3 SO 2 )(O 2 )] - . Distinctive reduction of O 2 - to O 2 2- concomitant with oxidation of U(v) to U(vi) reflects the relatively higher stability of hexavalent uranium versus neptunium and plutonium.

Uranium(vi) trans-bis(imido) complexes [U(κ4-{(tBu2ArO)2Me2-cyclam})(NPh)(NPhR)] react with CO2 to eliminate phenyl isocyanates and afford uranium(vi) trans-[O[double bond, length as m-dash]U[double bond, length as m-dash]NR]2+ complexes, including [U(κ4-{(tBu2ArO)2Me2-cyclam})(NPh)(O)] that was crystallographically characterized. DFT studies indicate that the reaction proceeds by endergonic formation of a cycloaddition intermediate; the secondary reaction to form a dioxo uranyl complex is both thermodynamically and kinetically hindered.

The diverse reactivity of [LnO 2 (NO 3 ) 2 ] - complexes with water in the gas phase, for Ln = Ce, Pr and Nd, examined in a quadrupole ion trap and complemented by ab initio computations, illuminates the chemical stability of Pr in the unusual +5 oxidation state.

Thermodynamic properties of the complexation of 2,2'-(trifluoroazanediyl)bis( N , N '-dimethylacetamide) (CF 3 ABDMA) with U(VI), Nd(III), and Np(V) have been studied in 1.0 M NaNO 3 at 25 °C. Equilibrium constants of the complexation were determined by potentiometry and spectrophotometry. In comparison with a series of structurally related amine-bridged diacetamide ligands, including 2,2'-(benzylazanediyl)bis( N , N '-dimethylacetamide) (BnABDMA), 2,2'-azanediylbis(N, N '-dimethylacetamide) (ABDMA), and 2,2'-(methylazanediyl)bis( N , N '-dimethylacetamide) (MABDMA), CF 3 ABDMA forms weaker complexes with U(VI), Nd(III), and Np(V) due to the lower basicity of the center N atom in CF 3 ABDMA resulting from the attachment of the strong electron-withdrawing CF 3 - moiety. The complexation strength of CF 3 ABDMA with the three metal ions follows the order: UO 2 2+ > Nd 3+ > NpO 2 + , consistent with the order of the "effective" charges of the metal ions. Structural information on the U(VI)/CF 3 ABDMA complexes in solution and in solid was obtained by theoretical computation, single crystal X-ray diffractometry, 19 F NMR, and electrospray ionization mass spectrometry. The structural data indicate that, similar to the three previously studied amine-bridged diacetamide ligands (BnABDMA, ABDMA, and MABDMA), the CF 3 ABDMA ligand coordinates to UO 2 2+ in a tridentate mode, through the center nitrogen and the two amide oxygen atoms.

Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO 2 + also called an "actinyl", requires activation of an An-O bond. It was previously found that such oxo exchange in the gas phase occurs for the first two actinyls, PaO 2 + and UO 2 + , but not the next two, NpO 2 + and PuO 2 + . The An-O bond dissociation energies (BDEs) decrease from PaO 2 + to PuO 2 + , such that the observation of a parallel decrease in the An-O bond reactivity is intriguing. To elucidate oxo exchange, we here extend experimental studies to AmO 2 + , americyl(V), and CmO 2 + , curyl(V), which were produced in remarkable abundance by electrospray ionization of Am 3+ and Cm 3+ solutions. Like other AnO 2 + , americyl(V) and curyl(V) adsorb up to four H 2 O molecules to form tetrahydrates AnO 2 (H 2 O) 4 + with the actinide hexacoordinated by oxygen atoms. It was found that AmO 2 + does not oxo-exchange, whereas CmO 2 + does, establishing a "turn" to increasing the reactivity from americyl to curyl, which validates computational predictions. Because oxo exchange occurs via conversion of an actinyl(V) hydrate, AnO 2 (H 2 O) + , to an actinide(V) hydroxide, AnO(OH) 2 + , it reflects the propensity for actinyl(V) hydrolysis: PaO 2 + hydrolyzes and oxo-exchanges most easily, despite the fact that it has the highest BDE of all AnO 2 + . A reexamination of the computational results for actinyl(V) oxo exchange reveals distinctive properties and chemistry of curyl(V) species, particularly CmO(OH) 2 + .

Electrospray ionization of solutions containing a tripodal hydroxylamine ligand, H3TriNOx ([((2-tBuNOH)C6H4CH2)3N]) denoted as L, and a hydrogen halide HX: HCl, HBr and/or HI, yielded gas-phase anion complexes [L(X)]- and [L(HX2)]-. Collision induced dissociation (CID) of mixed-halide complexes, [L(HXaXb)]-, indicated highest affinity for I- and lowest for Cl-. Structures and energetics computed by density functional theory are in accord with the CID results, and indicate that the gas-phase binding preference is a manifestation of differing stabilities of the HX molecules. A high halide affinity of [L(H)]+ in solution was also demonstrated, though with a highest preference for Cl- and lowest for I-, the opposite observation of, but not in conflict with, what is observed in gas phase. The results suggest a connection between gas- and condensed-phase chemistry and computational approaches, and shed light on the aggregation and anion recognition properties of hydroxylamine receptors.

The pertechnetate anion ( 99 TcO 4 - ) is a long-lived radioactive species that is soluble in aqueous solution, in contrast to sparingly soluble 99 TcO 2 . Results are reported for photocatalytic reduction and removal of perrhenate (ReO 4 - ), a nonradioactive surrogate for 99 TcO 4 - , using a TiO 2 (P25) nanoparticle suspension in formic acid under UV-visible irradiation. Re(VII) removal up to 98% was achieved at pH = 3 under air or N 2 . The proposed mechanism is Re(VII)/Re(IV) reduction mediated by reducing radicals ( · CO 2 - ) from oxidation of formic acid, not direct reduction by photogenerated electrons of TiO 2 . Recycling results indicate that photocatalytic reduction of ReO 4 - exhibits excellent regeneration and high activity with >95% removal even after five cycles. 99 Tc(VII) is more easily reduced than Re(VII) in the presence of NO 3 - with very slow redissolution of reduced 99 Tc. This study presents a novel method for the removal of ReO 4 - / 99 TcO 4 - from aqueous solution, with potential application for deep geological disposal.