RESUMEN
Californium (Cf) is currently the heaviest element accessible above microgram quantities. Cf isotopes impose severe experimental challenges due to their scarcity and radiological hazards. Consequently, chemical secrets ranging from the accessibility of 5f/6d valence orbitals to engage in bonding, the role of spin-orbit coupling in electronic structure, and reactivity patterns compared to other f elements, remain locked. Organometallic molecules were foundational in elucidating periodicity and bonding trends across the periodic table1-3, with a twenty-first-century renaissance of organometallic thorium (Th) through plutonium (Pu) chemistry4-12, and to a smaller extent americium (Am)13, transforming chemical understanding. Yet, analogous curium (Cm) to Cf chemistry has lain dormant since the 1970s. Here, we revive air-/moisture-sensitive Cf chemistry through the synthesis and characterization of [Cf(C5Me4H)2Cl2K(OEt2)]n from two milligrams of 249Cf. This bent metallocene motif, not previously structurally authenticated beyond uranium (U)14,15, contains the first crystallographically characterized Cf-C bond. Analysis suggests the Cf-C bond is largely ionic with a small covalent contribution. Lowered Cf 5f orbital energy versus dysprosium (Dy) 4f in the colourless, isoelectronic and isostructural [Dy(C5Me4H)2Cl2K(OEt2)]n results in an orange Cf compound, contrasting with the light-green colour typically associated with Cf compounds16-22.
RESUMEN
Molecular qubits offer an attractive basis for quantum information processing, but challenges remain with regard to sustained coherence. Qubits based on clock transitions offer a method to improve the coherence times. We propose a general strategy for identifying molecules with high-frequency clock transitions in systems where a d electron is coupled to a crystal-field singlet state of an f configuration, resulting in an MJ = ±1/2 ground state with strong hyperfine coupling. Using this approach, a 9.834 GHz clock transition was identified in a molecular Pr complex, [K(crypt)][Cp'3PrII], leading to 3-fold enhancements in T2 relative to other transitions in the spectrum. This result indicates the promise of the design principles outlined here for the further development of f-element systems for quantum information applications.
RESUMEN
The synthesis of previously unknown bis(cyclopentadienyl) complexes of the first transition metal, i.e., Sc(II) scandocene complexes, has been investigated using C5H2(tBu)3 (Cpttt), C5Me5 (Cp*), and C5H3(SiMe3)2 (Cpâ³) ligands. Cpttt2ScI, 1, formed from ScI3 and KCpttt, can be reduced with potassium graphite (KC8) in hexanes to generate dark-red crystals of the first crystallographically characterizable bis(cyclopentadienyl) scandium(II) complex, Cpttt2Sc, 2. Complex 2 has a 170.6° (ring centroid)-Sc-(ring centroid) angle and exhibits an eight-line EPR spectrum characteristic of Sc(II) with Aiso = 82.6 MHz (29.6 G). It sublimes at 200 °C at 10-4 Torr and has a melting point of 268-271 °C. Reductions of Cp*2ScI and Cpâ³2ScI under analogous conditions in hexanes did not provide new Sc(II) complexes, and reduction of Cp*2ScI in benzene formed the Sc(III) phenyl complex, Cp*2Sc(C6H5), 3, by C-H bond activation. However, in Et2O and toluene, reduction of Cp*2ScI at -78 °C gives a dark-red solution, 4, which displays an eight-line EPR pattern like that of 1, but it did not provide thermally stable crystals. Reduction of Cpâ³2ScI, in THF or Et2O at -35 °C in the presence of 2.2.2-cryptand, yields the green Sc(II) metallocene iodide complex, [K(crypt)][Cpâ³2ScI], 5, which was identified by X-ray crystallography and EPR spectroscopy and is thermally unstable. The analogous reaction of Cp*2ScI with KC8 and 18-crown-6 in Et2O gave the ligand redistribution product, [Cp*2Sc(18-crown-6-κ2O,O')][Cp*2ScI2], 6, as the only crystalline product. Density functional theory calculations on the electronic structure of these compounds are reported in addition to a steric analysis using the Guzei method.
RESUMEN
We present pulsed electron paramagnetic resonance (EPR) studies on three La(II) complexes, [K(2.2.2-cryptand)][La(Cp')3] (1), [K(2.2.2-cryptand)][La(Cpâ³)3] (2), and [K(2.2.2-cryptand)][La(Cptt)3] (3), which feature cyclopentadienyl derivatives as ligands [Cp' = C5H4SiMe3; Cpâ³ = C5H3(SiMe3)2; Cptt = C5H3(CMe3)2] and display a C3 symmetry. Long spin-lattice relaxation (T1) and phase memory (Tm) times are observed for all three compounds, but with significant variation in T1 among 1-3, with 3 being the slowest relaxing due to higher s-character of the SOMO. The dephasing times can be extended by more than an order of magnitude via dynamical decoupling experiments using a Carr-Purcell-Meiboom-Gill (CPMG) sequence, reaching 161 µs (5 K) for 3. Coherent spin manipulation is performed by the observation of Rabi quantum oscillations up to 80 K in this nuclear spin-rich environment (1H, 13C, and 29Si). The high nuclear spin of 139La (I = 7/2), and the ability to coherently manipulate all eight hyperfine transitions, makes these molecules promising candidates for application as qudits (multilevel quantum systems featuring d quantum states; d >2) for performing quantum operations within a single molecule. Application of HYSCORE techniques allows us to quantify the electron spin density at ligand nuclei and interrogate the role of functional groups to the electron spin relaxation properties.
RESUMEN
Initial definitions of sarcopenia included the age-associated loss of skeletal muscle mass that was presumed to be associated with late-life reduced functional capacity, disability and loss of independence. Because no method for determination of muscle mass was available for large cohort studies of aging men and women, lean body mass determined by dual X-ray absorptiometry or bioelectrical impedance was used as a surrogate measure of muscle mass. The data from these studies showed either no or a poor relationship between LBM and functional capacity and health related outcomes, leading to the conclusion of many that the amount of muscle may not be associated with these age-associated outcomes. It was assumed that some undefined index of muscle quality is the critical contributor. These studies also consistently showed that muscle strength is lost more quickly than lean mass. Total body muscle mass can now be measured directly, accurately and non-invasively using the D3creatine (D3Cr) dilution method. D3Cr muscle mass, but not DXA derived LBM, is strongly associated with functional capacity, falls and insulin resistance in older men and women. In addition, D3Cr muscle mass is associated with risk of disability, hip fracture and mortality. New and emerging data demonstrate that low muscle mass may serve as a diagnostic criterion for sarcopenia.
Asunto(s)
Fracturas de Cadera , Sarcopenia , Masculino , Humanos , Femenino , Anciano , Músculo Esquelético , Creatina , Gerociencia , Envejecimiento/fisiología , Absorciometría de Fotón , Composición Corporal , Fracturas de Cadera/complicacionesRESUMEN
Metal complexes with unpaired electrons in orbitals of different angular momentum quantum numbers (e.g., f and d orbitals) are unusual and opportunities to study the interactions among these electrons are rare. X-band electron paramagnetic resonance (EPR) data were collected at <10 and 77 K on 10 U(II) complexes with 5f36d1 electron configurations and on some analogous Ce(II), Pr(II), and Nd(II) complexes with 4fn5d1 electron configurations. The U(II) compounds unexpectedly display similar two-line axial signals with g|| = 2.04 and g⥠= 2.00 at 77 K. In contrast, U(II) complexes with 5f4 configurations are EPR-silent. Unlike U(II), the congenic 4f35d1 Nd(II) complex is EPR-silent. The Ce(II) complex with a 4f15d1 configuration is also EPR-silent, but a signal is observed for the Pr(II) complex, which has a 4f25d1 configuration. Whether or not an EPR signal is expected for these complexes depends on the coupling between f and d electrons. Since the coupling in U(II) systems is expected to be sufficiently strong to preclude an EPR signal from compounds with a 5f36d1 configuration, the results are viewed as unexplained phenomena. However, they do show that 5f36d1 U(II) samples can be differentiated from 5f4 U(II) complexes by EPR spectroscopy.
RESUMEN
The factors affecting the formation and crystal structures of unusual 6d1 Th(III) square planar aryloxide complexes, as exemplified by [Th(OArMe)4]1- (OArMe = OC6H2tBu2-2,6-Me-4), were explored by synthetic and reduction studies of a series of related Th(IV) tetrakis(aryloxide) complexes, Th(OArR)4 (OArR = OC6H2tBu2-2,6-R-4). Specifically, electronic, steric, and countercation effects were explored by varying the aryloxide ligand, the alkali metal reducing agent, and the alkali metal chelating agent. Salt metathesis reactions between ThBr4(DME)2 (DME = 1,2-dimethoxyethane) and 4 equiv of the appropriate potassium aryloxide salt were used to prepare a series of Th(IV) aryloxide complexes in high yields: Th(OArH)4 (OArH = OC6H3tBu2-2,6), Th(OArtBu)4 (OArtBu = OC6H2tBu3-2,4,6), Th(OArOMe)4 (OArOMe = OC6H2tBu2-2,6-OMe-4), and Th(OArPh)4 (OArPh = OC6H2tBu2-2,6-Ph-4). Th(OArH)4 can be reduced by KC8, Na, or Li in the absence or presence of 2.2.2-cryptand (crypt) or 18-crown-6 (crown) to form dark purple solutions that have EPR and UV-visible spectra similar to those of the square planar Th(III) complex, [Th(OArMe)4]1-. Hence, the para position of the aryloxide ligand does not have to be alkylated to obtain the Th(III) complexes. Furthermore, reduction of Th(OArOMe)4, Th(OArtBu)4, and Th(OArPh)4 with KC8 in THF generated purple solutions with EPR and UV-visible spectra that are similar to those of the previously reported Th(III) anion, [Th(OArMe)4]1-. Although many of these reduction reactions did not produce single crystals suitable for study by X-ray diffraction, reduction of Th(OArH)4, Th(OArtBu)4, and Th(OArOMe)4 with Li provided X-ray quality crystals whose structures had square planar coordination geometries. Reduction of Th(OArPh)4 with Li also gave a product with EPR and UV-visible spectra that matched those of [Th(OArMe)4]1-, but X-ray quality crystals of the reduction product were too unstable to provide data. Neither Th(Odipp)4(THF)2 (Odipp = OC6H3iPr2-2,6) nor Th(Odmp)4(THF)2 (Odmp = OC6H3Me2-2,6) could be reduced to Th(III) products under similar conditions. Reduction of U(OArH)3(THF) with KC8 in the presence of 2.2.2-cryptand (crypt) was examined for comparison and formed [K(crypt)][U(OArH)4], which has a tetrahedral arrangement of the aryloxide ligands. Moreover, no further reduction was observed when either [K(crypt)][U(OArH)4] or [K(crown)(THF)2][U(OArH)4] were treated with KC8 or Li.
RESUMEN
The reduction of a bimetallic yttrium ansa-metallocene hydride was examined to explore the possible formation of Y-Y bonds with 4d1 Y(II) ions. The precursor [CpAnY(µ-H)(THF)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2) was synthesized by hydrogenolysis of the allyl complex CpAnY(η3-C3H5)(THF), which was prepared from (C3H5)MgCl and [CpAnY(µ-Cl)]2. Treatment of [CpAnY(µ-H)(THF)]2 with excess KC8 in the presence of one equivalent of 2.2.2-cryptand (crypt) generates an intensely colored red-brown product crystallographically identified as [K(crypt)][(µ-CpAn)Y(µ-H)]2. The two rings of each CpAn ligand in the reduced anion [(µ-CpAn)Y(µ-H)]21- are attached to two yttrium centers in a "flyover" configuration. The 3.3992(6) and 3.4022(7) Å Y···Y distances between the equivalent metal centers within two crystallographically independent complexes are the shortest Y···Y distances observed to date. Ultraviolet-visible (UV-visible)/near infrared (IR) and electron paramagnetic resonance (EPR) spectroscopy support the presence of Y(II), and theoretical analysis describes the singly occupied molecular orbital (SOMO) as an Y-Y bonding orbital composed of metal 4d orbitals mixed with metallocene ligand orbitals. A dysprosium analogue, [K(18-crown-6)(THF)2][(µ-CpAn)Dy(µ-H)]2, was also synthesized, crystallographically characterized, and studied by variable temperature magnetic susceptibility. The magnetic data are best modeled with the presence of one 4f9 Dy(III) center and one 4f9(5dz2)1 Dy(II) center with no coupling between them. CASSCF calculations are consistent with magnetic measurements supporting the absence of coupling between the Dy centers.
RESUMEN
An experimental platform for dynamic diamond anvil cell (dDAC) research has been developed at the High Energy Density (HED) Instrument at the European X-ray Free Electron Laser (European XFEL). Advantage was taken of the high repetition rate of the European XFEL (up to 4.5â MHz) to collect pulse-resolved MHz X-ray diffraction data from samples as they are dynamically compressed at intermediate strain rates (≤103â s-1), where up to 352 diffraction images can be collected from a single pulse train. The set-up employs piezo-driven dDACs capable of compressing samples in ≥340â µs, compatible with the maximum length of the pulse train (550â µs). Results from rapid compression experiments on a wide range of sample systems with different X-ray scattering powers are presented. A maximum compression rate of 87â TPaâ s-1 was observed during the fast compression of Au, while a strain rate of â¼1100â s-1 was achieved during the rapid compression of N2 at 23â TPaâ s-1.
Asunto(s)
Diamante , Rayos Láser , Difracción de Rayos X , Presión , Rayos XRESUMEN
BACKGROUND: Bioelectrical impedance analysis (BIA) is a minimally invasive, safe, easy, and quick technology used to determine body composition. OBJECTIVES: We compared the relationship among impedance indices obtained using single-frequency BIA, multi-frequency BIA, bioelectrical impedance spectroscopy (BIS), and skeletal muscle mass (SMM) of physically active young men and athletes using the creatine (methyl-d3) dilution method. We also compared the SMM and intracellular water (ICW) of athletes and active young men measured using a reference stable isotope dilution and BIS method, respectively. METHODS: We analyzed data from 28 men (mean age, 20 ± 2 y) who exercised regularly. Single-frequency BIA at 5 kHz and 50 kHz (R5 and R50), multi-frequency BIA (R250-5), and BIS (RICW) methods of determining the SMM were compared. The deuterium and sodium bromide dilution methods of obtaining the total body water, ICW, and extracellular water measurements were also used, and the results were compared to those acquired using bioimpedance methods. RESULTS: The correlation coefficients between SMM and L2/R5, L2/R50, L2/R250-5, and L2/RICW were 0.738, 0.762, 0.790, and 0.790, respectively (P < 0.01). The correlation coefficients between ICW and L2/R5, L2/R50, L2/R250-5, and L2/RICW were 0.660, 0.687, 0.758, and 0.730, respectively (P < 0.001). However, the correlation coefficients of L2/R50, L2/R250-5, and L2/RICW for SMM and ICW were not significantly different. CONCLUSIONS: Our findings suggest that single-frequency BIA at L2/R50, multi-frequency BIA, and BIS are valid for assessing the SMM of athletes and active young men. Additionally, we confirmed that the SMM and ICW were correlated with single-frequency BIA, multi-frequency BIA, and BIS. Bioimpedance technologies may be dependable and practical means for assessing SMM and hydration compartment status of active young adult males; however, cross-validation is needed.
Asunto(s)
Agua Corporal , Agua , Masculino , Adulto Joven , Humanos , Adolescente , Adulto , Impedancia Eléctrica , Composición Corporal/fisiología , Atletas , Músculo Esquelético/fisiologíaRESUMEN
BACKGROUND: Given limited experience in applying the creatine-(methyl-D3) (D3Cr) dilution method to measure skeletal muscle mass (SMM) in young children, the feasibility of deployment in a fielding setting and performance of the method was assessed in a cohort of 4-year-old children in Dhaka, Bangladesh. METHODS: Following D3Cr oral dose (10 mg) administration, single fasting urine samples were collected at 2-4 days (n = 100). Twenty-four-hour post-dose collections and serial spot urine samples on days 2, 3 and 4 were obtained in a subset of participants (n = 10). Urinary creatine, creatinine, D3Cr and D3-creatinine enrichment were analyzed by liquid chromatography-tandem mass spectrometry. Appendicular lean mass (ALM) was measured by dual-energy x-ray absorptiometry and grip strength was measured by a hand-held dynamometer. RESULTS: SMM was measured successfully in 91% of participants, and there were no adverse events. Mean ± SD SMM was greater than ALM (4.5 ± 0.4 and 3.2 ± 0.6 kg, respectively). Precision of SMM was low (intraclass correlation = 0.20; 95% CI: 0.02, 0.75; n = 10). Grip strength was not associated with SMM in multivariable analysis (0.004 kg per 100 g of SMM; 95% CI: -0.031, 0.038; n = 91). CONCLUSIONS: The D3Cr dilution method was feasible in a community setting. However, high within-child variability in SMM estimates suggests the need for further optimization of this approach. IMPACT: The D3-creatine (D3Cr) stable isotope dilution method was considered a feasible method for the estimation of skeletal muscle mass (SMM) in young children in a community setting and was well accepted among participants. SMM was weakly associated with both dual-energy x-ray absorptiometry-derived values of appendicular lean mass and grip strength. High within-child variability in estimated values of SMM suggests that further optimization of the D3Cr stable isotope dilution method is required prior to implementation in community research settings.
Asunto(s)
Creatina , Músculo Esquelético , Humanos , Preescolar , Creatina/metabolismo , Creatinina/metabolismo , Músculo Esquelético/metabolismo , Composición Corporal/fisiología , Bangladesh , Absorciometría de Fotón/métodos , Isótopos/metabolismoRESUMEN
The sterically bulky aryloxide ligand OAr* (OAr* = -OC6H2-Ad2-2,6tBu-4; Ad = 1-adamantyl) has been used to generate Ln(II) complexes across the lanthanide series that are more thermally stable than complexes of any other ligand system reported to date for 4fnd1 Ln(II) ions. The Ln(III) precursors Ln(OAr*)3 (1-Ln) were synthesized by reacting 1.2 equiv of Ln(NR2)3 (R = SiMe3) with 3 equiv of HOAr* for Ln = La, Ce, Nd, Gd, Dy, Yb, and Lu. 1-Ce, 1-Nd, 1-Gd, 1-Dy, and 1-Lu were identified by single-crystal X-ray diffraction studies. Reductions of 1-Ln with potassium graphite (KC8) in tetrahydrofuran in the presence of 2.2.2-cryptand (crypt) yielded the Ln(II) complexes [K(crypt)][Ln(OAr*)3] (2-Ln). The 2-Ln complexes for Ln = Nd, Gd, Dy, and Lu were characterized by X-ray crystallography and found to have Ln-O bond distances 0.038-0.087 Å longer than those of their 1-Ln analogues; this is consistent with 4fn5d1 electron configurations. The structure of 2-Yb has Yb-O distances 0.167 Å longer than those predicted for 1-Yb, which is consistent with a 4f14 electron configuration. Although 2-La and 2-Ce proved to be challenging to isolate, with 18-crown-6 (18-c-6) as the potassium chelator, La(II) and Ce(II) complexes with OAr* could be isolated and crystallographically characterized: [K(18-c-6)][Ln(OAr*)3] (3-Ln). The Ln(II) complexes decompose at room temperature more slowly than other previously reported 4fn5d1 Ln(II) complexes. For example, only 30% decomposition of 2-Dy was observed after 30 h at room temperature compared to complete decomposition of [Dy(OAr')3]- and [DyCp'3]- under similar conditions (OAr' = OC6H2-2,6-tBu2-4-Me; Cp' = C5H4SiMe3).
RESUMEN
1,3,5-Trimethyl-1,3,5-triazacyclohexane (Me3tach) readily complexes uranium triiodide to form (Me3tach)2UI3. The complex is soluble in THF and arenes and can function as a source of UI3 to form organometallic U(III) complexes. When dissolved in pyridine (py), (Me3tach)2UI3 forms (Me3tach)UI3(py)2. A related complex with the larger 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3tacn) ligand, namely (Me3tacn)UI3(THF), was synthesized for comparison. Since X-ray quality crystals of (Me3tach)2UI3 can be synthesized in high yield even with small-scale reactions, the system is ideal for extension to transuranium elements. Accordingly, the neptunium and plutonium complexes (Me3tach)2NpI3 and (Me3tach)2PuI3 were synthesized in an analogous manner from NpI3(THF)4 and PuI3(THF)4, respectively.
RESUMEN
The high reactivity accessible from the reduction of the tris(amide) complexes Ln(NR2)3 (R = SiMe3) with potassium graphite in the presence of a variety of ethers is demonstrated by crystal structures of six different types of products of C-O bond cleavage reactions with Ln = Y, Ho, Er, and Lu. Specifically, 1,2-dimethoxyethane (DME) can be cleaved in Ln(NR2)3/KC8 reactions as shown by three different types of crystals: [K (crypt)][(R2N)3Y(OCH2CH2OCH3)], 1-Y, [(R2N)2Y(µ-OCH2CH2OCH3-κO,κO')]2, 2-Y, and [K2(18-c-6)3]{[(R2N)3Lu]2[(µ-OCH2CH2O)]}, 3-Lu (18-c-6 = 18-crown-6; crypt = 2.2.2-cryptand). THF can be ring opened by the Y(NR2)3/KC8 reaction system, as shown by crystals of the butoxide, [K(crypt)][(R2N)3Y(OCH2CH2CH2CH3)], 4-Y. The cyclic ether, oxetane, OC3H6, ring opens in Ln(NR2)3/KC8 reactions to form crystals of the propoxide, [K(18-c-6)(OC3H6)][(R2N)3Ln(OCH2CH2CH3)], 5-Ln, for Ln = Ho and Er. In Et2O, the Y(NR2)3/KC8 reactions do not attack the solvent, but C-O cleavage of 18-c-6 is observed to form {[(R2N)2]Y[µ-η1:η1-O2(C10H20O4)K]}2, 6-Y. These Ln(NR2)3/KC8 C-O cleavage reactions are typically accompanied by C-H bond activation reactions, which form cyclometalates such as [K(crypt)]{(R2N)2Ln[N(SiMe3)(SiMe2CH2)-κC,κN]}, 7-Ln (Ln = Y, Ho, Er), and [K(18-c-6)]{(R2N)2Y[N(SiMe3)(SiMe2CH2)-κC,κN]}, 8-Y, which are common decomposition products of Ln(NR2)3 reactions. In addition, in this study, the hydride complex, [K(18-c-6)][(R2N)3YH], 9-Y, was isolated. NMR analysis indicates that the yttrium reactions form mixtures that consistently contain the yttrium cyclometalates 7-Y and 8-Y as major components. These results show the diversity of available reaction pathways for the Ln(NR2)3/KC8 system and highlight the inherent difficulties in isolating Ln(II) complexes containing the [Ln(NR2)3]1- anion.
RESUMEN
The pursuit of a trivalent plutonium halide phosphine oxide compound, e.g., "PuBr3(OPR)3," instead led to the isolation of the tetravalent trans-PuIVBr4(OPCy3)2, PuBr/Cy, compound by spontaneous oxidation of PuIII. The donating nature of phosphine oxides has allowed the isolation and characterization of PuBr/Cy by crystallographic, multinuclear NMR, solid state, and solution phase UV-vis-NIR spectroscopic techniques. The presence of a putative plutonyl(VI) complex formulated as "trans-PuVIO2Br2(OPCy3)2" was also observed spectroscopically and tentatively by single-crystal X-ray diffraction as a cocrystal of PuBr/Cy. A series of trans-ThX4(OPCy3)2 (X = Cl, ThCl/Cy; Br, ThBr/Cy; I, ThI/Cy) complexes were synthesized for comparison to PuBr/Cy. The triphenylphosphine oxide, OPPh3, complexes, trans-AnI4(OPPh3)2 (An = Th, ThI/Ph; U, UI/Ph), were also synthesized for comparison, completing the series trans-UX4(OPPh3)2 (X = Cl, Br, I), UX/Ph. To enable the synthesis of ThI/Cy and ThI/Ph, a new nonaqueous thorium iodide starting material, ThI4(Et2O)2, was synthesized. The syntheses of organic solvent soluble ThI4L2 (L = Et2O, OPCy3, and OPPh3) are the first examples of crystallographically characterized neutral thorium tetraiodide materials beyond binary ThI4. To show the viability of ThI4(Et2O)2 as a starting material for organothorium chemistry, (C5Me4H)3ThI was synthesized and crystallographically characterized.
RESUMEN
INTRODUCTION: We have previously described negative energy balance (ie, -9.7±3.4 MJ/d) and weight loss (Δ-1.5 ± 0.7 kg) influenced by high levels of energy expenditure (ie, 17.4±2.6 MJ/d) during remote expeditionary hunting in Alaska. Despite negative energy balance, participants retained skeletal muscle. The purpose of this pilot study was to measure skeletal muscle protein synthesis and examine molecular markers of skeletal muscle protein metabolism under similar conditions of physical and nutrient stress. METHODS: The "virtual biopsy method" was used to evaluate integrated fractional synthetic rates (FSRs) of muscle protein from blood samples in 4 participants. Muscle biopsies were taken to measure molecular markers of muscle protein kinetics (ie, FSTL1, MEF2, MYOD1, B2M, and miR-1-3p, -206, -208b, 23a, and 499a) using real-time polymerase chain reaction. RESULTS: Our findings in 4 participants (2 females [28 and 62 y of age; 66.2 and 71.8 kg body weight; 25.5 and 26.7 kg/m2 body mass index] and 2 males [47 and 56 y of age; 87.5 and 91.4 kg body weight; 26.1 and 28.3 kg/m2 body mass index]) describe mean muscle FSRs of serum carbonic anhydrase (2.4%) and creatine kinase M-type (4.0%) and positive increments in molecular regulation. CONCLUSIONS: Preservation of skeletal muscle under conditions of physical and nutrient stress seems to be supported by positive inflection of skeletal muscle FSR and molecular activation.
Asunto(s)
Proteínas Relacionadas con la Folistatina , Proteínas Musculares , Masculino , Femenino , Humanos , Proteínas Musculares/metabolismo , Alaska , Caza , Proyectos Piloto , Músculo Esquelético , Peso Corporal , Metabolismo Energético , Proteínas Relacionadas con la Folistatina/metabolismoRESUMEN
Examination of the reduction chemistry of Nd(NR2)3 (R = SiMe3) under N2 has provided connections between the in situ Ln(III)-based LnIII(NR2)3/K reductions of N2 that form side-on bound neutral (N=N)2- complexes, [(R2N)2(THF)Ln]2[µ-η2:η2-N2], and the Ln(II)-based [LnII(NR2)3]1- reductions by Sc, Gd, and Tb that form end-on bound (N=N)2- complexes, {[(R2N)3Ln]2[µ-η1:η1-N2]}2-, which are dianions. The reduction of Nd(NR2)3 by KC8 under dinitrogen in Et2O in the presence of 18-crown-6 (18-c-6) forms dark yellow solutions of [K2(18-c-6)3]{[(R2N)3Nd]2N2} at low temperatures that become green as they warm up to -35 °C in a glovebox freezer. Green crystals obtained from the solution turn yellow-brown when cooled below -100 °C, and the yellow-brown compound has an end-on Nd2(µ-η1:η1-N2) structure. The yellow-brown crystals isomerize in the solid state on the diffractometer upon warming, and at -25 °C, the crystals are green and have a side-on Nd2(µ-η2:η2-N2) structure. Collection of X-ray diffraction data at 10 °C intervals from -50 to -90 °C revealed that the isomerization occurs at temperatures below -100 °C. In the presence of tetrahydrofuran (THF), the dianionic {[(R2N)3Nd]2N2}2- system can lose an amide ligand to provide the monoanionic [(R2N)3NdIII(µ-η2:η2-N2)NdIII(NR2)2(THF)]1-, characterized by X-ray crystallography. These data suggest a connection between the in situ Ln(III)/K reductions and Ln(II) reductions that depends on solvent, temperature, the presence of a chelate, and the specific rare-earth metal.
Asunto(s)
Amidas , Furanos , Isomerismo , Ligandos , Modelos Moleculares , SolventesRESUMEN
1,3,5-Trimethyltriazacyclohexane, Me3tach, readily adds to bismuth triiodide to form a variety of new coordination compounds depending on the stoichiometry, solvent, and crystallization conditions. X-ray crystallographic evidence has been obtained for both 2:1 and 1:1 Me3tach:Bi complexes with formulas of [(Me3tach)2BiI2][(Me3tach)BiI4], [(Me3tach)2BiI2]3[Bi2I9][I][HMe3tach]·THF, and (Me3tach)BiI3(py)2. The related chloride structure (Me3tach)BiCl3(py)2 forms from BiCl3. The structure of (Me3tacn)BiI3 with the larger chelate, 1,4,7-trimethyltriazacyclononane, Me3tacn, was obtained for comparison, and the polymeric structure of BiI3 in THF was defined as [BiI(THF)(µ-I)2]n.
RESUMEN
Heteroleptic U(III) complexes supported by bis(cyclopentadienyl) frameworks have been synthesized to examine their suitability as precursors to U(II) complexes. The newly synthesized (C5Me5)2U(OC6H2tBu2-2,6-Me-4), (C5Me5)2U(OC6H2Ad2-2,6-tBu-4) (Ad = 1-adamantyl), (C5Me5)2U(C5H5), and (C5Me5)2U(C5Me4H) are compared with (C5Me5)2U[N(SiMe3)2], (C5Me5)2U[CH(SiMe3)2], and (C5Me5)U[N(SiMe3)2]2. An improved synthesis of (C5Me5)2U(µ-Ph)2BPh2 was developed, which was used to synthesize (C5Me5)2U(C5Me4H). Since the X-ray crystal structure of (C5Me5)2U(OC6H2tBu2-2,6-Me-4) contained two very different molecules in the asymmetric unit with 115.7(5)° and 166.0(5)° U-O-Cipso angles, the (C5Me4H)2U(OC6H2tBu2-2,6-Me-4) and (C5Me5)2Ce(OC6H2tBu2-2,6-Me-4) analogues were synthesized and characterized by X-ray diffraction for comparison. Electrochemical studies in THF with a 100 mM [nBu4N][BPh4] supporting electrolyte showed U(IV)/U(III) and U(III)/U(II) redox couples for all the heteroleptic complexes except (C5Me5)2U(C5H5). Chemical reduction of all heteroleptic compounds formed dark blue solutions characteristic of U(II) when reacted with KC8 at -78 °C, but none formed isolable U(II) complexes. The targeted U(II) complexes, [(C5Me5)2U(OC6H2tBu2-2,6-Me-4)]1-, {(C5Me5)2U[CH(SiMe3)2]}1-, [(C5Me5)2U(C5H5)]1-, and [(C5Me5)2U(C5Me4H)]1-, were analyzed by density functional theory, and a 5f36d1 electron configuration was found to be the ground state in each case.
RESUMEN
The utility of γ irradiation for generating unstable, low oxidation state molecular species containing rare-earth metal ions in frozen solution has been examined. The method was evaluated by irradiating Ln(III) precursors (Ln = Sc, Y, and La) in a solid matrix of 2-methyltetrahydrofuran at 77 K with a 700 keV 137Cs source to generate free electrons capable of reducing the Ln(III) species. These experiments yielded EPR and UV-visible spectroscopic data that matched those of the known Ln(II) species [(C5H4SiMe3)3YII]1-, [(C5H4SiMe3)3LaII]1-, and {ScII[N(SiMe3)2]3}1-. Irradiation of the La(III) complex LaIII[N(SiMe3)2]3 by this method gave EPR and UV-visible absorption spectra consistent with {LaII[N(SiMe3)2]3}1-, a species that had previously eluded preparation by chemical reduction. Specifically, the irradiation product exhibited an axial EPR spectrum split into eight lines by the I = 7/2 139La nucleus (g⥠= 1.98, g|| = 2.06, Aave = 519.1 G). The UV-visible absorption spectrum contains broad bands centered at 390 and 670 nm that are consistent with a La(II) ion in a trigonal ligand environment based on time-dependent density functional theory which qualitatively reproduces the observed spectrum. Additionally, the rate of formation of the [(C5H4SiMe3)3YII]1- species during the irradiation of (C5H4SiMe3)3YIII was monitored by measuring the concentration via UV-visible spectroscopy over time to provide data on the rate at which a molecular species is reduced in a glass via γ irradiation.