Seasonality Affects Fluid Intake Behaviors among Young Adults in Hebei, China.

BACKGROUND: Evidence on the association between environmental factors and fluid intake behavior remains limited. The current study aims to explore seasonal variations in fluid intake behaviors among young adults in China. METHODS: A prospective cohort of 79 healthy young adults (43 males and 36 females) aged 19-21 in Hebei, China, was assessed for fluid intake behaviors for four seasons. For each assessment, the participants' anthropometric measurements were collected. Temperature and humidity on survey days were measured. Participants' total drinking fluid (TDF) was recorded using a self-administrative 7 d, 24 h fluid intake questionnaire. To calculate water from food (WFF), we weighed all foods consumed by participants. Duplicates of consumed food samples were collected to measure the water content via the drying method. RESULTS: The mean total water intake (TWI) was 2761 ± 881, 2551 ± 845, 2210 ± 551, and 1989 ± 579 for spring, summer, fall, and winter, respectively (F(2.37) = 42.29, p < 0.001). The volume and proportion of TWI from TDF and WFF varied across the four seasons. The volume of WFF in spring (1361 ± 281, F(2.61) = 17.21, p < 0.001) and TDF in summer (1218 ± 502, F(2.62) = 9.36, p < 0.001) was among the highest, while participants' fluid intake behaviors in spring and summer were less distinct than the other pairwise comparisons. A moderate association was found between outdoor temperature and TDF (r = 0.53, p < 0.01). Different general estimating equations suggested that gender, seasonality, outdoor temperature, differences in indoor and outdoor temperature, and mean temperature were independent factors of TDF. An interactive effect was found for gender and temperature, showing that the expected TDF of males may increase more as the temperature climbs. CONCLUSIONS: Gender, seasonality, and air temperature could significantly affect fluid intake behaviors, including the amount and type of fluid intake. However, the independent effect of BMI and humidity remains unclear.

The association between hydration state and the metabolism of phospholipids and amino acids among young adults: a metabolomic analysis.

Background: Water is vital for humans' survival and general health, which is involved in various metabolic activities. Objectives: The aim of this study was to investigate the variation in urine metabolome and associated metabolic pathways among people with different hydration states. Methods: A metabolomic analysis was conducted using 24-h urine samples collected during a cross-sectional study on fluid intake behavior from December 9 to 11, 2021, in Hebei, China. Subjects were divided into the optimal hydration (OH, ≤500 mOsm/kg, n = 21), middle hydration (500-800 mOsm/kg, n = 33), and hypohydration groups (HH, >800 mOsm/kg, n = 13) based on the 3-d average 24-h urine osmolality. Collected 24-h urine samples from 67 subjects (43 males and 34 females) were analyzed for urine metabolome using liquid chromatography-MS. Results: The untargeted metabolomic analysis yielded 1055 metabolites by peak intensities. Integrating the results of the orthogonal projections to latent structures discriminant analysis and fold change test, 115 differential metabolites between the OH and HH groups, including phospholipids (PLs) and lysophospholipids, were identified. Among the 115 metabolites identified as differential metabolites, 85 were recorded by the Human Metabolome Database and uploaded to the Kyoto Encyclopedia of Genes and Genomes databases for pathway analysis. Twenty-one metabolic pathways were recognized. Phenylalanine metabolism (0.50, P = 0.007), phenylalanine, tyrosine, and tryptophan biosynthesis (0.50, P = 0.051), glycerophospholipid metabolism (0.31, P < 0.001), sphingolipid metabolism (0.27, P = 0.029), and cysteine and methionine metabolism (0.10, P = 0.066) had the leading pathway impacts. Conclusions: We found variations in the urinary PLs and amino acids among subjects with different hydration states. Pathways associated with these differential metabolites could further impact various physiologic and pathologic functions. A more comprehensive and in-depth investigation of the physiologic and pathologic impact of the hydration state and the underlying mechanisms to elucidate and advocate optimal fluid intake habits is needed.This trial was registered at Chinese Clinical Trial Registry as ChiCTR2100045268.

Spectroscopic and Theoretical Identifications of Two Structural Motifs of (H2O)10 Cluster.

Precise characterization of archetypal systems of aqueous hydrogen-bonding networks is essential for developing accurate potential functions and universal models of water. The structures of water clusters (H2O)n (n = 2-9) have been verified recently through size-specific infrared spectroscopy with a vacuum ultraviolet free electron laser (VUV-FEL) and quantum chemical studies. For (H2O)10, the pentagonal prism and butterfly motifs were proposed to be important building blocks and were observed in previous experiments. Here we report the size-specific infrared spectra of (H2O)10 via a joint experimental and theoretical study. Well-resolved spectra provide a unique signature for the coexistence of pentagonal prism and butterfly motifs. These (H2O)10 motifs develop from the dominant structures of (H2O)n (n = 8, 9) clusters. This work provides an intriguing prelude to the diverse structure of liquid water and opens avenues for size-dependent measurement of larger systems to understand the stepwise formation mechanism of hydrogen-bonding networks.

On the highest oxidation states of the actinoids in AnO4 molecules (An = Ac - Cm): A DMRG-CASSCF study.

Actinoid tetroxide molecules AnO4 (An = Ac - Cm) are investigated with the ab initio density matrix renormalization group (DMRG) approach. Natural orbital shapes are used to read out the oxidation state (OS) of the f-elements, and the atomic orbital energies and radii are used to explain the trends. The highest OSs reveal a "volcano"-type variation: For An = Ac - Np, the OSs are equal to the number of available valence electrons, that is, AcIII , ThIV , PaV , UVI , and NpVII . Starting with plutonium as the turning point, the highest OSs in the most stable AnO4 isomers then decrease as PuV , AmV , and CmIII , indicating that the 5f-electrons are hard to be fully oxidized off from Pu onward. The variations are related to the actinoid contraction and to the 5f-covalency characteristics. Combined with previous work on OSs, we review their general trends throughout the periodic table, providing fundamental understanding of OS-relevant phenomena.

Norm-Conserving 4f-in-Core Pseudopotentials and Basis Sets Optimized for Trivalent Lanthanides (Ln = Ce-Lu).

We present here a set of scalar-relativistic norm-conserving 4f-in-core pseudopotentials, together with complementary valence-shell Gaussian basis sets, for the lanthanide (Ln) series (Ce-Lu). The Goedecker, Teter, and Hutter (GTH) formalism is adopted with the generalized gradient approximation (GGA) for the exchange-correlation Perdew-Burke-Ernzerhof (PBE) functional. The 4f-in-core pseudopotentials are built through attributing 4f-subconfiguration 4fn (n = 1-14) for Ln (Ln = Ce-Lu) into the atomic core region, making it possible to circumvent the difficulty of the description of the open 4fn valence shell. A wide variety of computational benchmarks and tests have been carried out on lanthanide systems including Ln3+-containing molecular complexes, aqueous solutions, and bulk solids to validate the accuracy, reliability, and efficiency of the optimized 4f-in-core GTH pseudopotentials and basis sets. The 4f-in-core GTH pseudopotentials successfully replicate the main features of lanthanide structural chemistry and reaction energetics, particularly for nonredox reactions. The chemical bonding features and solvation shells, hydrolysis energetics, acidity constants, and solid-state properties of selected lanthanide systems are also discussed in detail by utilizing these new 4f-in-core GTH pseudopotentials. This work bridges the idea of keeping highly localized 4f electrons in the atomic core and efficient pseudopotential formalism of GTH, thus providing a highly efficient approach for studying lanthanide chemistry in multi-scale modeling of constituent-wise and structurally complicated systems, including electronic structures of the condensed phase and first-principles molecular dynamics simulations.

The total fluids intake among college students from Hebei Province in spring and summer / 中国学校卫生

Objective@#To analyze the total fluids intake and sources of college students from Hebei in spring and summer, and to provide a scientific reference for appropriate fluids intake in different seasons.@*Methods@#Subjects were recruited in a university in Baoding, Hebei Province, and investigations were conducted in April and June 2021. The number of people who completed both spring and summer investigations was 80. Quantitative instruments and 7 day 24 h Fluid Intake Questionnaire were used to investigate the total drinking fluids, and it was recorded for 7 consecutive days in spring and summer respectively. The duplicate portion method was used to investigate the water from food. The total fluids intake and sources among subjects were analyzed in spring and summer.@*Results@#There was no statistical significance between the total drinking fluids and total fluids intake between spring and summer [1 141(715), 1 176(649)mL/d, (2 496±604)(2 458±554)mL/d] ( F=1.86, 0.59, P >0.05). Spring showed significantly higher water from food compared with summer [(1 318±274)(1 217±302)mL/d]( F=16.63, P <0.05). The proportions of total drinking fluids and water from food in spring were 46% and 54%, respectively, and both were 50% in summer, the differences were statistically significant ( F=12.97, 12.97, P <0.05). There were differences in total fluids intake,total drinking fluids and water from food of different genders in earch season ( t/Z =4.75, -3.63, 3.44; 4.80, -2.91, 4.01, P <0.05). There were differences in total water intake, total drinking fluids, the proportions of total drinking fluids and water from food of different BMI groups in each season ( F/H =8.08, 16.65, 3.03, 3.03; 7.11,17.97, 4.52, 4.52, P <0.05). In spring, only 13.8% of subjects achieved the recommended total drinking fluids of China, compared with 18.8% in summer. In spring and summer, the total fluids intake, total drinking fluids, the proportions of total drinking fluids in the group achieved the recommendation were all higher than those who did not reach the recommendation ( t/Z =6.64, -5.19, 5.79; 8.12, -5.97, 5.70, P <0.05).@*Conclusion@#Season is a factor that affects total fluids intake, and it should be taken into account when setting the recommendation on adequate water intake.

Association between sugar-sweetened beverage consumption and physical fitness index among college students / 中国学校卫生

Objective@#To understand the association between sugar sweetened beverage consumption with physical fitness index among college students, so as to provide a reference for the improvement and intervention of college students physical fitness.@*Methods@#From September to December 2021, a total of 5 520 college students from universities in Jilin, Anhui, Jiangxi, Xinjiang, and Shanghai, were surveyed with sugar sweetened beverage consumption and physical fitness using stratified cluster sampling. One way ANOVA and Logistic regression analysis were used to analyze the association between sugary drink consumption and physical fitness index (PFI).@*Results@#The frequencies of sugar-sweetened beverage consumption among college students were 10.3% , 67.2%, 13.9% , and 8.6% for 0, 1-3, 4-5, and ≥ 6 times/week, respectively. The differences in waist circumference, grip strength, standing long jumping, sit and reach, 50-meter running, and 1 000/800 meter running performance were statistically significant among college students with varying sugar-sweetened beverage consumption ( F =8.67, 7.22, 11.20, 13.47, 3.98, 2.86 , P <0.05). Logistic regression analysis showed that those who had sugary drinks 4-5 times/week, ≥ 6 times/week had a higher risk of low PFI compared to those who reported no sugary drinks ( OR =1.48, 1.56, P <0.05). With respect to gender, the risk of low PFI was also higher among male students who consumed sugary drinks ≥6 times/week ( OR =2.01, P <0.05), while there was no significant difference among female students.@*Conclusion@#Sugar-sweetened beverage consumption is negatively associated with the physical fitness index among college students with significant gender differences. College students, especially males, should be targeted to improve health literacy, reduce the consumption of sugar-sweetened beverages, so as to improve physical fitness.

Analysis on fluid intake and urination behaviors among the elderly in five cities in China: a cross-sectional study.

Background: Fluid intake in the elderly may influence urination behaviors and further influence their health status. This study investigated the behaviors of fluid intake, urination and their relationships among the elderly in China. Methods: Stratified random sampling was used to recruit the elderly participants who met the inclusion criteria from five cities in China. Participants' total fluid intake (TFI) level was investigated using a validated 7-day 24 h fluid intake questionnaire. Their urination behaviors in real time were also recorded using a validated 7-day 24 h urination behavior record. Results: A total of 524 participants completed the study, including 233 males and 291 females. The average age was 69.7 years. The median daily TFI was 1,241 mL, with a frequency of 8.1 times per day. Approximately 73.3% of the participants did not reach the amount of adequate fluid intake (1.7 L for males and 1.5 L for females) recommended in China. Fluid intake in the morning, afternoon, and evening among participants was 594 mL, 305 mL and 342 mL, with a frequency of 3.0 times, 1.7 times, and 2.0 times, respectively. The median urination frequency was 7.4 times per day. The percentage of participants who urinated >7 times during the day was 44.3%. The percentage of participants who urinated ≥1 time at night was 77.5%. Age and BMI were not the main influence factors for fluid intake and urination behaviors. The preliminary analysis showed that higher TFI, plain water intake, dairy products intake, and fluid intake frequency were significantly associated with higher urination frequency (t = 6.553, p < 0.05; t = 5.291, p < 0.05; t = 4.667, p < 0.05; t = 13.413, p < 0.05). Higher fluid intake per time was significantly associated with lower urination frequency (t = -3.562, p < 0.05). Correlations between TFI, fluid intake frequency, fluid intake in night, fluid intake frequency in night and urination at night were also found (r = 0.114, p < 0.05; r = 0.091, p < 0.05; r = 0.146, p < 0.05; r = 0.331, p < 0.05). Conclusion: Fluid intake was inadequate in terms of the elderly participants. Participants with higher fluid intake and frequency in night had a greater incidence of nocturia. Thus, correcting fluid intake behaviors can improve urination behavior and promote health. Clinical trial registration: https://www.chictr.org.cn/searchprojEN.html, identifier CTR1900023355.

Theoretical prediction of a graphene-like 2D uranyl material with p-orbital antiferromagnetism.

Versatile graphene-like two-dimensional materials with s-, p- and d-block elements have aroused significant interest because of their extensive applications while there is a lack of such materials with f-block elements. Herein we report a unique one composed of the f-block element moiety of uranyl (UO2 2+) through a global-minimum structure search. Its geometry is found to be similar to that of graphene with a honeycomb-like hexagonal unit composed of six uranyl ligands, where each uranyl is bridged by two superoxido groups and a pair of hydroxyl ligands. All the uranium and bridging oxygen atoms form an extended planar 2D structure, which shows thermodynamic, kinetic and thermal stabilities due to σ/π bonding as well as electrostatic interactions between ligands. Each superoxido ligand has one unpaired (2pπ*)1 electron and is antiferromagnetically coupled through uranyl bridges with 2pπ*-5f δ -2pπ* superexchange interactions, forming a rare type of one-dimensional Heisenberg chain with p-orbital antiferromagnetism, which might become valuable for application in antiferromagnetic spintronics.

Ultra-Efficient Americium/Lanthanide Separation through Oxidation State Control.

Lanthanide/actinide separation is a worldwide challenge for atomic energy and nuclear waste treatment. Separation of americium (Am), a critical actinide element in the nuclear fuel cycle, from lanthanides (Ln) is highly desirable for minimizing the long-term radiotoxicity of nuclear waste, yet it is extremely challenging given the chemical similarity between trivalent Am(III) and Ln(III). Selective oxidation of Am(III) to a higher oxidation state (OS) could facilitate this separation, but so far, it is far from satisfactory for practical application as a result of the unstable nature of Am in a high OS. Herein, we find a novel strategy to generate stable pentavalent Am (Am(V)) through coordination of Am(III) with a diglycolamide ligand and oxidation with Bi(V) species in the presence of an organic solvent. This strategy leads to efficient stabilization of Am(V) and an extraordinarily high separation factor (>104) of Am from Ln through one single contact in solvent extraction, thereby opening a new avenue to study the high-OS chemistry of Am and fulfill the crucial task of Ln/Am separation in the nuclear fuel cycle. The synergistic coordination and oxidation process is found to occur in the organic solvent, and the mechanism has been well elucidated by quantum-theoretical modeling.

Electronic Structure and Spectroscopic Properties of Group-7 Tri-Oxo-Halides MO3X (M = Mn-Bh, X = F-Ts).

The 24 trioxide halide molecules MO3X of the manganese group (M = Mn-Bh; X = F-Ts), which are iso-valence-electronic with the famous MnO4- ion, have been quantum-chemically investigated by quasi-relativistic density-functional and ab initio correlated approaches. Geometric and electronic structures, valence and oxidation numbers, vibrational and electronic spectral properties, energetic stabilities of the monomers in the gas phase, and the decay mode of MnO3F have been investigated. The light Mn-3d species are most strongly electron-correlated, indicating that the concept of a closed-shell Lewis-type single-configurational structure [Mn+7(d0) O-2(p6)3 F-(p6)] reaches its limits. The concept of real-valued spin orbitals φ(r)·α and φ(r)·ß breaks down for the heavy Bh-6d, At-6p and Ts-7p elements because of the dominating spin-orbit coupling. The vigorous decomposition of MnO3F at ambient conditions starts by the autocatalyzed release of n O2 and the formation of MnmO3m-2nFm clusters, triggered by the electron-depleted "oxylic" character of the oxide ligands in MnO3X.

Norm-Conserving Pseudopotentials and Basis Sets to Explore Actinide Chemistry in Complex Environments.

We have developed a new set of norm-conserving pseudopotentials and companion Gaussian basis sets for the actinide (An) series (Ac-Lr) using the Goedecker, Teter, and Hutter (GTH) formalism with the Perdew, Burke, and Ernzerhof (PBE) exchange-correlation functional of generalized gradient approximation. To test the accuracy and reliability of the newly parameterized An-GTH pseudopotentials and basis sets, a variety of benchmarks on actinide-containing molecules were carried out and compared to all-electron and available experimental results. The new pseudopotentials include both medium- ([Xe]4f14) and large-core ([Xe]4f145d10) options that successfully reproduce the structures and energetics, particularly redox processes. The medium-core size set, in particular, reproduces all-electron calculations over multiple oxidation states from 0 to VII, whereas the large-core set is suitable only for the early series elements and low oxidation states. The underlying reason for these transferability issues is discussed in detail. This work fills a critical void in the literature for studying the chemistry of 5f-block elements in the condensed phase.

Coordination Sphere of Lanthanide Aqua Ions Resolved with Ab Initio Molecular Dynamics and X-ray Absorption Spectroscopy.

To resolve the fleeting structures of lanthanide Ln3+ aqua ions in solution, we (i) performed the first ab initio molecular dynamics (AIMD) simulations of the entire series of Ln3+ aqua ions in explicit water solvent using pseudopotentials and basis sets recently optimized for lanthanides and (ii) measured the symmetry of the hydrating waters about Ln3+ ions (Nd3+, Dy3+, Er3+, Lu3+) for the first time with extended X-ray absorption fine structure (EXAFS). EXAFS spectra were measured experimentally and generated from AIMD trajectories to directly compare simulation, which concurrently considers the electronic structure and the atomic dynamics in solution, with experiment. We performed a comprehensive evaluation of EXAFS multiple-scattering analysis (up to 6.5 Å) to measure Ln-O distances and angular correlations (i.e., symmetry) and elucidate the molecular geometry of the first hydration shell. This evaluation, in combination with symmetry-dependent L3- and L1-edge spectral analysis, shows that the AIMD simulations remarkably reproduces the experimental EXAFS data. The error in the predicted Ln-O distances is less than 0.07 Å for the later lanthanides, while we observed excellent agreement with predicted distances within experimental uncertainty for the early lanthanides. Our analysis revealed a dynamic, symmetrically disordered first coordination shell, which does not conform to a single molecular geometry for most lanthanides. This work sheds critical light on the highly elusive coordination geometry of the Ln3+ aqua ions.

Norm-Conserving Pseudopotentials and Basis Sets To Explore Lanthanide Chemistry in Complex Environments.

A complete set of pseudopotentials and accompanying basis sets for all lanthanide elements are presented based on the relativistic, norm-conserving, separable, dual-space Gaussian-type pseudopotential protocol of Goedecker, Teter, and Hutter (GTH) within the generalized gradient approximation (GGA) and the exchange-correlation functional of Perdew, Burke, and Ernzerhof (PBE). The corresponding basis sets have been molecularly optimized (MOLOPT) using a contracted form with a single set of Gaussian exponents for the s, p, and d states. The f states are uncontracted explicitly with Gaussian exponents. Moreover, the Hubbard U values for each lanthanide element, for DFT+U calculations, are also tabulated, allowing for the proper treatment of the strong on-site Coulomb interactions of localized 4f electrons. The accuracy and reliability of our GTH pseudopotentials and companion basis sets optimized for lanthanides is illustrated by a series of test calculations on lanthanide-centered molecules, and solid-state systems, with the most common oxidation states. We anticipate that these pseudopotentials and basis sets will enable larger-scale density functional theory calculations and ab initio molecular dynamics simulations of lanthanide molecules in either gas or condensed phases, as well as of solid state lanthanide-containing materials, allowing further exploration of the chemical and physical properties of lanthanide systems.

The df-d Dative Bonding in a Uranium-Cobalt Heterobimetallic Complex for Efficient Nitrogen Fixation.

Single transition-metal site catalysts with s-, p-, or d-block atom anchor for nitrogen fixation have been extensively studied, and yet the studies of the f-block atom anchor are rarely reported. Thus, we investigate the feasibility of using a newly synthesized U-Co complex featuring a single CoI site coordinated by tetrakis(phophinoamide) and an UIV anchor for N2-to-NH3 conversion by theoretical modeling. We characterize the evolution of oxidation states of U and Co along the reaction pathways from ab initio density matrix renormalization group (DMRG) calculations, and we find that the variation of the Co → U dative bond is correlated with the changes of oxidation states. Both uranium and cobalt can serve as electron reservoirs to facilitate breaking the N-N bond. Our study demonstrates the viability of metal → metal dative bonds, particularly the df-d one, for the reduction of N2 to NH3, and thus, this opens up a new avenue to the rational design of efficient catalyst for nitrogen fixation.

Triple bonds between iron and heavier group-14 elements in the AFe(CO)3- complexes (A = Ge, Sn, and Pb).

Heteronuclear transition-metal-main-group element carbonyl anion complexes of AFe(CO)3- (A = Ge, Sn, and Pb) are prepared using a laser vaporization supersonic ion source in the gas phase, which were studied by mass-selected infrared (IR) photodissociation spectroscopy. The geometric and electronic structures of the experimentally observed species are identified by a comparison of the measured and calculated IR spectra. These anion complexes have a 2A1 doublet electronic ground state and feature an A[triple bond, length as m-dash]Fe triply bonded C3v structure with all of the carbonyl ligands bonded at the iron center. Bonding analyses of AFe(CO)3- (A = C, Si, Ge, Sn, Pb, and Fl) indicate that the complexes are triply bonded between the valence np atomic orbitals of bare group-14 atoms and the hybridized 3d and 4p atomic orbitals of iron.

Lanthanides with Unusually Low Oxidation States in the PrB3- and PrB4- Boride Clusters.

Lanthanide elements typically exhibit a +III oxidation state (OS) in chemical compounds with a few in +IV or even +V OS. Although lanthanides with +II OS have been observed recently in organometallic compounds, +I OS is extremely rare. Using a joint photoelectron spectroscopy and quantum theoretical study, we have found two low OS lanthanides in doped boron clusters, PrB3- and PrB4-. These two clusters are shown to have planar structures, in which the Pr atom is bonded to the aromatic boron clusters via two Pr-B σ bonds. Chemical bonding and electronic structure analyses reveal that the Pr atom is in a very low OS in the two boride clusters: +II in PrB3- and +I in PrB4-. The current finding suggests that there should exist a whole class of boride complexes featuring rather low-valent lanthanides and expands the frontier of lanthanide chemistry.

Polarizable force field parameterization and theoretical simulations of ThCl4 -LiCl molten salts.

Recycle of thorium is an essential process in the thorium-uranium closed fuel cycle of molten salt reactor (MSR). Pyrochemical treatment of spent nuclear fuel using chloride molten salts as medium has been considered as a promising method. In this article, we performed molecular dynamics simulations on the ThCl4 LiCl molten salts using a polarizable force field parameterized by us from first-principles calculations. The microscopic structures and macroscopic properties at different compositions were investigated using the developed force field to understand the structure/property relationship in the mixture. The differences between ThCl4 LiCl and ThF4 LiF MSs are compared to understand the behaviors of Th4+ in the fluoride-chloride mixed media. In the molten fluorides, the coordination number of Th4+ is larger, and the resulting more shared anions lead to lower ThF dissociation barrier and shorter lifetime of the Th4+ first solvation shell. Our results also indicate the Pauling's structural rules for crystals can be used to rationalize the local structures in molten salts. © 2018 Wiley Periodicals, Inc.