Miracle-dz/UniFAR-FTUs huggingface dataset:
Kinetic studies of raindrop chemistry: 1. Inorganic and organic processes

The chemistry of raindrops, thought not long ago to be adequately represented by a few simple ions and their equilibrium constants, is now recognized to include the complex reactions of ions, radicals, and molecules of both acidic and basic moieties. To describe this system, we have formulated a model which includes both inorganic and organic processes (but not metal catalysis) totaling 94 reactions in 53 species. Three sets of computations were performed for raindrops of different diameters. In the first two, the initial chemistry of the raindrops was set by the cloud chemistry measurements of APEX (Atmospheric Precipitation Experiment) in the northeastern United States. In the simulations the drops were released into tropospheric air characteristic of either the suburban or urban northeast. In the third set of computations, designed to simulate urban centers on the U.S. west coast, raindrops with composition typical of those over the oceans were dropped in urban tropospheric air. Among the results are the following: (1) Photochemical processes, including the photolysis of H2O2 to produce OH˙ and the photolysis of NO3− to produce ozone, are significant in raindrops chemistry. (2) Organic chemical reactions of interest and importance occur in raindrops, particularly those of small size (and thus long lifetime), with the oxidation of aldehydes to organic acids being perhaps the most important. (3) Significant differences in some species concentrations occur at different altitudes during the raindrop's fall and for drops of different diameters. These differences are related to the scavenging efficiencies and lifetimes of the drops. (4) Given constant initial concentrations of trace species in raindrops, the calculations show that ion concentrations in rainwater increase as the rain rate decreases and that in a steady rainfall the concentrations of scavenged ions decrease as the concentrations of the gaseous precursors decrease. Neither effect is large, however. (5) The model results are consistent with experimental data, suggesting that below-cloud processes do not significantly affect the concentration of strong inorganic acids in rain at ground level unless acid concentrations are low in droplets at cloud base.
Pyrolysis gas chromatography of humic substances from different origin

Pyrolytische Gaschromatografie von Huminstoffen unterschiedlichen Ursprungs. Die Pyrolyse von Huminstoffen liefert unter anderen niedrig siedenden Substanzen Alkane und Olefine, deren Anteil bei Fulvo- und Huminsauren unterschiedlich ist. Diese Verbindungen entstehen durch Radikalreaktionen aus aliphatischen oder alicyclischen Ketten; ihre Bildung wird zum Teil durch den Aschegehalt der Huminstoffe katalytisch beeinflust. Nach dem Erhitzen von Huminstoffen an der Luft werden weder Alkane noch Olefine pyrolytisch gebildet.
Reinvestigation of the Structure of Galbanic Acid by 2D NMR Techniques Including 2D INADEQUATE.

The galbanic acid (1) is a sesquiterpene coumarin ether occurred in the resin of Ferula assa-foetida L. (Umbelliferae) and also found in various species of the Ferula genus. It had been isolated for the first time from the gum resin of F. microloba in 19721 and its structure (2) was postulated by Borisov et al. in 1973.2 However, the proposed structure was completely revised as 1 in 1980 by an analysis of 300 MHz 'H NMR spectrum? On the other hand, Kajimoto and his co-worker had isolated a compound named asacoumarin B (3) from F. assa-foetida in 1989, and suggested a struc­ ture which had been quite different from that of I.4 They had proposed the structure of asacoumarin B particularly by the investigation of the ozonolysis product. However, the asacoumarin B was revealed recently to be a galbanic acid (1) by Appendino et al.5 They had investigated the structure of 3 by the aid of 2-D NMR techniques, which was not dep­ icted in detail in literature, and confirmed the structure of galbanic acid as 1 suggested by Bagirov et al. in 1980? In the process of searching for new compounds from the gum resin of F. assafoetida, we found the presumed same compound as 1 at least on the basis of the patterns and 나lemical 아)ifts of and 13C NMR. Although there are numerous indirect ways6 to elucidate the carbon skeleton of organic molecules, indirect approach fails and some ambig­ uities remain further in the assignment of carbon resonances when the proton spectra do not exhibit well resolved signals. All of these limitations could be solved if we could meas­ ure the direct carbon-carbon correlations. Because the importance of correct chemical shifts as­ signments even can never be overstated to unlock all the in­ formation present in the spectrum, it is worth reinvestigat­ ing the controversial structure of galbanic acid (1). Consequently, we reinvestigate the structure of 1 by 2D NMR techniques including 2D INADEQUATE and herein report the unambiguous results and correct stereochemistry of 1.
Formation and Growth Mechanisms of Imogolite-Like Aluminogermanate Nanotubes

The growth mechanisms of imogolite-like aluminogermanate nanotubes have been examined at various stages of their formation. The accurate determination of the nucleation stage was examined using a combination of local- (XAS at the Ge−K edge and 27Al NMR) and semilocal scale technique (in situ SAXS). For the first time, a model is proposed for the precursors of the nanotubular structure and consist in rooftile-shaped particles, up to 5 nm in size, with ca. 26% of Ge vacancies and varying curvatures. These precursors assemble to form short nanotubes/nanorings observed during the aging process. The final products are most probably obtained by an edge−edge assembly of these short nanotube segments.
A modified apparatus for quick and versatile sulphate sulphur analysis using hydriodic acid reduction

Abstract A simplified apparatus was tested for the distillation of H2S using hydriodic acid reagent in combination with bismuth sulphide detection. The digestion‐distillation flask is a modified Taylor tube. The tube facilitates sodium hypobromite digestion in a block digestor for total S analysis. The simplified apparatus does not include a water condenser and therefore distillation time is reduced. Thorough examination showed that the new apparatus gave essentially the same results as the Johnson‐Nishita method for sulphate and total soil S analyses. Transfer of all reduced sulphate into the collecting solution in the proposed apparatus took about one‐half the time that it took in the Johnson‐Nishita apparatus. Advantages of the proposed apparatus compared to Johnson‐Nishita and/or Tabatabai‐Bremner apparatus include low fabrication cost, flexibility to conduct both sodium hypobromite digested (total S) and undigested (sulphate S) analyses and economy of time for distillation.
Food Crushing Sounds: Comparisons of Objective and Subjective Data

SUMMARY The sounds produced when certain foodstuffs were chewed were tape recorded, and the amplitude of frequency-filtered or total sound was measured from the recordings. On the same occasions, the subjects' opinions about toughness/tenderness or about loudness were noted. Some correlations between objective and subjective data obtained in this way are presented and discussed.
10 nm Si pillars fabricated using electron‐beam lithography, reactive ion etching, and HF etching

This article reports the fabrication and preliminary photoluminescence (PL) study of free‐standing Si pillars with diameters of about 10 nm and aspect ratios greater than 15. The pillars were fabricated using electron‐beam lithography, chlorine based reactive ion etching (RIE), and subsequent HF wet etching. Using HF etching offers several advantages: (a) it is a relatively stress independent process and therefore preserves the original shape of the structure; (b) it is a room temperature process; (c) it has a very controllable etch rate, ∼1.9 nm/h; and (d) it can remove RIE damage and passivate the Si surface. PL with a peak at 720 nm was repeatedly observed from an array of nanoscale pillars with ∼20 nm diameters. However, the cause of such PL is still unclear.
Graphene-based materials for catalysis

Graphene is one of the most promising materials in nanotechnology. From a theoretical point of view, it provides the ultimate two-dimensional model of a catalytic support. Its unique physical, chemical and mechanical properties are outstanding, and could allow the preparation of composite-materials with unprecedented characteristics. Even though the use of a single graphene sheet as a catalytic support has not yet been reported, some promising results have already been obtained with few-layer graphene. In this review, we will briefly discuss the most relevant synthetic routes to obtain graphene. Then, we will focus our attention on the properties and characterization techniques of graphene that are of relevance to catalysis, with emphasis on adsorption. After presenting an overview of the most common and effective preparation methods, we will discuss the catalytic application of graphene and graphene-based composites, with particular attention on energy conversion and photocatalysis.
Highly hydrophilic fused aggregates (microsponges) from a C12 spermine bolaamphiphile

Bolaamphiphiles consist of two hydrophilic headgroups joined by a hydrophobic linker. They are known to self-assemble into vesicles, micelles, tubules and fibers. Here we report on the self-assembly of a 1,12-[N,N-bis(3-aminopropyl)-1,4-butane diamine] dodecane (12G1) in aqueous media into discrete nonbilayer nanoparticles and unusual fused highly hydrated sponge like structures. 12G1, 1,10-[ N,N-bis(3-aminopropyl)-1,4-butane diamine] decane (10G1), 1,8-[N,N-bis(3-aminopropyl)-1,4-butane diamine] octane (8G1), and 1-[N,N-bis(3-aminopropyl)-1,4-butane diamine] dodecane (12G0) were synthesized and their self-assembly studied. 12G0 was relatively insoluble in water and multilamellar vesicles were produced with this amphiphile and cholesterol. While no aggregation in aqueous media was recorded for either 10G1 or 8G1 up to a concentration of 20 mM, aggregation of 12G1 molecules was seen to take place at an aqueous concentration of 1.75 mM as determined using various fluorescent and colorimetric probes and surface tension measurements. Electron microscopy images revealed that 12G1 formed monolayer vesicles of 20 nm in size at a concentration of 2.6 mM and even larger fused aggregates when the concentration was increased to 35 mM. Fusion resulted from the bridging of vesicles by the bolaamphiphile molecules. 12G1 aggregates encapsulated 23X more low molecular weight (4kD) FITC-dextran than high (250kD) molecular weight FITC-dextran, an indication of the limited volume of the hydrophilic domains. 12G1 also encapsulated 137X more 4kD FITC-dextran than was encapsulated by conventional sorbitan monostearate vesicles. We conclude that highly hydrated aggregates consisting of fused monolayer vesicles with small discrete hydrophilic domains in a sponge like structure may be formed by the self-assembly of bolaamphiphiles.
(Iminophosphorane)copper(I) Complexes as Highly Efficient Catalysts for 1,3‐Dipolar Cycloaddition of Azides with Terminal and 1‐Iodoalkynes in Water: One‐Pot Multi‐Component Reaction from Alkynes and in situ Generated Azides

Treatment of water-soluble phosphanes PTA (1) and DAPTA (2) with an equimolecular amount of azides (RO)2P(=S)N3 (R = Et, Ph) leads to high-yield formation of the N-thiophosphorylated iminophosphorane derivatives 3b and 4a,b, respectively. The reaction of these new iminophosphorane ligands with [Cu(NCCH3)4][PF6] (in a 2:1 molar ratio) has been investigated. The resulting (iminophosphorane)copper(I) complexes 5b and 6a,b are efficient catalysts for the three-component cycloaddition reaction (organic halide, NaN3 and terminal alkynes) in aqueous media to afford regioselectively, under mild and aerobic conditions according to “click laws”, 1,4-disubstituted triazoles with a broad substrate scope and functional compatibility. The unprecedented application of the analogous (iminophosphorane)copper(I) catalyst 5a to a one-pot three-component reaction with 1-iodoalkynes as an internal alkyne in aqueous medium is also reported. ESI-MS analysis of 5a in water and DFT theoretical calculations [B3LYP/6-31G(d)] have been carried out providing valuable insight into the actual active species responsible for catalytic activity in water.
Surface Forces in Solutions Containing Rigid Polymers: Approaching the Rod Limit

In a recent paper,1 we investigated how the interaction between two adsorbing surfaces in a polymer solution responds to changes of the intrinsic stiffness of the polymer chains. We demonstrated that as the chain rigidity is increased, starting from the fully flexible limit, a free energy barrier develops. In this work, we shall continue our studies of semiflexible polymers but focus on the other extreme, where the stiffness is increased to the extent that the chains become rodlike. In this limit, the free energy barrier disappears and is replaced by a long-ranged attraction. A weak barrier at separations corresponding to the length of a fully stretched chain is, however, present. The approach to rodlike behavior is very slow at low polymer concentrations; i.e., rods will under these conditions behave in a manner which is qualitatively different from that of even extremely rigid semiflexible chains. At higher concentration, a slightly different picture emerges, since saturation effects will prevent an exc.
Three-dimensional microchanelled electrodes in flow-through configuration for bioanode formation and current generation

Three-dimensional microchannelled nanocomposite electrodes fabricated by ice-segregation induced self-assembly of chitosan-dispersed multiwall carbon nanotubes are shown to provide a scaffold for growth of electroactive bacteria for use as acetate-oxidizing bioanodes in bioelectrochemical systems. The hierarchical structure provides a conductive surface area available for G. sulfurreducens colonization, with a flow through configuration along the electrode providing a substrate for bacterial colonization and bio-electrochemical processes. This configuration, whilst resulting in sub-monolayer biofilm coverage over the three-dimensional surface, is capable of providing acetate oxidation current densities of up to 24.5 A m−2, equating to a volumetric current density of 19 kA m−3, in the flow-through configuration. Such bioanodes, when operated in non-optimized flow-through microbial fuel cell configuration, provide a maximum power density of 2.87 W m−2, which is equivalent to 2.0 kW m−3 volumetric power density.
Acquisition of object-robbing and object/food-bartering behaviours: a culturally maintained token economy in free-ranging long-tailed macaques

The token exchange paradigm shows that monkeys and great apes are able to use objects as symbolic tools to request specific food rewards. Such studies provide insights into the cognitive underpinnings of economic behaviour in non-human primates. However, the ecological validity of these laboratory-based experimental situations tends to be limited. Our field research aims to address the need for a more ecologically valid primate model of trading systems in humans. Around the Uluwatu Temple in Bali, Indonesia, a large free-ranging population of long-tailed macaques spontaneously and routinely engage in token-mediated bartering interactions with humans. These interactions occur in two phases: after stealing inedible and more or less valuable objects from humans, the macaques appear to use them as tokens, by returning them to humans in exchange for food. Our field observational and experimental data showed (i) age differences in robbing/bartering success, indicative of experiential learning, and (ii) clear behavioural associations between value-based token possession and quantity or quality of food rewards rejected and accepted by subadult and adult monkeys, suggestive of robbing/bartering payoff maximization and economic decision-making. This population-specific, prevalent, cross-generational, learned and socially influenced practice may be the first example of a culturally maintained token economy in free-ranging animals. This article is part of the theme issue ‘Existence and prevalence of economic behaviours among non-human primates'.
Stigma associated with parental depression or cancer: Impact on spouse and offspring's cortisol levels and socioemotional functioning

Abstract Stress associated with caring for a mentally ill spouse can adversely affect the health status of caregivers and their children. Adding to the stress of caregiving is the stigma often placed against spouses and children of people with mental illness. Contrary to mental illness, many physical disorders such as cancer may be less stigmatized (expect pulmonary cancer). In this study, we measured externalized and internalized stigma, as well as psychological (depressive symptoms and stressful life events) and physiological (basal salivary cortisol levels) markers of stress in 115 spouses and 154 children of parents suffering from major depressive disorder, cancer, or no illness (control group). The results show that spouses and children from families with parental depression present significantly more externalized stigma than spouses and children from families with parental cancer or no illness, although we find no group differences on internalized stigma. The analysis did not show a significant group difference either for spouses or their children on depressive symptomatology, although spouses from the parental depression group reported greater work/family stress. Finally, we found that although for both spouses children the awakening cortisol response was greater on weekdays than on weekend days, salivary cortisol levels did not differ between groups. Bayes factor calculated on the null result for cortisol levels was greater than 100, providing strong evidence for the null hypothesis H0. Altogether, these results suggest an impact of stigma toward mental health disorder on psychological markers of stress but no impact of stigma on physiological markers of stress. We suggest that these results may be due to the characteristics of the families who participated in the present study.
Wave-induced shallow-water monopolar vortex: large-scale experiments

Abstract Numerous field observations of tsunami-induced eddies in ports and harbours have been reported for recent tsunami events. We examine the evolution of a turbulent shallow-water monopolar vortex generated by a long wave through a series of large-scale experiments in a rectangular wave basin. A leading-elevation asymmetric wave is guided through a narrow channel to form a flow separation region on the lee side of a straight vertical breakwater, which coupled with the transient flow leads to the formation of a monopolar turbulent coherent structure (TCS). The vortex flow after detachment from the trailing jet is fully turbulent ($Re_h \sim O(10^{4}\text {--}10^{5}$)) for the remainder of the experimental duration. The free surface velocity field was extracted through particle tracking velocimetry over several experimental trials. The first-order model proposed by Seol & Jirka (J. Fluid Mech., vol. 665, 2010, pp. 274–299) to predict the decay and spatial growth of shallow-water vortices fits the experimental data well. Bottom friction is predicted to induce a $t^{-1}$ azimuthal velocity decay and turbulent viscous diffusion results in a $\sqrt {t}$ bulk vortex radial growth, where $t$ represents time. The azimuthal velocity, vorticity and free surface elevation profiles are well described through an idealised geophysical vortex. Kinematic free surface boundary conditions predict weak upwelling in the TCS-centre, followed by a zone of downwelling in a recirculation pattern along the water column. The vertical confinement of the flow is quantified through the ratio of kinetic energy contained in the secondary and primary surface velocity fields and a transition point towards a quasi-two-dimensional flow is identified.
Sympathetic nervous system dominance during stress recovery mediates associations between stress sensitivity and social anxiety symptoms in female adolescents

Abstract Social anxiety disorder (SAD) is commonly diagnosed during adolescence and is associated with psychological stress reactivity and heightened physiological arousal. No study, however, has systematically examined which aspects of autonomic nervous system function mediate likely links between stress sensitivity and social anxiety symptoms in adolescents. Here, we assessed 163 adolescents (90 females; 12.29 ± 1.39 years) with respect to life stress and social anxiety symptoms, and measured respiratory sinus arrhythmia (RSA) and skin conductance levels (SCL) during a psychosocial stress paradigm. We operationalized stress sensitivity as the residual variance in subjective stress severity after accounting for objective severity and changes in autonomic regulation using standardized change scores in RSA and SCL. In females only, stress sensitivity and social anxiety symptoms were significantly correlated with each other (p < .001) and with autonomic regulation during both reactivity and recovery (all ps < 0.04). Further, sympathetic nervous system dominance during recovery specifically mediated associations between stress sensitivity and social anxiety symptoms (B = 1.06, 95% CI: 0.02–2.64). In contrast, in males, stress sensitivity, autonomic regulation during reactivity or recovery, and social anxiety symptoms were not significantly associated (all ps > 0.1). We interpret these results in the context of psychobiological models of SAD and discuss implications for interventions targeting autonomic processes.
Ensemble average and nearest particle statistics in disperse multiphase flows

Abstract A relation between the ensemble average and the nearest particle statistics is derived. The relation accounts for interactions among all the particles, not only the nearest one, and can be used to study long-range particle interactions without the difficulty of a divergent integral. As an example, this relation is applied to calculate the particle sedimentation velocity to the first order of the particle volume fraction. Using the relation, an important particle–fluid–particle stress is introduced for general multiphase flows.
P-V-T equation of state of hydrous phase A up to 10.5 GPa

Abstract Pressure-volume-temperature (P-V-T) data of synthetic Mg7Si2O8(OH)6 phase A were collected under P-T conditions up to ~10.5 GPa and 900 K by energy-dispersive X‑ray diffraction using a cubic type multi-anvil apparatus, MAX80, located at the Photon Factory–Advanced Ring (PF-AR) at the High Energy Accelerator Research Organization (KEK). P-V EoS using only room-temperature data yielded V0 = 511.6(2) Å3, KT0 = 106.8(18) GPa, and pressure derivative K T ′ = $K_{T}^{\prime}=$ 3.88(38). These parameters were consistent with the subsequent equation of state (EoS) analysis. The compressibility of phase A was anisotropic, with its a-axis being ~26% more compressible than the c-axis, which is normal to the plane of the distorted close-packed layers. A fit of the present data to the high-temperature Birch-Murnaghan EoS yielded V0 = 511.7(3) Å3, K0 = 104.4(24) GPa, K′ = 4.39(48), (∂KT/∂T)P = –0.027(5) GPa K–1, and thermal expansion α = a + bT with values of a = 2.88(27) × 10–5 K–1 and b = 3.54(68) × 10–8 K–2. The lattice dynamical approach by the Mie-Grüneisen-Debye EoS yielded θ0 = 928(114) K, q = 2.9(10), and γ0 = 1.19(8). The isobaric heat capacity C P of phase A at 1 atm. was calculated based on the Mie-Grüneisen-Debye EoS fit of present P-V-T data. In addition, the density profiles of subducting slabs with different degrees of serpentinization were also calculated along the cold geotherm up to ~13 GPa. The serpentinization of subducting slab will significantly lower the density of slab at shallower depth; however, this effect becomes negligible when antigorite dehydrates to phase A. Because the phase A bearing subducting slab is supposed to be denser than the surrounding mantle, the water can transport into deeper parts of the upper mantle and the transition zone.