Miracle-dz/UniFAR-FTUs huggingface dataset:
Pyridinolyses of 2,4-Dinitrophenyl Phenyl Carbonate and 2,4-Dinitrophenyl Benzoate: Effect of Nonleaving Group on Reactivity and Mechanism † †

o , has been found to be 8.5 and 9.5 for the reactions of 2 and 1, respectively. Dissection of kN into the microscopic rate constants (e.g., k1 and k2/k-1 ratio) has revealed that the reactions of 2 result in larger k1 values than those of 1, indicating that PhO behaves as a stronger electron-withdrawing group than Ph. However, the k2/k-1 ratio has been found to be independent of the electronic nature of Ph and PhO.
Detecting and Understanding Nitric Oxide Formation during Nitrogen Cycling in Microbial Biofilms

Nitric oxide (NO) is a ubiquitous biomolecule that is known as a signaling compound in eukaryotes and prokaryotes. In addition, NO is involved in all conversions of the biogeochemical nitrogen cycle: denitrification, nitrification, and the anaerobic oxidation of ammonium (Anammox). Until now, NO has not been measured with high spatial resolution within microbial communities, such as biofilms, sediments, aggregates or microbial mats, because the available sensors are not robust enough and their spatial resolution is insufficient. Here we describe the fabrication and application of a novel Clark-type NO microsensor with an internal reference electrode and a guard anode. The NO microsensor has a spatial resolution of 60-80 μm, a sensitivity of 2 pA μM, and a detection limit of ~30 nM. Hydrogen sulfide (H2S) was found to be a major interfering compound for the electrochemical detection of NO. The application of the novel NO microsensor to nitrifying biofilms and marine sediments revealed dynamic NO concentration profiles with peaks in the oxic parts of the samples. The local concentrations suggested that NO may be an important bioactive compound in natural environments. The consumption and production of NO occurs in separate regions of stratified microbial communities and indicates that it is linked to distinct biogeochemical cycles.
High-speed diode laser measurements of temperature and water vapor concentration in the intake manifold of a diesel engine

A diode laser–based sensor system, utilizing absorption spectroscopy, has been developed to provide high-speed (5 kHz) simultaneous measurements of temperature and water vapor concentration in the intake manifold of a diesel engine. A fiber-coupled 1.38 µm diode laser was used to probe absorption transitions of water vapor for the high-speed gas temperature and water vapor concentration measurements. Water vapor readily absorbs in the near-infrared region, and distributed feedback diode lasers as well as optics for near-infrared region are readily available because of their use in telecommunications. Fresh charge and combustion products are the only sources of water vapor in an engine’s gas exchange path; therefore, water vapor concentration at various locations in the intake manifold is a useful measure of the recirculated exhaust gas distribution in the intake manifold. Measurements were performed on a six-cylinder Cummins diesel engine using compact fiber optic–coupled connectors. The chosen water vapor absorption transitions provided good absorption strength even without exhaust gas recirculation and water vapor concentration of as low as 0.7 vol.% could be measured with a signal-to-noise ratio of ∼35 leading to very good spectral fits. The sensor output was within 2% of the thermocouple readings and within 10% of the water vapor concentration derived from mean CO2 analyzer measurements for steady-state engine operation. For transient engine operation, the time response of the diode laser sensor was shown to be vastly superior to that of the installed thermocouple and the gas analyzer system.
Free energy surfaces of miniproteins with a ββα motif: Replica exchange molecular dynamics simulation with an implicit solvation model

Designed miniproteins with a ββα motif, such as BBA5, 1FSD, and 1PSV can serve as a benchmark set to test the validity of all‐atom force fields with computer simulation, because they contain all the basic structural elements in protein folding. Unfortunately, it was found that the standard all‐atom force fields with the generalized Born (GB) implicit solvation model tend to produce distorted free energy surfaces for the ββα proteins, not only because energetically those proteins need to be described by more balanced weights of the α‐ and β‐strands, but also because the GB implicit solvation model suffers from overestimated salt bridge effects. In an attempt to resolve these problems, we have modified one of the standard all‐atom force fields in conjunction with the GB model, such that each native state of the ββα proteins is in its free energy minimum state with reasonable energy barriers separating local minima. With this modified energy model, the free energy contour map in each protein was constructed from the replica exchange molecular dynamics REMD simulation. The resulting free energy surfaces are significantly improved in comparison with previous simulation results and consistent with general views on small protein folding behaviors with realistic topology and energetics of all three proteins. Proteins 2006. © 2005 Wiley‐Liss, Inc.
Thyroid dysfunction diagnosis from routine laboratory tests based on machine learning

Approximately 2.4 million patients need treatment for thyroid disease, including Graves disease and Hashimoto's disease, in Japan. However, only 450,000 of them are receiving treatment, and many patients with thyroid dysfunction remain largely overlooked. In this retrospective study, we aimed to screen patients with hyperthyroidism and hypothyroidism who would greatly benefit from prompt medical treatment, and examined routine laboratory finding data and machine learning algorithms to investigate whether such accurate and robust screening is possible to prevent overlooking and misdiagnosing thyroid dysfunction. We succeeded in developing a machine learning method to construct the classification model for detecting hyperthyroidism and hypothyroidism in patients using 11 routine laboratory tests. We collected electronic health record and medical checkup data from four hospitals in Japan. As a result of cross-validation and external evaluation, we achieved a high classification accuracy for the hyperthyroidism and hypothyroidism models.
Investigating the Anti-Oestrogenic Effects of Ephedrine and De novo Design of Oestrogen Modulating Molecules

Ephedrine is a thermogenic compound extracted from the shrub plant Ephedra sinica which has enjoyed worldwide use as the active ingredient in weight loss products prior to being banned from use by the FDA in 2004 following numerous adverse effect reports including cardiac arrest. A study published by Arbo et al. in 2008 hypothesised the potential antioestrogenic effects of ephedrine following a series of in vivo uterotrophic assays in immature female rats. Through this study we report the validation of this hypothesis by means of comparison of in silico ligand binding affinities of the isomers of ephedrine with that of 17-β-oestradiol. Furthermore the ephedrine scaffold was used as a pharmacophore for the de novo creation of high affinity novel ligands for the oestrogen receptor on the basis that the absence of the steroidal scaffold and the use of a hitherto unutilised pharmacophoric platform would mitigate many of the adverse effects associated with 17-βoestradiol analogs and also those of the Selective Oestrogen Receptor Modulators in contemporary use.
Exploring the effect of elevated storage temperature on wine composition

Temperature can play a significant role in the development of wine at many stages during its lifetime. Elevated temperature, however, poses a significant risk to the sensory attributes of wine and its resultant shelf-life. Wines often experience difficult environmental conditions during transport and storage, and this can directly impact on the colour, aroma and mouthfeel of the wine. Higher and/or fluctuating temperature can essentially accelerate the ageing process. Unfortunately, these changes often go unnoticed until the wine reaches the consumer. Numerous studies have investigated the impact of elevated temperature on wines, with noticeable effect, such as reduction of sulfur dioxide, colour development (especially browning of white wines) and changes in the profile of volatile compounds, being common. Unfortunately, most of these studies tend to have a narrow scope and tend to focus only on a limited number of wine types or on specific compounds. The chemistry changes involved in heat-affected red wines are generally more complex than they are in white wines, but it is arguable that white wines are more sensitive to the effect of heat and therefore require the same or a greater level of research consideration with respect to temperature effects. The focus of this review is to highlight the common effects that different wine types and styles can experience when subjected to elevated storage temperature that are considered to be beyond the limits that most winemakers and consumers would accept. This review will also summarise the fundamental chemical kinetics that play a significant role in wine development at elevated temperature.
Mechanism of vinyl acetate emulsion polymerization

The emulsion polymerization of vinyl acetate was investigated with the use of block copolymers of ethylene and propylene oxides (commercially known as Pluronic surfactants) as emulsifying agents. By electron microscopy, the average polymer particle size was determined as a function of conversion of monomer to polymer and as a function of the surfactant concentration. It was found that the number of polymer particles remained constant during the reaction. The polymer surface area per unit volume of completely polymerized emulsion was proportional to the surfactant concentration. In contrast with styrene polymerization, the number of particles varied with the cube of the emulsifier concentration, and the number of particles per unit of surfactant was much less than the number that would have been expected with styrene. It was concluded that the results were consistent with polymerization theory. An expression giving the number of polymer particles produced in the reactions proved to be much simpler than the accepted equation used in the case of water insoluble monomers such as styrene. This simplicity arises from the partial water solubility of vinyl acetate, which enables the monomer to diffuse completely into the polymer particles very early in the reaction. The variation of latex viscosity with polymer particle size was also investigated. At constant solids concentration, the logarithm of the viscosity was proportional to the polymer surface area per unit of latex.
Recent advances in the recycling of homogeneous catalysts using membrane separation

Membrane filtration is an attractive approach for soluble catalyst recycling. Applications of nanofiltration have demonstrated their great potential as a method for process intensification in enzyme, organo-, and homogeneous catalysis, both in laboratory practice and on an industrial scale. Selected, recent advances in catalyst recovery by means of membrane filtration are discussed, together with their implication for future developments. These examples demonstrate that this strategy is applicable in many different transformations.
Controlled synthesis and properties of palladium nanoparticles

In our research, the preparation processes of Pd nanoparticles (Pd NPs) with different methods by adding a certain amount of silver nitrate, iron chloride or sodium iodide are presented in order to control their size and morphology. Various sizes and shapes of Pd NPs are observed by alcohol reduction. The results show the size and morphology control of Pd NPs with chemical reductions of Pd salts by ethanol and ethylene glycol (EG) that have very different reduction processes. The modified polyol method with the gradual addition of Pd and polyvinylpyrollidone precursors in EG at 160°C has led to control their size and morphology in the 10 nm range using 0.02 M AgNO3. It is observed that the Pd nanorod is also formed. The main factors that will control the shapes of Pd NPs have been presented to explain their growth and formation mechanisms in a control process.
Tissue distribution of Curcumol in rats after intravenous injection of zedoary turmeric oil fat emulsion

Aim To determine the concentration of curcumol in different tissues and investigate the tissue distribution of curcumol in rats after intravenous injection of zedoary turmeric oil fat emulsion. Methods Wister rats were intravenously injected with a dose of 10.0 mg·kg -1 zedoary turmeric oil fat emulsions. The tissue samples (heart, liver, lung, kidney and brain) were collected at scheduled times. Curcumol was extracted with chloroform/isopropyl alcohol (95:5, v/v) from tissue homogenates and separated on a C18 column with a mobile phase of acetonitrile (0.3M ammonium acetate containing 0.1% formic acid)/water (0.1% formic acid) (95:5, v/v). Detection was carried out by positive elevtrospray ionization (ESI) in multiple reactions monitoring (MRM) mode of 254.3→219.4 (m/z) for curcumol and 220.3→128.1 (m/z) for ornidazole (I.S.), respectively. Results Curcumol was distributed to liver, kidney, brain, heart, lung 10 min after intravenous injection and obtained the maximum concentration of 108.85±65.91, 105.19±42.92, 92.38±17.63, 82.96±38.06, 10.01±2.97 µg·g -1 , respectively. Conclusions The method was successfully applied in the tissue distribution study. The results showed that the curcumol was markedly decreased after 0.5 h and almost eliminated at 5 h after administration.
Conformational specific heat of polymers

A method to evaluate the conformational specific heat of polymers is proposed. The change in Cv at Tg is identified with the conformational specific heat and calculated from thermodynamic data on 14 polymers. The equation for specific heat of a two‐state model yields the energy difference between the two states, e, from the experimental data for ΔCv(Tg). The basic premise of this work is also shown to be derivable from the Gibbs‐DiMarzio theory of glass formation. Derived values of e are in agreement with results calculated from Tg data and the dependence of Tg upon molecular weight using G‐D theory.
XRD total pattern fitting applied to study of microstructure of TiO2 films

New XRD total pattern fitting software MSTRUCT was used to study the microstructure of magnetron-deposited TiO2 thin films. MSTRUCT is an extension of the FOX program for structure determination from powder diffraction data. MSTRUCT makes corrections for refraction and absorption, residual stress, and preferred orientation that are necessary for thin-film analysis using the parallel-beam geometry and an asymmetric detector scan with small angles of incidence. The program also corrects for crystallite size broadening in terms of log-normal distribution, two models of strain (phenomenological and dislocation models), as well as the influence of stacking faults in the most common cubic and hexagonal structures. The microstructure results obtained by this study show that during crystallization of the amorphous TiO2 films, tensile stresses were generated resulting in anisotropic shifts of diffraction peaks. This was confirmed by in situ crystallization and direct stress measurements. The consideration of the stress effect in terms of the weighted Reuss-Voigt model improved the fits significantly. The stresses were found to depend systematically on the TiO2 film thickness, and their values determined by total pattern fitting agree well with the values measured directly by XRD stress analysis.
Computational Study on the Effects of Substituents and Functional Groups in the Isomerization of 1‐ and 2‐Substituted Propenes, Acetaldimines, and Aldehydes

We have performed ab initio molecular orbital calculations on 1- and 2-substituted propenes, acetaldimines, and aldehydes — H3CC(X)=Y and XCH2CH=Y (Y = CH2, NH, O; X = H, CH3, NH2, OH, F) — to investigate the effects that substituents and functional groups have on their isoelectronic (except X = H) tautomerism. Structures for all stationary points (keto forms, enol forms, and transitions states) were optimized at the HF/6−31G**, MP2(full)/6−31G*, and B3LYP/6−31G** levels of theory and were characterized by frequency calculations. We performed intrinsic reaction coordinate (IRC) calculations at the HF/6−31G** level of theory to connect the transition structures with their local minima along the reaction path. In the transition structures, the migrating H4 atom is slightly out of plane, with a dihedral angle H4−C2−C1−Y3 (d4) of < 12°. In the keto−enol and imine−enamine series, the keto forms are thermodynamically more stable than their counterparts by ca. 30 kcal·mol−1 regardless of the site of substitution. In the 2-substituted propene (Y = CH2) series, the enol forms are lower in energy than the keto forms by ca. 3−10 kcal·mol−1. There is a very good linear correlation between the relative energies and the electronegativity (Pauling scale) of the non-hydrogen atom in Y of the functional group C=Y; the coefficient of the linear regression ranges from 0.98624 to 0.99963 for the six tautomeric series at the G2 level of theory. We explain the effects that the substituents have on the relative energies in terms of the changes in bond dissociation energies (by means of isodesmic reactions) and the dispersion of the charge through resonance effects (NBO analysis). These “enolization” processes all have rather high activation energies of 56−78 kcal·mol−1 at the G2 levels of theory. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
PageRuler™ Prestained Protein Ladder Plus

Description PageRulerTM Prestained Protein Ladders (PageRulerTM Prestained Protein Ladder Plus and PageRulerTM Prestained Protein Ladder) are designed for monitoring protein separation during SDS-polyacrylamide gel electrophoresis, verification of Western transfer efficiency and approximate sizing of proteins (1-3). The PageRulerTM Prestained Protein Ladder Plus contains two orange reference bands for easy orientation. It is a mixture of 9 Home Contacts Order Catalog Support
SWAP Version 3.2. Theory description and user manual

SWAP 3.2 simulates transport of water, solutes and heat in the vadose zone. It describes a domain from the top of canopy into the groundwater which may be in interaction with a surface water system. The program has been developed by Alterra and Wageningen University, and is designed to simulate transport processes at field scale and during whole growing seasons. This is a new release with special emphasis on numerical stability, macro pore flow, and options for detailed meteorological input and linkage to other models. This manual describes the theoretical background, model use, input requirements and output tables.
Experimental Study of Aerodynamic Sound from a Rotating Disk

The broad‐band sound generated aero‐dynamically by a smooth disk rotating in its own plane was measured. The low‐frequency part of the spectrum was caused by vortex formation at the disk edge, and appeared acoustically as a point pressure dipole on the disk axes and aligned with the axis. The high‐frequency part of the spectrum was caused by the interaction, with the disk edge, of the boundary layers on both faces and on the periphery. The location of the effective source moved closer to the edge with increasing frequency, and was pressure dipole in nature. Addition of a sandpaper ring to both faces caused generation of high‐frequency sound at the point of roughness as predicted by [J. Acoust. Soc. Am 37, 516–522 (1965)]. Acoustically, the source appeared as dipoles whose axes were about 70° to the axis. Edge and roughness caused sounds are exceptions to the concept that surface dipoles account only for reflection of quadrupole sources [Powell, J. Acoust. Soc. Am. 32, 982–990 (1960)].
Sampling and Characterization of Sub-Micrometer High-Temperature Particles Present in the Product Gas from a Circulating Fluidized-Bed Biomass Gasifier

The removal of particulate fine fractions by a proper high-temperature cleaning device is a very important issue in the development of the biorefinery concept. Therefore, in this investigation, particles from a 100 kWth steam–O2 blown circulating fluidized-bed (CFB) gasifier were sampled and characterized. The sampling was performed with a specially designed heated dilution probe downstream of a high-temperature candle filter element. The dilution probe was followed by a bed of activated carbon to separate the condensed phase from the particle phase by reducing the supersaturation of the volatile material. Parallel measurements were performed by a scanning mobility particle sizer (SMPS) and sample collection by a cascade impactor assembly to obtain information about the particle size distribution and elemental analysis, respectively. The measured particle mass was found to be dominated by coarse particles from bed material together with high amounts of potassium, which is thought to have penetrated throug.
Three-dimensional graphene materials: preparation, structures and application in supercapacitors

Three-dimensional (3D) graphene materials (3DGMs) are of great importance due to their unique properties and practical applications. A number of 3DGMs with novel structures have been developed in recent years. This review presents the current progress of 3DGMs. After introducing the preparation strategies of 3DGMs, we summarize the reported 3DGMs based on their different structures, and then focus on the description of their preparation methods, properties and applications. Lastly, the applications of 3D graphene-based materials in supercapacitors are described.
Health Effects of Ambient Particulate Matter—Biological Mechanisms and Inflammatory Responses to In Vitro and In Vivo Particle Exposures

In this article, we review and analyze different modes of exposure to ultrafine particles in order to assess particle-induced inflammatory responses and the underlying mechanisms in vitro and in vivo. Based on results from monocytic cells cultured under submerged conditions, we discuss (1) the impact of particle properties such as surface area and oxidative potential on lipid metabolism as a highly sensitive regulatory pathway and (2) the interference of diesel exhaust particles with toll-like receptor-mediated inflammatory responses. Furthermore, new developments of air–liquid interface exposure used as an alternative approach to simulate cell particle interactions are presented. In addition to the in vitro approaches, animal exposure studies are described that apply selected mouse models to elucidate potential allergic and inflammatory pulmonary responses and mast-cell-related mechanisms after particle exposure. Long-term inhalation of ultrafine particles might lead to irreversible changes in lung structure and function. Clinical studies addressing the characteristics of inflammatory airway cells are a promising approach to understand underlying pathophysiological mechanisms in chronic obstructive pulmonary disease. Finally, a potential outcome of human particle exposure is chronic cough in children. Here, discrimination between asthmatic and nonasthmatic cough by means of immunological parameters appears to be an important step toward improving diagnosis and therapy.
A Simple, Highly Sensitive, and Label-Free Impedimetric Immunosensor for Detection of Microcystin-LR in Water

A simple, highly sensitive, and label-free impedimetric immunosensor for detection of microcystin-LR (MC-LR) has been developed by immobilizing anti-microcystin-LR on gold nanoparticle/L-cysteine coated electrode. Under optimal conditions, MC-LR could be determined with a detection limit of 1.82 × 10−2 ng mL−1 and a linearity between 0.05 and 300.0 ng mL−1. Moreover, the immunosensor exhibited long-term stability, and good reproducibility of the signal could be obtained up to 42 times with an R.S. D. of 3.58%. The average recovery rate was in the range of 96.8 ∼ 112.5%. In addition, the whole detection time was only 15 min.