Miracle-dz/UniFAR-FTUs huggingface dataset:
Nanodiamond Decorated with Silver Nanoparticles as a Sensitive Film Modifier in a Jeweled Electrochemical Sensor: Application to Voltammetric Determination of Thioridazine

Nanodiamondgraphite (NDG) decorated with Ag nanoparticles (AgNPs-NDG) was prepared and used to construct a novel sensitive sensor for the voltammetric determination of thioridazine (TR). The results indicate a remarkable increase in the oxidation peak currents together with a negative shift in the oxidation peak potentials, in comparison to the bare pyrolytic graphite electrode. Remarkable enhancement in microscopic area of the electrode along with strong adsorption of TR on the surface of the modified electrode resulted in a considerable increase in the peak current of TR. The surface morphology and the nature of the composite film deposited on PGE were characterized by scanning electron microscopy, atomic force microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Experimental variables, such as the deposited amount of the modifier suspension, pH of the supporting electrolyte, the accumulation potential and time are optimized by monitoring the CV responses of TR. Under the optimal conditions, the modified electrode showed a wide linear response to the concentration of TR in the range of 0.08–100 µM with a detection limit of 0.01 µM. The prepared modified electrode showed several advantages: simple preparation method, high stability and uniformity in the composite film, high sensitivity, long-term stability and remarkable voltammetric reproducibility in response to TR. The modified electrode can be successfully applied for accurate determination of trace amounts of TR in pharmaceutical and clinical preparations.
Enhanced Electrochromism with Rapid Growth Layer‐by‐Layer Assembly of Polyelectrolyte Complexes

In this work, a facile method to deposit fast growing electrochromic multilayer films with enhanced electrochemical properties using layer‐by‐layer (LbL) self‐assembly of complex polyelectrolyte is demonstrated. Two linear polymers, poly(acrylic acid) (PAA) and polyethylenimine (PEI), are used to formulate stable complexes under specific pH to prepare polyaniline (PANI)/PAA‐PEI multilayer films via LbL deposition. By introducing polymeric complexes as building blocks, [PANI/PAA‐PEI]n films grow much faster compared with [PANI/PAA]n films, which are deposited under the same condition. Unlike the compact [PANI/PAA]n films, [PANI/PAA‐PEI]n films exhibit porous structure that is beneficial to the electrochemical process and leads to improved electrochromic properties. An enhanced optical modulation of 30% is achieved with [PANI/PAA‐PEI]30 films at 630 nm compared with the lower optical modulation of 11% measured from [PANI/PAA]30 films. The switching time of [PANI/PAA‐PEI]30 films is only half of that of [PANI/PAA]30 films, which indicates a faster redox process. Utilizing polyelectrolyte complexes as building blocks is a promising approach to prepare fast growing LbL films for high performance electrochemical device applications.
Rhenium(II) nitrosyl complexes: synthesis, characterization, DFT calculations and DNA nuclease activity

The rhenium(II) dinitrosyl and mononitrosyl complexes, i.e. [Re(NO)2(CN)4]·(Phen)2·2H2O (1) and PhenH[Re(NO)(CN)4(H2O)]·(Phen)·3H2O (2) have been isolated and characterized. The X-ray crystal structure of 2 reveals that Re(II) is octahedrally coordinated with one nitrosyl, four cyanides, and one water, with one phenanthroline protonated to compensate the charge of the Re(II) center. The crystal structure shows chemically significant non-covalent interactions like hydrogen bonding involving the uncoordinated water and π–π interactions between phenanthrolinium and phen. The structures of both complexes have been optimized by DFT. Absorption and emission spectral studies and viscosity measurements indicate that both 1 and 2 interact with calf thymus DNA through partial intercalation of DNA bases. The intrinsic-binding constants, obtained from UV–vis spectroscopic studies, are 1.2 × 104 and 7.2 × 104 M−1 for 1 and 2, respectively. Both 1 and 2 are capable of inducing cleavage of plasmid DNA in the presence of H2O2 to form the supercoiled form to nicked circular form. The spectroscopic results of DNA binding are supported by molecular docking studies. Graphical Abstract The synthesis of mono and dinitrosyl rhenium(II) complexes were done. Mono nitrosyl complex was characterized by single crystal X-ray diffraction, which was further supported by DFT and Hirshfeld surface analysis. DNA binding and nuclease activity of both complexes were performed.
Residual stresses and fracture properties of magnetron sputtered Ti films on Si microelements

The influence of different deposition parameters on the microstructure, the residual stress, and the mechanical properties of thin Ti films has been investigated. Ti films were deposited onto Si (001) wafers with a native oxide layer, held at a temperature <250 °C, by dc magnetron sputtering. The film thickness was 1 μm. The microstructure of the films, as determined by x‐ray diffraction (XRD) and transmission electron microscopy (TEM), was varied by changing the Ar sputtering pressure PAr between 0.8 and 8.3 mTorr, and by applying a negative substrate bias Vs between 0 and 300 V. The residual stresses in the films were determined by both a beam curvature technique and the XRD sin2 ψ method. For Vs=0, the residual stress in the films changed abruptly from tensile to compressive as PAr decreased below 2.5 mTorr. A maximum tensile stress of 0.4 GPa was obtained at 3 mTorr. The compressive stress reached at PAr=0.8 mTorr was 0.4 GPa. TEM showed accompanying structural changes from columnar structure with a h.
Influence of Molecular and Supramolecular Structure on the Gas-Liquid Interfacial Reactivity of Hydrocarbon Liquids with O(3P) Atoms

We have investigated the interfacial reactivity of gas-phase O(3P) atoms with a representative range of long-chain liquid hydrocarbons. These consisted of two branched molecules, squalane (C30H62, 2,6,10,15,19,23-hexamethyltetracosane) and pristane (C19H40, 2,6,10,14-tetramethylpentadecane), and three linear ones, n-docosane (C22H46), n-tetracosane (C24H50) and n-octacosane (C28H58). This represents the first systematic investigation of reactions of this type for molecules other than squalane. The O(3P) atoms were generated by 355-nm laser photolysis of a low pressure of NO2 above the liquid surface. The nascent gas-phase OH radical products were detected by laser-induced fluorescence (LIF). Measurements for the linear hydrocarbons were constrained by their vapor pressures to single temperatures slightly (∼1 K) above their respective melting points. Pristane was studied at the lowest temperature practically achievable. Squalane was compared as a reference at the full set of temperatures. Appearance profil.
Growth and characterization of semiorganic NLO crystals of LAHClBr

Single crystals of non‐linear optical (NLO) LAHClBr were grown by slow evaporation technique from its aqueous solution. Good optical quality crystals having dimensions up to 12 × 9 × 7 mm3 were obtained. The lattice parameters and morphology for the grown crystals were determined using single crystal XRD. The crystals were characterized by FT‐Raman, optical absorption, thermal (DTA and TGA) and dielectric studies. LAHClBr was found to be thermally stable up to 124.3°C. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
THE EFFECTS ON PORK STORAGE LIFE OF OXYGEN CONTAMINATION IN NOMINALLY ANOXIC PACKAGINGS1

The microbial floras that developed on controlled atmosphere [CA: oxygen (O2) free carbon dioxide (CO2) contained in gas impermeable pouches], modified atmospheres (MA: O2 free CO2 contaminated with specific amounts of air contained in gas impermeable pouches), and vacuum packages (VP: evacuated pouches of low gas permeability in atmospheres containing specific amounts of O2) stored at −1.5°C were composed of lactobacilli and enterobacteria. Microbial spoilage was manifested as putrid odors and flavors starting at 6 weeks in VP and at 9 weeks in MA. Flora development was not affected by varied exposure to O2, and varied exposure to O2 contamination or ingress degraded the appearance of pale, soft, exudative (PSE) meat to unacceptable levels. Microbial spoilage rendered the appearance of all samples unacceptable. Oxygen ingress into VP did not affect pork flavor profiles, but O2 contamination of MA intensified an “off” aromatic. Pork flavor deteriorated progressively with prolonged storage, but only the overall flavor perception of VP cuts was adversely affected.
Structure and binding of Lennard‐Jones clusters: 13≤N≤147

An efficient lattice based search and optimization procedure has been developed and used with various assumed pair potentials to find minimal energy structures on an icosahedrally derived lattice. These were then taken as initial configurations and allowed to relax freely under the Lennard‐Jones pair potential to the adjacent energy minimum. The initial configurations and relaxed energies of the most tightly bound structures found for each N are presented for the range 13≤N≤147. While the energies obtained are rigorously only upper bounds to the absolute minimal energy of an N‐atom Lennard‐Jones cluster, they appear to be less than or equal to that of any other structures proposed previously. They are believed to be the most tightly bound structures of the multilayer icosahedral type, and to be reasonable candidates for the absolutely minimal energy structures in this size range. The most tightly bound configuration found was the truncated icosahedral structure at N=135.
Flow Injection Chemiluminescence Determination of Retinol and α-Tocopherol in Blood Serum and Pharmaceuticals

A simple and sensitive flow-injection method is reported for the determination of retinol and α-tocopherol in human blood serum and pharmaceuticals. The method is based on the reduction of vanadium(V) by retinol and α-tocopherol and subsequent reaction of reduced vanadium with luminol to generate chemiluminescence signal. The optimized conditions allow a linear calibration range of 30–2850 µg L−1 and 5–4300 µg L−1 for retinol and α-tocopherol, with relative standard deviations of 1.2–4.6% and 1.5–5.6%, respectively. The detection limits for retinol and α-tocopherol, defined as three times the standard deviation of measured blanks were 23 µg L−1 and 2.15 µg L−1, respectively. The proposed method allowed up to 20 determinations h−1. The tolerance amount of foreign ions/compounds on the determination of retinol and α-tocopherol was also examined. The method was applied to the determination of retinol and α-tocopherol in human blood serum and pharmaceutical samples using hexane extraction with recoveries in the range of 92 ± 2 to 96 ± 1%, and the results obtained were compared with HPLC reference method.
Arsenic removal by coagulation using ferric chloride and chitosan from water

Aims: In this study, the effect of arsenite and arsenate removal in synthetic water by coagulation using ferric chloride (FeCl 3 ) as coagulant and chitosan as coagulant aid were investigated. b>Materials and Methods: A conventional jar test apparatus was used to evaluate the coagulation process. The effects of different conditions of pH (5.5-9), coagulant doses of FeCl 3 0-60 mg/l), Arsenic speciation (As (V) and As (III)), Chitosan as coagulant aid, and initial arsenic concentrations (0.2-2 mg/l) to Arsenic removal was investigated by considering the residual arsenic and iron after coagulation. Results: The finding showed that the optimum pH for FeCl 3 as a coagulant to As (V) and As (III) removal was 7. As (V) removal efficiency of 90% or higher by FeCl 3 alone were achieved for initial As (V) concentration 0.2-2 mg/l at optimum dosages (15-30 mg/l). In contrast with As (V) removal, about 60% of the As (III) were removed in comparable conditions. The optimal dosage of chitosan was determined to be 0.5 mg/l. When chitosan (0.5 mg/l) was used as coagulant aid with FeCl 3 , the efficiency removal was enhanced almost to 100% and 80% for As (V) and As (III) removal, respectively. The optimum dosage of FeCl 3 was reduced, especially at low initial concentration of arsenic. Conclusions: Chitosan as natural coagulant aid improved arsenic removal efficiency by coagulation process using FeCl 3 . This method can be used for regions with drinking water contaminated with initial arsenic concentration less than 1 000 μg/l.
A statistical theory of globular polyelectrolyte complexes

A microscopic statistical theory of a symmetrical polyelectrolyte complex (PEC) is developed. PEC is shown to form a polymer globule. The equilibrium density of PEC, the width of a PEC surface layer, and the surface tension of PEC are calculated as a function of salt concentration. Description of PEC as a polymer globule enables us to simplify theoretical treatment of the phenomenon of phase separation in poly- electrolyte solutions (complex coacervation). Numerous experimental facts concerning complex coacerva- tion are easily explained within this approach. Complex coacervation is considered as precipitation of polymer globules owing to minimization of surface energy. The theory is based on the Lifshitz-Grosberg theory of polymer globules and our previous work concerning the equation of state of polyelectrolyte solutions. It is limited to the case of polyions with the low linear density of charge, which is most clear from the theoretical point of view and is also of practical and, in particular, of biological interest.
Synthesis of a doubly thermo-responsive schizophrenic diblock copolymer based on poly[N-(4-vinylbenzyl)-N,N-diethylamine] and its temperature-sensitive flip-flop micellization

Synthesis of a doubly thermo-responsive schizophrenic diblock copolymer, poly(tert-butyl methacrylate)-block-poly[N-(4-vinylbenzyl)-N,N-diethylamine] (PtBMA-b-PVEA), by reversible addition–fragmentation chain transfer (RAFT) polymerization and its temperature-sensitive flip-flop micellization are discussed. By employing 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid as the RAFT agent, the schizophrenic PtBMA-b-PVEA diblock copolymers with different block lengths were prepared. The poly(tert-butyl methacrylate) (PtBMA) block exhibits insoluble-to-soluble phase transition at the upper critical solution temperature (UCST) and the poly[N-(4-vinylbenzyl)-N,N-diethylamine] (PVEA) block exhibits soluble-to-insoluble phase transition at the lower critical solution temperature (LCST) in methanol, respectively. At temperatures below the UCST of the PtBMA block, PtBMA@PVEA micelles containing a PtBMA core and a PVEA corona are formed in methanol. At temperatures above the UCST of the PtBMA block while below the LCST of the PVEA block, PtBMA-b-PVEA is molecularly soluble in methanol. At temperatures above the LCST of the PVEA block, inverse PVEA@PtBMA micelles containing a PVEA core and a PtBMA corona are formed. The polymerization degree of the PtBMA block or the PVEA block affecting the UCST/LCST of the schizophrenic diblock copolymer and the size of the PtBMA@PVEA or PVEA@PtBMA micelles is investigated.
Aging-Induced Self-Assembly of Zn/ZnO Treelike Nanostructures from Nanoparticles and Enhanced Visible Emission

The self-assembly formation of Zn/ZnO treelike nanostructures was achieved by simply aging the corresponding stable colloidal solution, produced by laser ablation in liquid, at room temperature without any further heating treatment. The self-assembled treelike structures consist of oriented attached nanoparticles with small misorientations and greatly improved crystallinity and exhibit significantly enhanced visible emission with two peaks in the blue and green regions, accompanying the decrease of the plasma resonance absorption of the core-part Zn nanocrystal. The self-assembly mechanism was attributed to the imperfect oriented attachment. The small misorientations among the attached nanoparticles were observed, and their accumulation guided the self-assembly formation of the multibranched nanostructures. As compensation for the insufficient driving force, adequate colloid stability and aging time were crucial for the accomplishment of the self-assembly process. This work could deepen the understanding .
Eliminations from (E)-2,4-Dinitrobenzaldehyde O-Aryloximes Promoted by R3N/R3NH + in 70 mol % MeCN(aq). Effects of Leaving Group and Base-Solvent on the Nitrile-Forming Transition-State

Elimination reactions of (E)-2,4-(NO2)2C6H2CH=NOC6H3-2-X-4-NO2 (1a-e) promoted by R3N/R3NH + in 70 mol % MeCN(aq) have been studied kinetically. The reactions are second-order and exhibit Bronsted β = 0.800. 84 and |βlg| = 0.39-0.42, respectively. For all leaving groups and bases employed in this study, the β and |βlg| values remained almost the same. The results can be described by a negligible pxy interaction coefficient, pxy = ∂β/pKlg = ∂βlg/pKBH ≈ 0, which describes the interaction between the base catalyst and the leaving group. The negligible pxy interaction coefficient is consistent with the (E1cb)irr mechanism. Change of the base-solvent system from R3N/MeCN to R3N/R3NH + -70 mol % MeCN(aq) changed the reaction mechanism from E2 to (E1cb)irr. Noteworthy was the relative insensitivity of the transition state structure to the reaction mechanism change.
Biodegradation of aromatic hydrocarbons by aquifer microorganisms under denitrifying conditions

A series of laboratory tests were conducted to evaluate whether denitrification would be a suitable alternative for biorestoration of an aquifer contaminated with JP-4 jet fuel. Microcosms were prepared from both uncontaminated and contaminated aquifer material from the site, in an anaerobic glovebox, amended with nitrate, nutrients, and aromatic hydrocarbons, and incubated under a nitrogen atmosphere at 12C. With uncontaminated core material, there was no observable lag period prior to removal of toluene whereas 30 days was required before biodegradation commenced for xylenes, ethylbenzene, and 1,2,4-trimethylbenzene. An identical test with contaminated aquifer material exhibited not only much longer lag periods but decreased rates of biodegradation; benzene, ethylbenzene, and o-xylene were not significantly degraded within the 6-month time period even though active denitrification occurred at this time. First-order biodegradation rate constants ranged from 0.016 to 0.38 day{sup {minus}1} for uncontaminated core material and from 0.022 to 0.067 day{sup {minus}1} for contaminated core material. Tests with individual compounds in uncontaminated core indicated that benzene and m-xylene inhibited the basal rate of denitrification. These data demonstrate that several aromatic compounds can be degraded under denitrifying conditions, but rates of biodegradation may be lower in material contaminated with JP-4 jet fuel.
The crystal structure of monoclinic metaboric acid

All atoms are in general positions. Least-square refinements based on 844 reflections gave R = 0.06. The position coordinates have been determined to a precision of 0.006/~ for boron, 0"003/~ for oxygen and 0.07 A for hydrogen. The structure consists of endless zigzag chains of composition [BaO4(OH)(OH2)]o o directed along the b-axis with hydrogen bonds between the chains. Two thirds of the boron atoms are in triangular and one third in tetrahedral configuration. The water oxygen is an unshared corner of a BO 4 tetrahedron, the hydroxyl oxygen an unshared corner of a BO a triangle, while each of the other oxygen atoms is bonded to two boron atoms.
Results of Ab Initio Calculations on Formamide

Ab initio calculations on formamide, HCONH2, have been carried out for 44 nuclear configurations with a (s, p) = (11, 7) basis set for C, O, and N and a (s, p) = (5, 3) set for the hydrogens, and for three nuclear configurations with a (s, p, d) = (11, 7, 1) basis set for C, O, and N and a (s, p) = (5, 3) set for the hydrogens. Primarily, a structure from microwave work was assumed. Within the range of experimental errors of the C=O, the C–N, and the N–H distances the molecular energy was shown to pass through minima. The calculated dipole moment and the barrier to internal rotation around the C, N bond are in satisfactory agreement with experiments. Also, the changes of molecular geometry occurring if HCONH2 is twisted around its amide CN bond are consistent with qualitative expectations. The calculated barrier to NH2 inversion in HCONH2 of 30–40 cm−1 is too low by a factor of ∼ 10.
Second‐harmonic generation of poled BaTiO3 thin films

Second‐harmonic generation of 1.064 μm incident light was measured on BaTiO3 thin films prepared by metalorganic chemical vapor deposition. Upon corona poling of the film, the second‐harmonic signal was significantly enhanced. The second‐order nonlinear optical susceptibility, d, of the poled film reaches ∼7.5 times that of the quartz. The enhanced second‐harmonic generation shows a very slow decay at room temperature.
Influence of Carbon Dioxide on the Characteristics of a Limiting Current Oxygen Sensor

The influences of CO2 on the characteristics of a limiting current oxygen sensor in CO2- O2-N2 atmospheres were investigated. The studies indicated that the I-V curves appeared two-stage current plateau at (0~2) V operation voltage in CO2-O2-N2 atmospheres with CO2 concentration changed from 2.03% up to 12.18% and oxygen concentration remained at 5%、7.5%、10%, respectively. The first saturated current IL1 appeared in the voltage range of 0.8～1.4 V while the second saturated current IL2 appeared in 1.65～1.82 V, respectively. The difference between the two current platforms (IL2-IL1) and (-ln(1-XCO2)) showed a good linear relationship. And the oxygen sensor’s up-response time and down-response time to CO2 were both within 30s. The concentration of CO2 can be detected at a high working voltage.