Observation of bulk like magnetic ordering below the blocking temperature in nanosized zinc ferrite

We investigated the magnetic behavior of nanosized zinc ferrite with the help of vibrating sample magnetometry and in-field Mössbauer spectroscopy. The nanoparticles of zinc ferrite with crystallite size ranging from 10 to 62 nm were synthesized by a nitrate method. The structure and phase were determined with the help of X-ray diffraction. Attributes of cation inversion were found with the calculated values of lattice parameter. The saturation magnetization decreases with the increase in crystallite size at room temperature, while these values are almost the same at 10 K for all the samples except the one with crystallite size of 10 nm. The thermal magnetization measurement shows a decrease in blocking temperature with increase in particle size for these samples. The synthesized samples exhibit the presence of antiferromagnetic ordering below the blocking temperature as investigated by in-field Mössbauer spectroscopy.     

Methanol diffusion rates through the anode diffusion layer in direct methanol fuel cells from limiting current measurements

Metal foams may be used in direct methanol fuel cells to feed reactants to the catalyst layer and to collect current from the resulting electrochemical reaction. Although the mass transfer from the metal foam to the underlying gas diffusion layer (GDL) is diffusion-dominated, it is found that at a fixed methanol concentration, the limiting current density increases with increasing methanol flow rates. This unexpected result is attributed to the more efficient removal of product CO₂ from the GDL. A methodology is developed to estimate the effective diffusion coefficient of methanol in the anode diffusion layer from limiting current density measurements, and to extract the fraction of GDL volume occupied by CO₂.     

Minimal formulation of joint motion for biomechanisms

Biomechanical systems share many properties with mechanically engineered systems, and researchers have successfully employed mechanical engineering simulation software to investigate the mechanical behavior of diverse biological mechanisms, ranging from biomolecules to human joints. Unlike their man-made counterparts, however, biomechanisms rarely exhibit the simple, uncoupled, pure-axial motion that is engineered into mechanical joints such as sliders, pins, and ball-and-socket joints. Current mechanical modeling software based on internal-coordinate multibody dynamics can formulate engineered joints directly in minimal coordinates, but requires additional coordinates restricted by constraints to model more complex motions. This approach can be inefficient, inaccurate, and difficult for biomechanists to customize. Since complex motion is the rule rather than the exception in biomechanisms, the benefits of minimal coordinate modeling are not fully realized in biomedical research. Here we introduce a practical implementation for empirically-defined internal-coordinate joints, which we call "mobilizers." A mobilizer encapsulates the observations, measurement frame, and modeling requirements into a hinge specification of the permissible-motion manifold for a minimal set of internal coordinates. Mobilizers support nonlinear mappings that are mathematically equivalent to constraint manifolds but have the advantages of fewer coordinates, no constraints, and exact representation of the biomechanical motion-space-the benefits long enjoyed for internal-coordinate models of mechanical joints. Hinge matrices within the mobilizer are easily specified by user-supplied functions, and provide a direct means of mapping permissible motion derived from empirical data. We present computational results showing substantial performance and accuracy gains for mobilizers versus equivalent joints implemented with constraints. Examples of mobilizers for joints from human biomechanics and molecular dynamics are given. All methods and examples were implemented in Simbody?-an open source multibody-dynamics solver available at https://Simtk.org.     

Ethanol production in a membrane bioreactor

Pilot plant trials were conducted in a corn wet mill with a 7000-L membrane recycle bioreactor (MRB) that integrated ceramic microfiltration membranes in a semi-closed loop configuration with a stirred-tank reactor. Residence times of 7.5–10 h with ethanol outputs of 10–11.5% (v/v) were obtained when the cell concentration was 60–100 g/L drywt of yeast, equivalent to about 10⁹−10¹⁰ cells/mL. The performance of the membrane was dependent on the startup mode and pressure management techniques. A steady flux of 70 L/(m²·h) could be maintained for several days before cleaning was necessary. The benefits of the MRB include better productivity; a clear productstream containing no particulates or yeast cells, which should improve subsequent stripping and distillation operations; and substantially reduced stillage handling. The capital cost of the MRB is $21–$34/(m³·yr) ($0.08–$0.13/[gal·yr]) of ethanol capacity. Operating cost, including depreciation, energy, membrane replacement, maintenance, labor, and cleaning, is $4.5–9/m³ ($0.017–$0.034/gal) of ethanol.     

Five coordinate complexes of N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamide with copper Crystal and molecular structures of dichloro(N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamido)copper(II) and chloro(perchlorato)(N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamido)copper(II)

The title compound N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamide (DEAP) forms a 1:1 complex with anhydrous CuCl₂, [Cu(DEAP)Cl₂], (1) which was crystallized from EtOH solution in the monoclinic space group P2_{1/ n} with cell constant, a = 10.024(1); b = 13.122(1); c = 14.404(1) Å β = 101.31(1)° V = 1857.8(3) ų and Z = 4. The chloro-perchlorato complex, [Cu(DEAP)Cl(ClO₄)], (2) obtained in near quantitative yield by reacting (1) with an excess of NaClO₄ in EtOH, crystallized in the monoclinic space group P2_{1/ n} with cell constants, a = 7.965(1); b = 25.827(2); c = 10.046(1) Å β = 98.81(1)° V = 2042.2(4) ų and Z = 4. Both (1) and (2) contain 5-coordinated copper linked to DEAP through O～N～O donor set of atoms with covalently bonded chlorine atoms in (1) and chlorine and perchlorate groups in (2). The coordination geometry is intermediate between square pyramidal and trigonal bipyramidal, and is probably best described as a trigonally distorted rectangular pyramid.     

Matching tyre size to weight, speed and power available for maximising pulling ability of agricultural tractors

The desirable weight-to-axle power ratio for agricultural tractors is determined by the necessity for the optimum utilisation of the available axle power to produce the required drawbar pull at a preselected slip. For a vehicle designed to operate in a given speed range, the weight-to-axle power ratio should be within a particular limit, so that a specific level of conversion efficiency can be maintained. In this paper attempts have been made to select suitable tyres for Indian two-wheel drive tractors operating in sandy clay loam soils on the basis of weight-to-power utiisation and maximum pull-to-optimum weight ratio at a preselected slip using the developed traction prediction equations. A comparison has also been made between the desired and actual weight on a single traction wheel and suitable tyre and tyre normally fitted in Indian two wheel drive tractors up to 35 kW.     

Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state

The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Here, we demonstrate that out-of-plane torsional deformation and vibrational excitation of stretching motions in the electronic ground state modulate the charge-density distribution in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change, visualised by transient absorption spectroscopy with a mid-infrared pump and a visible probe, is mechanistically resolved by ab initio molecular dynamics simulations. Mapping the potential energy landscape attributes the observed charge-coupled coherent nuclear motions to the population of the initial segment of a double-bond isomerization channel, also seen in biological molecules. Our results illustrate the pivotal role of pre-twisted molecular geometries in enhancing the transfer of vibrational energy to specific molecular modes, prior to thermal redistribution. This motivates the search for synthetic strategies towards achieving potentially new infrared-mediated chemistry.

Channelling vibrational excitation energy to achieve ground-state charge-transfer (CT)-assisted isomerization in a donor-bridge-acceptor molecule in solution.     

Bismuth-Oxide-Decorated Graphene Oxide Hybrids for Catalytic and Electrocatalytic Reduction of CO2

Global warming challenges are fueling the demand to develop an efficient catalytic system for the reduction of CO₂, which would contribute significantly to the control of climate change. Herein, as-synthesized bismuthoxide-decorated graphene oxide (Bi₂O₃@GO) was used as an electro/thermal catalyst for CO₂ reduction. Bi₂O₃@GO is found to be distributed uniformly, as confirmed by scanning electron and transmission electron microscopic analysis. The X-ray diffraction (XRD) pattern shows that the Bi₂O₃ has a β-phase with 23.4 m² g⁻¹ BET surface area. Significantly, the D and G bands from Raman spectroscopic analysis and their intensity ratio (I_D/I_G) reveal the increment in defective sites on GO after surface decoration. X-ray photoelectron spectroscopic (XPS) analysis shows clear signals for Bi, C, and O, along with their oxidation states. An ultra-low onset potential (−0.534 V vs. RHE) for the reduction of CO₂ on Bi₂O₃@GO is achieved. Furthermore, potential-dependent (−0.534, −0.734, and −0.934 vs. RHE) bulk electrolysis of CO₂ to formate provides Faradaic efficiencies (FE) of approximately 39.72, 61.48, and 83.00 %, respectively. Additionally, in time-dependent electrolysis at a potential of −0.934 versus RHE for 3 and 5 h, the observed FEs are around 84.20 % and 87.17 % respectively. This catalyst is also used for the thermal reduction of CO₂ to formate. It is shown that the thermal reduction provides a path for industrial applications, as this catalyst converts a large amount of CO₂ to formate (10 mm ).     

Hydrogen-bonded cluster of nitroxyl: many-body analysis and spectroscopic characterization

Structural Chemistry - Hydrogen bonding interactions in linear and cyclic clusters of nitroxyl are studied using density functional theory at PBEPBE/aug-cc-pvdz level. Many-body analysis technique...     

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me₂NC₆H₄)Bi]²⁺ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me₂NC₆H₄}Bi{OP(NMe₂)₃}₃][B(3,5-C₆H₃Cl₂)₄]₂. These observations led us to generate dicationic organobismuth catalyst, [(Me₂NC₆H₄)Bi(L)₃]²⁺ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si−H addition.