Hydrogenation of dinitriles on Raney-type Ni catalysts: kinetic and mechanistic aspects

The mechanism of the hydrogenation of aliphatic C₄–C₆ dinitriles (succinonitrile, glutaronitrile, and adiponitrile) over Raney-type Ni catalysts was investigated in a fed-batch autoclave at 350 K and 5.0 MPa. The results are interpreted based on the strength of adsorption, the interaction with the solvent and intramolecular interactions. The kinetics of the hydrogenation of aliphatic dinitriles is highly dependent on the hydrocarbon chain length. Short dinitriles like succinonitrile adsorb stronger on the catalyst surface than longer dinitriles like adiponitrile. The yield of the intermediate aminonitriles decreases with increasing hydrocarbon chain length, due to the enhanced competitiveness of dinitrile and aminonitrile for the same active sites. It is proposed that the reactivity of dinitriles and aminonitriles is caused by difference in solvent interaction. It is remarkable that the stronger the adsorption, the higher the reactivity. The reactivity decreases in the order: succinonitrile > glutaronitrile > adiponitrile. In contrast, the reaction rate of the aminonitriles is fairly independent of the hydrocarbon chain length. The formation of undesired secondary amines in the form of cyclic compounds is under kinetic control and increases with decreasing chain length. It is found that adiponitrile can be very selectively hydrogenated to primary diamines. Promoting Raney-type Ni catalysts with traces of Mo, Cr or Fe enhances the performance in the hydrogenation of dinitriles. This gives the best opportunity for process improvement towards the desired primary amines.     

Chip geometry and cutting force prediction in gear hobbing

This paper presents a tri-dexel geometric engine integrated simulation model for the gear hobbing operation. The process kinematics are modeled and validated using CNC signals from a Liebherr LC500 hobbing machine. Workpiece geometry updating and cutter-workpiece engagement (CWE) calculations are efficiently realized in the tri-dexel engine. 3D force contributions at discretized nodes along the hob's cutting edges are computed considering the localized principal cutting directions, and rake and inclination angles. To measure cutting forces, a rotary dynamometer is successfully adapted and used alongside a Kalman filter to compensate for structural dynamics. The predicted forces agree well with their experimental counterparts.     

Lead and cadmium in teeth,bone and kidneys of rats with a standard Pb‐Cd supply

Male Wistar rats received a combination of 25 ppm PbCl₂ and 5 ppm CdCl₂ in drinking water at different developmental stages. Pb and Cd levels of incisors, molars, epiphyses, diaphyses and kidney cortex were recorded by atomic absorption spectrophotometry. The results confirmed that Pb has an affinity for hard tissue and especially to teeth, but it also accumulated in soft tissues under the above conditions. In addition, the results indicated none or only a moderate placental or mammary barrier for Pb, and suggested a high absorption of lead from the intestine of sucklings. The results also confirmed that kidney cortex is a primary target for Cd, and indicated that Cd has crossed the placental and mammary barriers to some degree. The positive significant correlation between Cd levels in molars and kidney cortex suggested that rodent molars indicate a degree of Cd absorption, whereas incisors do not. It is supposed that rodent molars are comparable to human deciduous teeth. It is thus confirmed that human deciduous teeth indicate previous lead exposure. It is further inferred that they also can be used as indicators of previous Cd‐exposures.     

Effective construction planning

This paper examines the relationships between construction planning efforts and construction planning effectiveness. The influence of the project's environment and organizational characteristics of construction firms on planning efforts and planning effectiveness is also investigated. A sample of 26 building projects was studied and the results were analysed using simple correlations. Three factors were found to have a significant effect on improving construction planning effectiveness: increases in planning time prior to commencement of work on site, the extent to which emphasis is placed on the determination of construction methods during construction planning and the frequency of revision of construction plans after commencement of work on site. Significant relationships were also found between project environment variables and organizational characteristics of construction firms and planning efforts and planning effectiveness. Implications of the results are that construction planners should systematically evaluate alternative plans, sufficient time should be allowed for proper planning, thorough reviews are needed whilst work is in progress, the planning effort needs to be relevant to the environmental context of the project and the firm should be appropriately organized. Suggestions are given for future research studies.     

Scaling Effects in Perovskite Ferroelectrics: Fundamental Limits and Process‐Structure‐Property Relations

Ferroelectric materials are well‐suited for a variety of applications because they can offer a combination of high performance and scaled integration. Examples of note include piezoelectrics to transform between electrical and mechanical energies, capacitors used to store charge, electro‐optic devices, and nonvolatile memory storage. Accordingly, they are widely used as sensors, actuators, energy storage, and memory components, ultrasonic devices, and in consumer electronics products. Because these functional properties arise from a noncentrosymmetric crystal structure with spontaneous strain and a permanent electric dipole, the properties depend upon physical and electrical boundary conditions, and consequently, physical dimension. The change in properties with decreasing physical dimension is commonly referred to as a size effect. In thin films, size effects are widely observed, whereas in bulk ceramics, changes in properties from the values of large‐grained specimens is most notable in samples with grain sizes below several micrometers. It is important to note that ferroelectricity typically persists to length scales of about 10 nm, but below this point is often absent. Despite the stability of ferroelectricity for dimensions greater than ~10 nm, the dielectric and piezoelectric coefficients of scaled ferroelectrics are suppressed relative to their bulk counterparts, in some cases by changes up to 80%. The loss of extrinsic contributions (domain and phase boundary motion) to the electromechanical response accounts for much of this suppression. In this article, the current understanding of the underlying mechanisms for this behavior in perovskite ferroelectrics is reviewed. We focus on the intrinsic limits of ferroelectric response, the roles of electrical and mechanical boundary conditions, grain size and thickness effects, and extraneous effects related to processing. In many cases, multiple mechanisms combine to produce the observed scaling effects.     

Effect of Mechanical Constraint on Domain Reorientation in Predominantly {111}‐Textured Lead Zirconate Titanate Films

Ferroelectric/ferroelastic domain reorientation was measured in 2.0 μm thick tetragonal {111}‐textured PbZr_0.30Ti_0.70O₃ thin films using synchrotron X‐ray diffraction (XRD). Lattice strain from the peak shift in the 111 Bragg reflection and domain reorientation were quantified as a function of applied electric field amplitude. Domain reorientation was quantified through the intensity exchange between the 112 and 211 Bragg reflections. Results from three different film types are reported: dense films that are clamped to the substrate (as‐processed), dense films that are partially released from the substrate, and films with 3% volume porosity. The highest amount of domain reorientation is observed in grains that are misoriented with respect to the {111} preferred (domain engineered) orientation. Relative to the clamped films, films that were released from the substrate or had porosity exhibited neither significant enhancement in domain reorientation nor in 111 lattice strain. In contrast, similar experiments on {100}‐textured and randomly oriented films showed significant enhancement in domain reorientation in released and porous films. Therefore, {111}‐textured films are less susceptible to changes in properties due to mechanical constraints because there is overall less domain reorientation in {111} films than in {100} films.     

Subunit‐Specific Labeling of Ubiquitin Chains by Using Sortase: Insights into the Selectivity of Deubiquitinases

Information embedded in different ubiquitin chains is transduced by proteins with ubiquitin‐binding domains (UBDs) and erased by a set of hydrolytic enzymes referred to as deubiquitinases (DUBs). Understanding the selectivity of UBDs and DUBs is necessary for decoding the functions of different ubiquitin chains. Critical to these efforts is the access to chemically defined ubiquitin chains bearing site‐specific fluorescent labels. One approach toward constructing such molecules involves peptide ligation by sortase (SrtA), a bacterial transpeptidase responsible for covalently attaching cell surface proteins to the cell wall. Here, we demonstrate the utility of SrtA in modifying individual subunits of ubiquitin chains. Using ubiquitin derivatives in which an N‐terminal glycine is unveiled after protease‐mediated digestion, we synthesized ubiquitin dimers, trimers, and tetramers with different isopeptide linkages. SrtA was then used in combination with fluorescent depsipeptide substrates to effect the modification of each subunit in a chain. By constructing branched ubiquitin chains with individual subunits tagged with a fluorophore, we provide evidence that the ubiquitin‐specific protease USP15 prefers ubiquitin trimers but has little preference for a particular isopeptide linkage. Our results emphasize the importance of subunit‐specific labeling of ubiquitin chains when studying how DUBs process these chains.