The Instability of Ni{N(SiMe3)2}2: A Fifty Year Old Transition Metal Silylamide Mystery

The characterization of the unstable Ni^II bis(silylamide) Ni{N(SiMe₃)₂}₂ ( 1 ), its THF complex Ni{N(SiMe₃)₂}₂(THF) ( 2 ), and the stable bis(pyridine) derivative trans‐Ni{N(SiMe₃)₂}₂(py)₂ ( 3 ), is described. Both 1 and 2 decompose at ca. 25 °C to a tetrameric Ni^I species, [Ni{N(SiMe₃)₂}]₄ ( 4 ), also obtainable from LiN(SiMe₃)₂ and NiCl₂(DME). Experimental and computational data indicate that the instability of 1 is likely due to ease of reduction of Ni^II to Ni^I and the stabilization of 4 through dispersion forces.     

Coordination Complexes of a Neutral 1,2,4‐Benzotriazinyl Radical Ligand: Synthesis,Molecular and Electronic Structures,and Magnetic Properties

A series of d‐block metal complexes of the recently reported coordinating neutral radical ligand 1‐phenyl‐3‐(pyrid‐2‐yl)‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl ( 1 ) was synthesized. The investigated systems contain the benzotriazinyl radical 1 coordinated to a divalent metal cation, Mn^II, Fe^II, Co^II, or Ni^II, with 1,1,1,5,5,5‐hexafluoroacetylacetonato (hfac) as the auxiliary ligand of choice. The synthesized complexes were fully characterized by single‐crystal X‐ray diffraction, magnetic susceptibility measurements, and electronic structure calculations. The complexes [Mn( 1 )(hfac)₂] and [Fe( 1 )(hfac)₂] displayed antiferromagnetic coupling between the unpaired electrons of the ligand and the metal cation, whereas the interaction was found to be ferromagnetic in the analogous Ni^II complex [Ni( 1 )(hfac)₂]. The magnetic properties of the complex [Co( 1 )(hfac)₂] were difficult to interpret owing to significant spin–orbit coupling inherent to octahedral high‐spin Co^II metal ion. As a whole, the reported data clearly demonstrated the favorable coordinating properties of the radical 1 , which, together with its stability and structural tunability, make it an excellent new building block for establishing more complex metal–radical architectures with interesting magnetic properties.     

Antibody-free lanthanide-based fluorescent probe for determination of protein tyrosine kinase and phosphatase activities

A single-labeled peptide probe for measuring peptide phosphorylation status was developed by using a phosphate sensitive terbium chelate. The activity of Abl protein tyrosine kinase and T-cell protein Tyrosine phosphatase (TC PTP) was monitored in real time. To study the probe design in detail, variable substrate peptide sequences, where the enzyme target site was located from two to five amino acids apart from the nearest tyrosine residue, were synthesized. The maximum change observed in fluorescence intensity after phosphorylation was up to 320%, when the phosphorylated tyrosine was located two amino acids from the lysine coupled to the phosphate sensitive terbium chelate, demonstrating an excellent performance for a homogeneous assay. Also the longer distance of five amino acids between the phosphorylated tyrosine residue and terbium chelate resulted up to 260% change in fluorescence intensity.

Functional fluid jetting performance optimization

The manufacturing method utilizing digital printing technology offers alternatives to create electronic structures to be used even in microelectronic applications. Material deposition based on digital inkjet technology offers advantages over both traditional mask-etch technologies and other printing methods. Inkjet technology works in an additive manner, reducing material consumption and the amount of created waste. Additionally, the digital nature of the process allows flexible production, e.g., rapid design changes, quick prototyping, and small, customized series. This research paper introduces ink jetting performance optimization utilized in a concept where discrete components and bare silicon chips were integrated in a single module with ink jetted interconnections. Jetting optimization of fluids enhances the droplet placement and volume accuracy that is a critical issue when forming interconnections for dense IC circuits. The overall drop placement error in jet printing is a combination of several error sources such as mechanical, dynamical and material related issues. However, the largest error portion is induced by a single printhead. The printhead related errors can be detected by observing the flight behavior after firing from the printhead nozzle. This paper focuses on optimizing the performance of ejected droplets during flight, i.e., drop formation sequence and minimum flight time variance. The average drop velocities of drops fired from separate printhead nozzles can be used to evaluate the difference in placement on substrate, which in worse case may lead to electrical wiring failures. The performance optimization was done by analyzing the initial state, modeling the drop velocity during flight, optimizing the process parameters to satisfy the model, and accepting the model after verification. Two inks, conductive and dielectric, were evaluated and improvement in placement accuracy was achieved through enhanced uniformity in drop average velocities, a dimensionless number, coefficient of variation was enhanced from 0.051 to 0.040,with conductive ink and from 0.111 to 0.049 with dielectric ink, thus decreasing the velocity related drop placement error.     

Electron ionization induced fragmentation of some oxadiazole and thiadiazole derivatives

The mass spectrometric behaviour under electron ionization of several 3,4-(alkyl/aryl)-disubstituted 1,2,4-oxadiazole-5(4H)-ones (1-13) and 1,2,4-thiadiazole-5(4H)-thiones (14-17), and that of 3-aryl-5-alkyl- or arylthio-1,2,4-thiadiazoles (18-24), was studied. These five-membered rings split similarly to the corresponding 1,2,4-thiadiazole-5(4H)-ones, although substitution has also a clear effect on the routes of fragmentation and the magnitude of secondary processes. In particular, the fragmentation of 1,2,4-oxadiazole-5(4H)-ones (1-6), which do not bear aromatic substituents, was, in addition to the ring ruptures, fairly complicated. The other compounds fragmented more systematically and relatively few unpredictable fragmentations occurred.     

Encapsulation of diquats by resorcinarenes: a novel staggered anion-solvent mediated hydrogen bonded capsule

Crystallisation studies of ethyl resorcinarene with diquats 2b and 3a (1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane dibromide and 1,4-diazoniabicyclo[2.2.2]octane dichloride, respectively) resulted in hydrogen bonded molecular capsules in which the cations are encapsulated in between the cavities of two resorcinarene molecules and anions are located in the middle of the lower rim ethyl chains.     

Multivariate moment based extreme value index estimators

Modeling extreme events is of paramount importance in various areas of science—biostatistics, climatology, finance, geology, and telecommunications, to name a few. Most of these application areas involve multivariate data. Estimation of the extreme value index plays a crucial role in modeling rare events. There is an affine invariant multivariate generalization of the well known Hill estimator—the separating Hill estimator. However, the Hill estimator is only suitable for heavy tailed distributions. As in the case of the separating multivariate Hill estimator, we consider estimation of the extreme value index under the assumptions of multivariate ellipticity and independent identically distributed observations. We provide affine invariant multivariate generalizations of the moment estimator and the mixed moment estimator. These estimators are suitable for both light and heavy tailed distributions. Asymptotic properties of the new extreme value index estimators are derived under multivariate elliptical distribution with known location and scatter. The effect of replacing true location and scatter by estimates is examined in a thorough simulation study. We also consider two data examples: one financial application and one meteorological application.     

Utilizing inkjet printing to fabricate electrical interconnections in a system-in-package

The printed interconnections for encapsulated electronic packages using nanoparticle metal inks and polymer dielectrics have been demonstrated. The printing has utilized a digital printing method, inkjet printing. The printing process has been adopted rather well, but process yield improvement required more attention to the control of individual manufacturing stages and error sources. The sources for possible errors can be roughly divided into separate groups: the substrate-ink interaction and treatment procedure related, ink jetting related, and moving stage related. In this paper, the individual stages were taken under consideration. The process performance was studied using statistical methods. The affecting factors were classified, and designed experiments were carried out to determine the most significant factors and to create a model to describe the behavior. According to the models, optimized process parameters were achieved, and implemented in practice.     

Smith meets Smith: Smith normal form of Smith matrix

In 1861, Henry John Stephen Smith [H.J.S. Smith, On systems of linear indeterminate equations and congruences, Philos. Trans. Royal Soc. London. 151 (1861), pp. 293–326] published famous results concerning solving systems of linear equations. The research on Smith normal form and its applications started and continues. In 1876, Smith [H.J.S. Smith, On the value of a certain arithmetical determinant, Proc. London Math. Soc. 7 (1875/76), pp. 208–212] calculated the determinant of the n?×?n matrix ((i,?j)), having the greatest common divisor (GCD) of i and j as its ij entry. Since that, many results concerning the determinants and related topics of GCD matrices, LCM matrices, meet matrices and join matrices have been published in the literature. In this article these two important research branches developed by Smith, in 1861 and in 1876, meet for the first time. The main purpose of this article is to determine the Smith normal form of the Smith matrix ((i,?j)). We do this: we determine the Smith normal form of GCD matrices defined on factor closed sets.     

Characteristics of multivariate distributions and the invariant coordinate system

We consider a semiparametric multivariate location–scatter model where the standardized random vector of the model is fixed using simultaneously two location vectors and two scatter matrices. The approach using location and scatter functionals based on the first four moments serves as our main example. The four functionals yield in a natural way the corresponding skewness, kurtosis and unmixing matrix functionals. Affine transformation based on the unmixing matrix transforms the variable to an invariant coordinate system. The limiting properties of the skewness, kurtosis, and unmixing matrix estimates are derived under general conditions. We discuss related statistical inference problems, the role of the sample statistics in testing for normality and ellipticity, and connections to invariant coordinate selection and independent component analysis.