Cutting process dynamics by nonlinear time series and wavelet analysis

We have modeled the dynamics of a cutting process by a two-degree-of-freedom mass-spring system with dry friction. Using nonlinear time series and wavelet analysis, we have investigated the vibrational instabilities of the system for different values of the cutting force. By constructing the phase portraits and calculating the Lyapunov exponents we have delineated the conditions for which a periodic or chaotic motion can occur. The results are verified by means of a time-scale representation of the wavelet power spectrum.     

Dynamical response of a pendulum driven horizontally by a DC motor with a slider–crank mechanism

Nonlinear Dynamics - The pendulum is excited horizontally by a system of a DC motor and a slider–crank mechanism. Mathematical modeling is realistic and based on experimental rig, taking into...     

Study of the shock-induced acceleration of hexane droplets

An experimental study of the interaction of a shock wave with a hexane droplet is presented. The main goal of the experiments was to record images of the process and measure basic parameters describing movement, dispersion and evaporation of the droplets engulfed by a shock wave propagating in air. A shock tube with a visualization section was used for this research. Photography of the process allowed one to measure the positions, velocities and sizes of mist clouds created by the interaction processes. Analysis of the pictures shows that there is no qualitative difference between cases for different size droplets, but shock Mach number had a significant effect on the process. Quantitative analysis shows that under certain conditions, a catastrophic breakup mechanism of dispersion occurred. The droplets are shattered into a mist cloud before they achieve mechanical equilibrium with the surrounding gas. The approximate time for the complete dispersion and acceleration of the fuel droplet varies from 300 to 500 μs, and depends both on the droplet diameter and shock velocity. The dispersion time is controlled principally by the droplet diameter, and to a lesser extent, the shock Mach number. This paper is based on work that was presented at the 20th International Colloquium on the Dynamics of Explosions and Reactive Systems, Montreal, Canada, July 31–August 5, 2005.     

Towards More Photostable,Brighter, and Less Phototoxic Chromophores: Synthesis and Properties of Porphyrins Functionalized with Cyclooctatetraene

Free base and zinc porphyrins functionalized with cyclooctatetraene (COT), a molecule known as a good triplet-state quencher, have been obtained and characterized in detail by structural, spectral, and photophysical techniques. Substitution with COT leads to a dramatic decrease of the intrinsic lifetime of the porphyrin triplet. As a result, photostability in oxygen-free solution increases by two to three orders of magnitude. In non-degassed solutions, improvement of photostability is about tenfold for zinc porphyrins, but the free bases become less photostable. Similar quantum yields of photodegradation in free base and zinc porphyrins containing the COT moiety indicate a common mechanism of photochemical decomposition. The new porphyrins are expected to be much less phototoxic, since the quantum yield of singlet oxygen formation strongly decreases because of the shorter triplet lifetime. The reduction of triplet lifetime should also enhance the brightness and reduce blinking in porphyrin chromophores emitting in single-molecule regime, since the duration of dark OFF states will be shorter.     

Correction to: Unexpected Z/E isomerism of N-methyl-O-phosphothioyl benzohydroxamic acids,their oxyphilic reactivity and inertness to amines

Structural Chemistry - A Correction to this paper has been published: https://doi.org/10.1007/s11224-021-01744-8     

Intramolecular transformation of an antifungal antibiotic nystatin A1 into its isomer,iso‐nystatin A1 – structural and molecular modeling studies

Nystatin A₁, a polyene macrolide antifungal antibiotic, in a slightly basic or acidic solution undergoes an intramolecular transformation, yielding a structural isomer, the translactonization product, iso‐nystatin A₁ with lactone ring diminished by two carbon atoms. Structural evidence is provided by advanced NMR and Mass Spectrometry (MS) studies. Molecular dynamics simulations and quantum mechanics calculations gave the insight into the course and mechanism of the transformation and its effect on the conformation of the subject molecule. Copyright © 2016 John Wiley & Sons, Ltd.     

Quantitative analysis of crystallization kinetics by light depolarization technique. Possibilities and limitations

The kinetics of isothermal crystallization of various polymers was investigated by light depolarization technique (LDT) using the new setup with direct registration of depolarization ratio. Experimental data were analyzed using new method proposed by Ziabicki who shown that degree of crystallinity is a non-linear function of degree of depolarization, crystal thickness, and its birefringence. Other experimental methods were involved providing supplementary information on crystal thickness (SAXS) and allowing comparison of crystallization kinetics (WAXS, DSC). The advantage of LDT relies on high sampling rate allowing on-line measurements and lack of inertia effects that exist in other methods like calorimetry. The limitations of the applicability of the method are discussed. The method needs supplementary information not only on crystal thickness but also on variable optical birefringence of real crystals. Our results show that LDT can be used in a simple way for investigation of crystallization kinetics at relatively high temperatures, providing large and perfect crystals. In such a case it is sufficient to use crystal intrinsic birefringence and final crystal thickness typical at particular temperature of crystallization. On the other hand, depolarization ratio combined with measurements by other methods (crystallinity and crystal thickness) can be used for estimation of crystal birefringence.     

Semiderivative real filter for microoptical elements quality control

The article presents a proposal for a new method of automatic quality control of microlenses arrays, which is based on a semiderivative real filter. The use of the semiderivative filter for examining pure-phase objects involves modifying the spatial frequency. The basis of the proposed setup is a 4f correlator setup with coherent light. The phase object examined is placed in the input plane of the correlator. Next, the light passes through a filter located in the frequency plane, which gives an intensity signal. In the output plane a charge-coupled device (CCD) camera registers the light intensity, the range of which informs the shape of the phase object. The proposed method is shift invariant, so it allows for examination of single elements or a set of micro-optical elements simultaneously. Additionally, the same setup allows for measuring the phase of objects whose thickness is either considerably smaller or much bigger than 2π.     

Oligomeric complexes of some heteroaromatic ligands and aromatic diamines with rhodium and molybdenum tetracarboxylates: 13C and 15N CPMAS NMR and density functional theory studies

Seven new oligomeric complexes of 4,4′‐bipyridine; 3,3′‐bipyridine; benzene‐1,4‐diamine; benzene‐1,3‐diamine; benzene‐1,2‐diamine; and benzidine with rhodium tetraacetate, as well as 4,4′‐bipyridine with molybdenum tetraacetate, have been obtained and investigated by elemental analysis and solid‐state nuclear magnetic resonance spectroscopy, ¹³C and ¹⁵N CPMAS NMR. The known complexes of pyrazine with rhodium tetrabenzoate, benzoquinone with rhodium tetrapivalate, 4,4′‐bipyridine with molybdenum tetrakistrifluoroacetate and the 1 : 1 complex of 2,2′‐bipyridine with rhodium tetraacetate exhibiting axial–equatorial ligation mode have been obtained as well for comparison purposes. Elemental analysis revealed 1 : 1 complex stoichiometry of all complexes. The ¹⁵N CPMAS NMR spectra of all new complexes consist of one narrow signal, indicating regular uniform structures. Benzidine forms a heterogeneous material, probably containing linear oligomers and products of further reactions. The complexes were characterized by the parameter complexation shift Δδ (Δδ = δ_complex ? δ_ligand). This parameter ranged from around ?40 to ?90 ppm in the case of heteroaromatic ligands, from around ?12 to ?22 ppm for diamines and from ?16 to ?31 ppm for the complexes of molybdenum tetracarboxylates with 4,4′‐bipyridine. The experimental results have been supported by a density functional theory computation of ¹⁵N NMR chemical shifts and complexation shifts at the non‐relativistic Becke, three‐parameter, Perdew‐Wang 91/[6‐311++G(2d,p), Stuttgart] and GGA–PBE/QZ4P levels of theory and at the relativistic scalar and spin‐orbit zeroth order regular approximation/GGA–PBE/QZ4P level of theory. Nucleus‐independent chemical shifts have been calculated for the selected compounds. Copyright © 2015 John Wiley & Sons, Ltd.