Phase behaviour of the discotic mesogen 5,10,15,20-tetrakis (4-n-dodecylphenyl)porphyrin under pressure

The phase behaviour of the discotic mesogen 5,10,15,20-tetrakis(4-n -dodecylphenyl)porphyrin (C12TPP) was investigated under hydrostatic pressures up to 300MPa by high pressure DTA and wide angle X-ray diffraction methods. The typical enantiotropic phase transitions of C12TPP, low- to high-temperature crystal (Cr2-Cr1), Cr1-discotic lamellar phase (DL), and DL-isotropic liquid (I) are observed at pressures up to 10MPa. Application of hydrostatic pressure to the sample generates a pressure-induced crystal polymorph (Cr3) between the Cr2 and Cr1 phases, and the phase transitions Cr2-Cr3-Cr1-DL-I occur reversibly in the pressure region between 10 and 180MPa. On heating at higher pressures above 180MPa, the fourth crystal polymorph (Cr4) is formed between the Cr2 and Cr3 phases at lower temperatures, and at the same time the fifth crystal polymorph (Cr5) appears abruptly between the Cr1 and DL phases at high temperatures. The Cr2-Cr4-Cr3-C1-(Cr5)-DL-I transition processes were observed at 180 200MPa. Further increasing the pressure above 270MPa induces entirely different thermal behaviour: only two peaks for the pressure-induced transition between the sixth and fifth polymorphs (Cr6-Cr5) and the Cr5-I transitions are detected at low and high temperatures on heating, while both the DTA and WAXD experiments on cooling show the formation of the DL phase as a monotropic phase between the I and Cr5 phases, indicating the I DL Cr5 Cr6 process. The thermal behaviour was ambiguous and complex in the pressure region between 200 and 260MPa because the peaks for the intermediate crystal transitions were too small to detect with confidence. The two different sequences of the Cr2-Cr4-Cr3-Cr1-DL-I and Cr6-Cr5-(DL)-I processes seems to occur competitively. The T vs. P phase diagram of a sample cooled at 300MPa was studied to determine the triple point of the DL phase and to investigate the phase stability of the pressure-induced crystal polymorphs. The Cr6-Cr5-I transition process was observed on heating at 200 and 300MPa, while the Cr6-Cr5-DL-I process was detected at lower pressures below 100MPa. Since the Cr5-DL transition temperature changes linearly with a slope dT/dP 40 degrees C/100 MPa, while the DL-I transition temperature changes slightly (dT/dP 5.5 degrees C/100MPa), the DL phase forms a triangle in the T vs. P diagram. The triple point of the DL phase was found to be 240.8MPa and 168.8 C. The Cr6 polymorph reorganized to the stable Cr2 form under atmospheric pressure on annealing at room temperature overnight.     

Supersonic Flow Past a Bent Delta Wing and Its Aerodynamic Characteristics

The supersonic flow past a bent delta wing and its aerodynamic characteristics, both local and integral, are studied using approximate analytic estimates and numerical calculations. The flow regimes with the shock attached to the leading edges are considered. It is established that at M = 4–6 and angles of attack as high as 6° the lift-drag ratio of the wing can be increased by 10% by deflecting the wing nose downwards. This is confirmed by the results obtained earlier in the hypersonic thin-shock-layer approximation. The effect is also obtained in calculations made within the framework of the Navier-Stokes equations.     

High-pressure alkylation of bis(benzylidene)phenylenediamines

The reactions of alkyl chlorides with bisanils (obtained from o-, m-, and p-phenylenediamines) under high pressure (10 kbar) were studied. Depending on the structure of the starting diamines and the solvent nature, hydrolysis of the reaction mixtures gave pure N-monoalkyl- or N,N"-dialkylphenylenediamines in high yields. The effect of the phase transition of the solvent on the direction of alkylation is discussed.     

Formal intramolecular [5 + 2] photocycloaddition reactions of maleimides: a novel approach to the CDE ring skeleton of (-)-cephalotaxine

A concise approach to the cephalotaxine CDE ring skeleton based on the intramolecular formal [5 + 2] photocycloaddition of cyclopentenyl-substituted maleimides is described. An investigation of the diastereoselectivity afforded by various protected alkoxy groups demonstrated that the best selectivity (3.5:1) was afforded by the free hydroxyl group, strongly suggesting a hydrogen-bonded excited state. Reaction: see text.     

Measurement of dense plasma temperature of the shock-compressed silicon

Measurements of the brightness temperature and compressibility of a dense silicon plasma formed by powerful shock waves (SWs) passing through a single-crystal sample have been carried out. Plane SWs were created using an explosive technique: the traditional plane acceleration of a steel driver plate made it possible to obtain pressures in silicon up to 133 GPa, and the use of “Mach” cumulative generators realized the pressures up to 510 GPa. The shock Hugoniot of silicon was determined by the impedance matching with α-quartz as the reference. The intensity of emitted thermal radiation was measured in the infrared range λ ∼ 1.5 μm, where silicon is optically transparent, and in the visible range of the spectrum. A significant (up to five times) understatement of the measured values of the brightness temperature in comparison with the values calculated by the equation of state was found. Taking into account the reflective properties of the SW in silicon does not lead to an agreement with the experiment. The estimates of relaxation processes behind the shock front suggest the presence of a zone of the establishment of ionization equilibrium with a width of ∼10 μm.     

Tandem queueing system with infinite and finite intermediate buffers and generalized phase-type service time distribution

A tandem queueing system with infinite and finite intermediate buffers, heterogeneous customers and generalized phase-type service time distribution at the second stage is investigated. The first stage of the tandem has a finite number of servers without buffer. The second stage consists of an infinite and a finite buffers and a finite number of servers. The arrival flow of customers is described by a Marked Markovian arrival process. Type 1 customers arrive to the first stage while type 2 customers arrive to the second stage directly. The service time at the first stage has an exponential distribution. The service times of type 1 and type 2 customers at the second stage have a phase-type distribution with different parameters. During a waiting period in the intermediate buffer, type 1 customers can be impatient and leave the system. The ergodicity condition and the steady-state distribution of the system states are analyzed. Some key performance measures are calculated. The Laplace–Stieltjes transform of the sojourn time distribution of type 2 customers is derived. Numerical examples are presented.     

BMAP|SM⥻1 model with Markov modulated retrials

This paper deals with the single server queueing system with a Batch Markovian Arrival Process (BMAP), the semi-Markovian (SM) service process, and the retrial process of a MMPP (Markov Modulated Poisson Process) type. The stationary distribution of orbit size at the embedded and arbitrary epochs is the subject of research. We appreciate the INTAS program for the financial support of this research via project #96-828.     

Monitoring in situ catalytically active states of Ru catalysts for different methanol oxidation pathways

One of the prerequisites for the detailed understanding of heterogeneous catalysis is the identification of the dynamic response of the catalyst surface under variable reaction conditions. The present study of methanol oxidation on different model Ru pre-catalysts, performed approaching the realistic catalytic reaction conditions, provides direct evidence of the significant effect of reactants' chemical potentials and temperature on the catalyst surface composition and the corresponding catalytic activity and selectivity. The experiments were carried out for three regimes of oxygen potentials in the 10(-1) mbar pressure range, combining in situ analysis of the catalyst surface by synchrotron-based photoelectron core level spectroscopy with simultaneous monitoring of the products released in the gas phase by mass spectroscopy. Metallic Ru with adsorbed oxygen and transient 'surface oxide', RuO(x), with varying x have been identified as the catalytically active states under specific reaction conditions, favouring partial or full oxidation pathways. It has been shown that the composition of catalytically active steady states, exhibiting different activity and selectivity, evolves under the reaction conditions, independent of the crystallographic orientation and the initial pre-catalyst chemical state, metallic Ru or RuO(2).     

Multi-dimensional asymptotically quasi-Toeplitz Markov chains and their application in queueing theory

Multi-dimensional asymptotically quasi-Toeplitz Markov chains with discrete and continuous time are introduced. Ergodicity and non-ergodicity conditions are proven. Numerically stable algorithm to calculate the stationary distribution is presented. An application of such chains in retrial queueing models with Batch Markovian Arrival Process is briefly illustrated. AMS Subject Classifications Primary 60K25 · 60K20     

Study of the dielectric properties of water in the frequency range 75–120 GHz

We study experimentally the frequency dependences of the refractive index n and the absorption coefficient k of distilled, sea, and river water. The measurements were performed using a quasioptical device with a backward-wave oscillator as the radiation source and OAP-7 optical-acoustic receivers at a water temperature of 27°C in the cell. The quantities n and k were determined from the measured transmission and reflection coefficients of the cell with water by means of joint numerical solution of the equations for these quantities. For distilled water in the frequency range f = 75–120 GHz, we obtained n = 6.142–3.926 · 10–2f[GHz] + 1.307 · 10–4(f[GHz])² and k = 3.607–2.101 · 10⁻² f[GHz] + 5.252 · 10–5(f[GHz])². On the whole, these data are in good agreement with the measurement results obtained by other authors at several frequencies of the indicated range and coincide with the calculation data based on the models by Meissner and Wentz and by Liebe et al. within the limits of the rms determination errors 0.05 and 0.02 for the parameters n and k, respectively. The values of n and k for different seawater samples and river water containing insoluble admixtures coincide with the values of these quantities for distilled water within the limits of the experimental measurement errors 3–5% and 1–2%, respectively. The dependences n(f) and k(f) obtained experimentally for seawater are compared with those calculated on the basis of the developed models. Measurements of the transmission spectrum of a cell with double distilled water were performed for low power density of radiation (less than μW/cm²) to reproduce the effect of water resonant transparency reported many times in the literature. Our measurements did not reveal any resonant features in the spectral behavior of the refractive index n and the absorption coefficient k of water and gave the same result as for a power density exceeding the threshold of appearance of this effect. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 49, No. 6, pp. 489–501, June 2006.