Investigation of the Catalytic Activity of a 2‐Phenylidenepyridine Palladium(II) Complex Bearing 4,5‐Dicyano‐1,3‐bis(mesityl)imidazol‐2‐ylidene in the Mizoroki‐Heck Reaction

The phenylidenepyridine (ppy) palladacycles [PdCl(ppy)(IMes)] ( 4 ) [IMes = 1,3‐bis(mesityl)imidazol‐2‐ylidene] and [PdCl(ppy){(CN)₂IMes}] ( 6 ) [(CN)₂IMes = 4,5‐dicyano‐1,3‐bis(mesityl)imidazol‐2‐ylidene] were prepared by facile two step syntheses, starting with the reaction of palladium(II) chloride with 2‐phenylpyridine followed by subsequent addition of the NHC ligand to the precatalyst precursor [PdCl(ppy)]₂. Suitable crystals for the X‐ray analysis of the complexes 4 and 6 were obtained. It was shown that 6 has a shorter NHC‐palladium bond than the IMes complex 4 . The difference of the palladium carbene bond lengths based on the higher π‐acceptor strength of (CN)₂IMes in comparison to IMes. Thus, (CN)₂IMes should stabilize the catalytically active central palladium atom better than IMes. As a measure for the π‐acceptor strength of (CN)₂IMes compared to IMes, the selone (CN)₂IMes · Se ( 7 ) was prepared and characterized by ⁷⁷Se‐NMR spectroscopy. The π‐acceptor strength of 7 was illuminated by the shift of its ⁷⁷Se‐NMR signal. The ⁷⁷Se‐NMR signal of 7 was shifted to much higher frequencies than the ⁷⁷Se‐NMR signal of IMes · Se. Catalytic experiments using the Mizoroki‐Heck reaction of aryl chlorides with n‐butyl acrylate showed that 6 is the superior performer in comparison to 4 . Using complex 6 , an extensive substrate screening of 26 different aryl bromides with n‐butyl acrylate was performed. Complex 6 is a suitable precatalyst for para‐substituted aryl bromides. The catalytically active species was identified by mercury poisoning experiments to be palladium nanoparticles.     

Infrared camera based on a curved retina

Design of miniature and light cameras requires an optical design breakthrough to achieve good optical performance. Solutions inspired by animals' eyes are the most promising. The curvature of the retina offers several advantages, such as uniform intensity and no field curvature, but this feature is not used. The work presented here is a solution to spherically bend monolithic IR detectors. Compared to state-of-the-art methods, a higher fill factor is obtained and the device fabrication process is not modified. We made an IR eye camera with a single lens and a curved IR bolometer. Images captured are well resolved and have good contrast, and the modulation transfer function shows better quality when comparing with planar systems.     

Smart Antennas with Two-Dimensional Array Configurations for Performance Enhancement of a Joint Detection CDMA Mobile Radio System

Smart antennas for base stations of cellular mobile radio systems offer the potential of system performance enhancement by taking advantage of the directionally inhomogeneous signal reception at the receiver. In this paper, two-dimensional array configurations employed at the uplink receiver of a joint detection CDMA (JD-CDMA) mobile radio system are investigated. This smart antenna concept can be split up into a novel channel estimator and data detector which incorporate explicitely the information of the direction-of-arrival (DOA) of signals emerging from users assigned to the considered base station. Proceeding from channel models that model the directional inhomogeneity of the mobile radio channel with single DOAs, the link level performance of a JD-CDMA mobile radio system using this smart antenna concept is evaluated for the rural propagation environment. The performance evaluation is based on Monte Carlo simulations of data transmission and average bit error rates versus the average signal to noise ratio per net information bit are presented for different array configurations. Although these results should be considered as upper bounds for the link level performance, they reveal the advantages of implementing two-dimensional array configurations at the uplink receiver of a JD-CDMA mobile radio system.     

Synthesis and characterization of semifluorinated polymers and block copolymers

The goal of the investigation presented here was to evaluate the influence of semifluorinated side chains on the bulk structure and the surface properties of polysulfones with different chain structure. Thus, segmented block copolymers consisting of polysulfone and semifluorinated aromatic polyester segments as well as polysulfones having semifluorinated side chains randomly distributed over the polymer backbone were synthesized and characterized. Oxydecylperfluorodecyl side chains were used because of their strong tendency for self-organization. The influence of the chain architecture on the self-organization as well as on the surface properties, particularly the wetting behavior, was examined. It could be shown that despite of the higher self-organizing tendency of block copolymers the surface properties of both polymer types are comparable and depend only on the concentration of side chains.     

A Refined Version of the Lang-Trotter Conjecture

Let E be an elliptic curve defined over the rational numbersand r a fixed integer. Using a probabilistic model consistentwith the Chebotarev density theorem for the division fieldsof E and the Sato–Tate distribution, Lang and Trotterconjectured an asymptotic formula for the number of primes upto x which have Frobenius trace equal to r, where r is a fixedinteger. However, as shown in this note, this asymptotic estimatecannot hold for all r in the interval with a uniform bound for the error term, becausean estimate of this kind would contradict the Chebotarev densitytheorem as well as the Sato–Tate conjecture. The purposeof this note is to refine the Lang–Trotter conjecture,by taking into account the "semicircular law," to an asymptoticformula that conjecturally holds for arbitrary integers r inthe interval , with auniform error term. We demonstrate consistency of our refinementwith the Chebotarev density theorem for a fixed division field,and with the Sato–Tate conjecture. We also present numericalevidence for the refined conjecture.     

Theoretical approach to estimate laser process parameters for drilling in crystalline silicon

This paper presents a simple method for estimating the ablation rate during drilling processes in crystalline silicon wafers. Using data from literature, the physical process of material heating, melting, and ejection can be estimated on a time scale and leads to a temporal separation of the pulse duration in two parts. The latter one offers a theoretical determination of the expected average ablation rate. The results of this approximation coincide with experimental values and offer solutions to increase drilling efficiency. The experiments were done with a q‐switched solid‐state laser emitting at 1064 nm wavelength at pulse durations between 810 ns and 1440 ns. Copyright © 2010 John Wiley & Sons, Ltd.     

Issues in HgCdTe Research and Expected Progress in Infrared Detector Fabrication

The purpose of this paper is to review the trends in HgCdTe research, illustrating the discussed ideas with the latest results obtained at DEFIR (CEA-LETI and Sofradir joint laboratory). The beginning of this paper is devoted to an extended introduction to today’s issues concerning HgCdTe photodiode performance enhancement. In fact, very high-quality material is mandatory for ultrahigh performance at low temperature as well as for high noise operability at high operating temperature (HOT). Therefore, a strong effort has been carried out during the last few years for lattice-matched CdZnTe substrate and HgCdTe active layer growth improvement, leading to very large substrates and ultraflat liquid-phase epitaxy layers. The same analysis holds for diode process quality and passivation. Therefore, the photodiode process has been completely revisited in order to optimize HOT operability. Also necessary for the next generation of HOT devices, some significant progress has been made in small-pixel-pitch interconnection on silicon read-out circuits. Indeed, the first 10-μm focal-plane arrays (FPAs) have been successfully fabricated this year in the mid-wave infrared (IR) band. The latest avalanche photodiode (APD) realizations are also presented with 15-μm-pitch FPAs for passive imaging and 30-μm-pitch ultrafast arrays running at 1.5 kHz full frame rate. Linear-mode photon counting using APDs is also briefly discussed. Finally, the paper concludes on more complex structures for the third generation of IR detectors, discussing the latest achievements in dual-band FPA fabrication in various spectral bands.     

Metabolic and Proteomic Analysis of Chlorella sorokiniana,Chloroidium saccharofilum,and Chlorella vulgaris Cells Cultured in Autotrophic,Photoheterotrophic, and Mixotrophic Cultivation Modes

Chlorella is one of the most well-known microalgal genera, currently comprising approximately a hundred species of single-celled green algae according to the AlgaeBase. Strains of the genus Chlorella have the ability to metabolize both inorganic and organic carbon sources in various trophic modes and synthesize valuable metabolites that are widely used in many industries. The aim of this work was to investigate the impact of three trophic modes on the growth parameters, productivities of individual cell components, and biochemical composition of Chlorella sorokiniana, Chloroidium saccharofilum, and Chlorella vulgaris cells with special consideration of protein profiles detected by SDS-PAGE gel electrophoresis and two-dimensional gel electrophoresis with MALDI-TOF/TOF MS. Mixotrophic conditions with the use of an agro-industrial by-product stimulated the growth of all Chlorella species, which was confirmed by the highest specific growth rates and the shortest biomass doubling times. The mixotrophic cultivation of all Chlorella species yielded a high amount of protein-rich biomass with reduced contents of chlorophyll a, chlorophyll b, carotenoids, and carbohydrates. Additionally, this work provides the first information about the proteome of Chloroidium saccharofilum, Chlorella sorokiniana, and Chlorella vulgaris cells cultured in molasses supplementation conditions. The proteomic analysis of the three Chlorella species growing photoheterotrophically and mixotrophically showed increased accumulation of proteins involved in the cell energy metabolism and carbon uptake, photosynthesis process, and protein synthesis, as well as proteins involved in intracellular movements and chaperone proteins.     

A remark on the least n with χ (n) ≠ 1

Suppose that a > 2. We prove that the number of positive integers q ≦ Q such that there exists a primitive character χ modulo q with χ (n) = 1 for all n ≦ (log Q)^a is O(Q^1/(1-a)+ε). Received: 7 December 2004