Core-modified, meso-alkylidenyl porphyrins and their expanded analogues: a new family of nonplanar porphyrinoids

New core-modified, meso-alkylidenyl porphyrinoids bearing multiple exocyclic double bonds were synthesized and characterized. The synthesis was accomplished using a typical "3 + 1"-type condensation approach. Stable exocyclic tautomers bearing double bonds at the meso positions, as well the corresponding endocyclic tautomers, were isolated in the case of both thiabenziporphyrin and thiapyriporphyrin products prepared in the course of this study. On the other hand, only the exocyclic tautomer was isolated in the case of the congeneric oxapyriporphyrin and oxabenziporphyrin. Expanded analogues of the exocyclic forms of oxabenziporphyrin and thiabenziporphyrin were also isolated as minor products. A single-crystal X-ray diffraction analysis of the expanded thiabenziporphyrin (20) revealed that all four pyrrole rings displayed an inverted geometry, presumably reflecting the strong hydrogen-bonding extant between the pyrrole N-H proton and the carbonyl group of the malonate moiety in the solid state. On the other hand, the expanded oxabenziporphyrin (14) was found to possess a severely distorted geometry with only one pyrrole ring being inverted. Careful analysis of the structure revealed that the solid-state geometry of the expanded macrocycles correlates well with the internal angle defined by the 2- and 5 substituents and the centers of the furan (14) or thiophene (20) subunits.     

The Primal-Dual Second-Order Cone Approximations Algorithm for Symmetric Cone Programming

Given any open convex cone K, a logarithmically homogeneous, self-concordant barrier for K, and any positive real number r < 1, we associate, with each direction , a second-order cone containing K. We show that K is the interior of the intersection of the second-order cones , as x ranges over all directions in K. Using these second-order cones as approximations to cones of symmetric, positive definite matrices, we develop a new polynomial-time primal-dual interior-point algorithm for semidefinite programming. The algorithm is extended to symmetric cone programming via the relation between symmetric cones and Euclidean Jordan algebras.     

Roles of wave impedance and refractive index in photonic crystalswith magnetic and dielectric properties

We investigated the roles of wave impedance and refractive index in photonic crystals by means of analytical expressions for edges frequencies of a photonic bandgap (PBG) in a one-dimensional photonic crystal with magnetic and dielectric properties. The analytical expressions were derived when the optical thicknesses of layers are the same. The wave impedance governs the formation of PBG's and the intensity of defect modes. Meanwhile, the position of PBG's and the creation of defect modes are related to the refractive index     

Wireless broadband communications: some research activities inSingapore

Almost a decade ago, Singapore started crafting and implementing its IT2000 master plan to transform the city-state into an information-technology-based intelligent island. Since 1997, the main infrastructure of a high-speed ATM-based backbone network, called SingaporeONE, has been in place along with a host of commercial and governmental application service sites providing a plethora of online services. Because of its small size and extensive wired infrastructure, broadband access to homes and offices is currently provided via ADSL and cable modems. There is, however, interest in the use of wireless broadband communication technologies to access SingaporeONE, motivated primarily by its lower cost and faster deployment. In this article we describe some of our R&D activities motivated by the above interest to provide wireless broadband access to SingaporeONE. Specifically, we describe our study of LMDS, and the design and development of a wireless ATM LAN     

Psychrotolerant Mesorhizobium sp. Isolated from Temperate and Cold Desert Regions Solubilizes Potassium and Produces Multiple Plant Growth Promoting Metabolites

Soil potassium (K) supplement depends intensively on the application of chemical fertilizers, which have substantial harmful environmental effects. However, some bacteria can act as inoculants by converting unavailable and insoluble K forms into plant-accessible forms. Such bacteria are an eco-friendly approach for enhancing plant K absorption and consequently reducing utilization of chemical fertilization. Therefore, the present research was undertaken to isolate, screen, and characterize the K solubilizing bacteria (KSB) from the rhizosphere soils of northern India. Overall, 110 strains were isolated, but only 13 isolates showed significant K solubilizing ability by forming a halo zone on solid media. They were further screened for K solubilizing activity at 0 °C, 1 °C, 3 °C, 5 °C, 7 °C, 15 °C, and 20 °C for 5, 10, and 20 days. All the bacterial isolates showed mineral K solubilization activity at these different temperatures. However, the content of K solubilization increased with the upsurge in temperature and period of incubation. The isolate KSB (Grz) showed the highest K solubilization index of 462.28% after 48 h of incubation at 20 °C. The maximum of 23.38 µg K/mL broth was solubilized by the isolate KSB (Grz) at 20 °C after 20 days of incubation. Based on morphological, biochemical, and molecular characterization (through the 16S rDNA approach), the isolate KSB (Grz) was identified as Mesorhizobium sp. The majority of the strains produced HCN and ammonia. The maximum indole acetic acid (IAA) (31.54 µM/mL) and cellulase (390 µM/mL) were produced by the isolate KSB (Grz). In contrast, the highest protease (525.12 µM/mL) and chitinase (5.20 µM/mL) activities were shown by standard strain Bacillus mucilaginosus and KSB (Gmr) isolate, respectively.     

Adaptive error coding using channel prediction

In this paper, we construct a finite-state Markov chain model for a Rayleigh fading channel by partitioning the range of the received signal envelope into K intervals. Using a simulation of the classic two-ray Rayleigh fading model, a Markov transition probability matrix is obtained. Using this matrix to predict the channel state, we introduce an adaptive forward error correction (FEC) coding scheme. Simulation results are presented to show that the adaptive FEC coding scheme significantly improves the performance of a wireless communication system.     

Energy transfer and migration in highly forbidden transitions of lanthanide ion doped crystals

Förster–Dexter theory for resonant energy transfer is extended to higher order and applied to explain the rates of energy transfer and migration processes in highly forbidden transitions for some solid-state lanthanide (Ln) ion systems for which experimental results are available. The second-order two-body energy transfer mechanism involves two inter-ion correlated dipole electrostatic interactions, i.e. dipole dipole–dipole dipole (dd–dd) energy transfer, also termed Axe–Axe energy transfer in view of the similarity of the theoretical formalism with that for two-photon transitions. Each of the dipolar transitions consists of a transition from the 4fⁿ configuration to an opposite-parity configuration, taken to be 4fⁿ⁻¹5d. dd–dd energy transfer is a short-range (R⁻¹²) interaction so that it is most important in systems with short donor Ln–acceptor Ln separations. The energy transfer formalism is extended to include spin-forbidden transitions at one or two sites, the so-called Axe–Judd–Pooler (Axe–JP) and JP–JP energy transfer. In some cases the dd–dd mechanism is the dominant energy transfer process, as exemplified herein for energy migration in the ⁵D₀ state of Sm²⁺ in SrF₂, and also in the ⁵D₀ state of Eu³⁺ in Cs₂NaEuCl₆.     

配位滴定法测定锌含量的合适酸度条件

调节待测体系的pH值是配位滴定中一种重要的选择性滴定手段。采用CTE1.0程序计算了不同酸度条件下的终点误差,同时用配位滴定法测定了模拟样品和市售药品中的锌含量。计算结果和实测结果均表明,在不含钙离子的待测体系中,测定锌离子含量的合适酸度条件为pH=6;在钙、锌混合离子溶液中,测定锌含量的合适酸度条件为pH=5。平行测定实验的相对标准误差为1.63%,加标回收率为99.1%-101.8%。     

Effect of the liquid–liquid phase separation on the crystallization behavior of a poly(ethylene‐ran‐vinyl acetate) and paraffin wax blend

The effect of liquid–liquid phase separation (LLPS) on the crystallization behavior of poly(ethylene‐ran‐vinyl acetate) with a vinyl acetate content of 9.5 wt % (EVA‐H) in the critical composition of a 35/65 (wt/wt) EVA‐H/paraffin wax blend was investigated by small‐angle light and X‐ray scattering methods and rheometry. This blend exhibited an upper critical solution temperature (UCST) of 98°C, and an LLPS was observed between the UCST and the melting point of 88°C for the EVA‐H in the blend. As the duration time in the LLPS region increased before crystallization at 65°C, both the spherulite size and the crystallization rate of the EVA‐H increased, but the degree of the lamellar ordering in the spherulite and the degree of crystallinity of the EVA‐H in the blend decreased. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 707–715, 2000     

Understanding Dark Spot Formation and Growth in Organic Light‐Emitting Devices by Controlling Pinhole Size and Shape

We report on our in‐situ experimental observations of dark spots in organic light‐emitting diodes using optical microscopy. Uniformly sized silica microparticles are used to intentionally create size‐ and shape‐controllable pinholes on the cathode protective layer. Subsequently, the pinholes trigger the initial formation of dark spots, which we then monitor. Due to the use of particles of various diameters, we are able to linearly associate the growth rate with pinhole size. This allows us to estimate the original pinhole sizes that give rise to the dark spots and to study their distribution. Our studies verify that pinholes on the protective layer create pathways for water or oxygen diffusion, which controls the dark spot growth rate. The pinhole size dependence illustrates that the pinhole perimeter (not the area) determines the amount of water or oxygen diffusing into the diodes at a certain time.