Synthesis, characterization, and spectroscopic analysis of antiaromatic benzofused metalloporphyrins

A two-electron oxidation of the Cu(II) (9) and Zn(II) (12) complexes of tetraphenyltetrabenzoporphyrin (TPTBP) results in the formation of stable antiaromatic [(TPTBP)Cu(II)(H(2)O)](2+)?2?[SbF(6)](-) (10) and [(TPTBP)Zn(II)(H(2)O)(2)](2+)?2?[SbF(6)](-) (13) with 16π electrons on the inner ligand perimeter. X-ray structures of the parent TPTBP complexes, the dications, and singly oxidized species [(TPTBP)Cu(II)](?+)[SbF(6)](-) (11) reveal that the use of TPTBP rather than a porphyrin ligand reduces the degree of nonplanarity in the 16π-electron species relative to the parent 18π complex. Significant high-field shifts of the (1)H?NMR signals of the outer ring protons and large positive values in calculations of nucleus-independent chemical shifts on the central cavity of the porphyrin ring provide unambiguous evidence for the antiaromatic character of the 16π Zn(II) species. A combination of magnetic circular dichroism spectroscopic studies and TD-DFT calculations on both the Zn(II) and Cu(II) species demonstrates that the main electronic bands of the dicationic species can be readily assigned by using Michl's 4N perimeter model. Femtosecond transient absorption studies clearly demonstrated that the number of π electrons on the inner ligand perimeter and the configuration of the central metal ion play a critical role in the excited-state relaxation dynamics. Redox potentials for conversion between the 16π, 17π, and 18π systems were measured by cyclic voltammetry in dichloromethane and benzonitrile, and UV/Vis spectra of each oxidation/reduction product were monitored by thin-layer spectroelectrochemistry.     

Relative contributions of porosity and mineralized matrix properties to the bulk axial ultrasonic wave velocity in human cortical bone

Velocity of ultrasound waves has proved to be a useful indicator of bone biomechanical competence. A detailed understanding of the dependence of ultrasound parameters such as velocity on bone characteristics is a key to the development of bone quantitative ultrasound (QUS). The objective of this study is to investigate the relative contributions of porosity and mineralized matrix properties to the bulk compressional wave velocity (BCV) along the long bone axis. Cross-sectional slabs from the diaphysis of four human femurs were included in the study. Seven regions of interest (ROIs) were selected in each slab. BCV was measured in through-transmission at 5 MHz. Impedance of the mineralized matrix (Z_m) and porosity (Por) were obtained from 50 MHz scanning acoustic microscopy. Por and Z_m had comparable effects on BCV along the bone axis (R = −0.57 and R = 0.72, respectively).     

Formulation study on retinoic acid gel composed of iota-carrageenan, polyethylene oxide and Emulgen® 408

In the present study, all-trans retinoic acid (RA) gels formulated with various compositions of polyethylene oxide (Emulgen?) and iota-carrageenan (ι-CG) were prepared and their physicochemical properties were evaluated. The compression energy, which is the work required to compress the product through a fixed distance, increased with increasing amount of ι-CG or Emulgen?. The adhesion energy and displacement decreased with increasing amount of ι-CG or Emulgen? due to the progression of gel formation. From the results of the sensory tests, the properties of RA gels such as adhesiveness, gel strength and spreadability seemed to be adjustable depending on the condition of skin by varying the components of RA gels. Through photostability study, the expiration date and storage conditions of RA gels were determined as "4°C for 28?d with no exposure to light."     

On a synchronization queue with two finite buffers

In this paper, we consider a synchronization queue (or synchronization node) consisting of two buffers with finite capacities. One stream of tokens arriving at the system forms a Poisson process and the other forms a PH-renewal process. The tokens are held in the buffers until one is available from each flow, and then a group-token is instantaneously released as a synchronized departure. We show that the output stream of a synchronization queue is a Markov renewal process, and that the time between consecutive departures has a phase type distribution. Thus, we obtain the throughput of this synchronization queue and the loss probabilities of each type of tokens. Moreover, we consider an extended synchronization model with two Poisson streams where a departing group-token consists of several tokens in each buffer. This revised version was published online in June 2006 with corrections to the Cover Date.     

K-Carrageenan Stimulates Pre-Osteoblast Proliferation and Osteogenic Differentiation: A Potential Factor for the Promotion of Bone Regeneration?

Current cell-based bone tissue regeneration strategies cannot cover large bone defects. K-carrageenan is a highly hydrophilic and biocompatible seaweed-derived sulfated polysaccharide, that has been proposed as a promising candidate for tissue engineering applications. Whether κ-carrageenan can be used to enhance bone regeneration is still unclear. In this study, we aimed to investigate whether κ-carrageenan has osteogenic potential by testing its effect on pre-osteoblast proliferation and osteogenic differentiation in vitro. Treatment with κ-carrageenan (0.5 and 2 mg/mL) increased both MC3T3-E1 pre-osteoblast adhesion and spreading at 1 h. K-carrageenan (0.125–2 mg/mL) dose-dependently increased pre-osteoblast proliferation and metabolic activity, with a maximum effect at 2 mg/mL at day three. K-carrageenan (0.5 and 2 mg/mL) increased osteogenic differentiation, as shown by enhanced alkaline phosphatase activity (1.8-fold increase at 2 mg/mL) at day four, and matrix mineralization (6.2-fold increase at 2 mg/mL) at day 21. K-carrageenan enhanced osteogenic gene expression (Opn, Dmp1, and Mepe) at day 14 and 21. In conclusion, κ-carrageenan promoted MC3T3-E1 pre-osteoblast adhesion and spreading, metabolic activity, proliferation, and osteogenic differentiation, suggesting that κ-carrageenan is a potential osteogenic inductive factor for clinical application to enhance bone regeneration.     

Ethylene and propylene polymerization behavior of a series of bis(phenoxy–imine)titanium complexes

This contribution reports ethylene and propylene polymerization behavior of a series of Ti complexes bearing a pair of phenoxy–imine chelate ligands. The bis(phenoxy–imine)Ti complexes in conjunction with methylalumoxane (MAO) can be active catalysts for the polymerization of ethylene. Unexpectedly, this C₂ symmetric catalyst produces syndiotactic polypropylene. ¹³C NMR spectroscopy has revealed that the syndiotacticity arises from a chain-end control mechanism. Substitutions on the phenoxy–imine ligands have substantial effects on both ethylene and propylene polymerization behavior of the complexes. In particular, the steric bulk of the substituent ortho to the phenoxy–oxygen is fundamental to obtaining high activity and high molecular weight for ethylene polymerization and high syndioselectivity for the chain-end controlled propylene polymerization. The highest ethylene polymerization activity, 3240 kg/mol-cat h, exhibited by a complex having a t-butyl group ortho to the phenoxy–oxygen, represents one of the highest reported to date for Ti-based non-metallocene catalysts. Additionally, the polypropylene produced exhibits a T_m, 140 °C, and syndioselectivity, rrrr 83.7% (achieved by a complex bearing a trimethylsilyl group ortho to the phenoxy–oxygen) that are among the highest for polypropylenes produced via a chain-end control mechanism. Hence, the bis(phenoxy–imine)Ti complexes are rare examples of non-metallocene catalysts that are useful for the polymerization of not only ethylene but also propylene.     

Polystyrene-supported TBD catalyzed ring-opening of N-tosylaziridines with silylated nucleophiles

Polystyrene-supported TBD (PS-TBD) catalyzes the ring-opening of N-tosylaziridines with silylated nucleophiles to give the corresponding products in high yields. PS-TBD was easily recovered and reused without significant loss of catalytic activity.     

Preparation and characteristics of photocrosslinkable hydrophilic polymer having cinnamate moiety

The reaction of copolymer of N,N-dimethylacrylamide (DMAA) and bromoethyl methacrylate with potassium cinnamate produced water-soluble photosensitive polymers. Photosensitive polyDMAA films were irradiated with a 400 W high-pressure mercury lamp (λ > 280 nm) to produce crosslinked polymers, which were swollen in water. The degree of swelling was controlled by the irradiation time and content of cinnamate moieties in copolymers. Higher cinnamoylation and longer irradiation time resulted in higher yield of crosslinked polymers and less swellability. Partial degelation upon irradiation at λ ～ 254 nm was observed. The advantage of gelation via photodimerization over conventional chemical crosslinking methods is discussed in conjunction with biomedical applications. © 1992 John Wiley & Sons, Inc.