Adduct formation properties of mono- and bidentate phosphine oxide compounds in the liquid—liquid extraction of some divalent metals with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone

The bidentate phosphine oxide compounds bis(diphenylphosphinyl)methane (BDPPM) and bis(diphenylphosphinyl)ethane (BDPPE) were synthesized and the liquid—liquid extraction equilibria of some divalent metal ions such as Co(II), Ni(II), Zn(II) and Cd(II) with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP) and the neutral phosphine oxide compounds were investigated. BDPPM was found to be much more powerful than BDPPE and the monodentate neutral ligand trioctylphosphine oxide (TOPO). The composition of the extracted species were determined by a graphical method to be M(PMBP)₂(TOPO)_s (s = 2 for Co, Ni, Cd and s = 1 for Zn), M(PMBP)₂(BDPPM) and M(PMBP)₂(BDPPE). The adduct formation constants between the acylpyrazolone chelates and the neutral ligands were determined and are discussed in terms of the molecular structure.     

A Convenient Preparation of p-Chloromethyl-Styrene and its Reactions

In the present communication we would like to describe a novel method for the preparation of p-chloromethylstyrene and some reactions of this compound.     

Biodegradable Polyurethanes from Plant Components

Abstract

Polyurethane (PU) sheets and foams having plant components in their network were prepared by using the following procedure. Polyethylene glycol (PEG) was mixed with one of the following; molasses, lignin, woodmeal, or coffee grounds. The mixture obtained was reacted with diphenylmethane diisocyanate (MDI) at room temperature, and precured PUs were prepared. The precured PUs were heat-pressed and PU sheets were obtained. In order to make PU foam, the above mixture was reacted with MDI after the addition of plasticizer, surfactant (silicone oil), catalyst (di-n-butyltin dilaurate), and droplets of water under vigorous stirring. The glass transition temperature, tensile and compression strengths, and Young's modulus of the PU sheets and foams increased with an increasing amount of plant components. This suggests that saccharide and lignin residues act as hard segments in PUs. It was found that the PUs obtained were biodegradable in soil. The rate of biodegradation of the PUs derived from molasses and coffee grounds was between that of cryptomeria (Cryptomeria japonica) and beech (Fagus sieboldi).     

X-ray structure analysis of trans-1,4-polybutadiene

The crystal structure of trans-1,4-polybutadiene has been reported by Natta et al. to be pseudo-hexagonal below its solid-phase transition temperature. In the present X-ray structure analysis, it is revealed that the crystal belongs to the monoclinic system with the space group P2¹/a. The unit cell, with the lattice constants a = 8.63 Å, b = 9.11 Å, c = 4.83 Å, and β = 114°, includes four molecular segments.     

Design of Chitosan-5Fu Conjugate Exhibiting Antitumor Activity

In order to provide a macromolecular prodrug of 5-fluorouracil (5FU) reducing the side effects, having an affinity for tumor cells, and exhibiting strong antitumor activity, the covalent attachments of 5FUs to chitosan and chitosamino-oligosaccharide (COS) through hexamethylene spacer groups via urea, urea bonds were carried out. The effect of prolongation of life was tested in vivo against p388 lyrnphocytic leukemia in female CDF, mice by intra-peritoneal (i.p.) transplantation/i.p. injection and the growth-inhibitory effect on Meth-A fibrosarcoma or MH-134Y heputoma was evaluated in vivo in SPF-C3H/He scl male or Balb/c male mice by subcutaneous (s.c.) implantation/intravenous (i.v.) injection. The effects of the degree of polymerization of chitosan and     

Optical Polymer Having a High Refractive Index and High Abbe Number Prepared by Radical Polymerization Using 2,5-BiS(2-Thia-3-Butenyl)-1,4-Dithiane

Abstract

Novel poly(vinylsulfide)s were prepared by addition polymerization using 2,5-bis(2-thia-3-butenyl)-1,4-dithiane (TBD) with a radical initiator for an optical polymer having a high refractive index (n_D) and Abbe number (v). Homopolymerization of TBD (72.9% conversion) and copolymerization with acrylonitrile or acrylates having nonpolar groups (50.4–81.3% conversion according to the comonomers used) in a limited composition range yielded hard and transparent polymers suitable for application in optics. The methacrylates used yielded no polymeric product as a result of the copolymerization. The obtained polymers had T_g, n_D and v ranging between 41.0–124.0°C, 1.678–1.546 and 34.1–43.8, respectively, except that poly(TBD) did not exhibit T_g below 200°C, and it had the highest n_D Most of the polymers have higher n_D and v than those of other conventional optical polymers and moreover, their values are comparable to those of flint glasses. The copolymerizability of TBD and the group contribution to n_D and v are discussed based on the Q-e scheme and on the Lorentz-Lorenz equation, respectively. This work shows that TBD serves as a useful material for the preparation of polymers having high n_D and v along with a T_g of more than 100°C, and that the polymers thus obtained are promising optical materials.

     

The Effect of β-Nitro Group on the Reactivity and the Stereoselectivity of Amidation of Bicyclic Acids by Dehydration with DCC

Amidation of exo/endo mixture of β-nitro bicyclic acids by dehydration with DCC, gives only the corresponding exo-amides.     

A novel condition for capillary electrophoretic analysis of reductively aminated saccharides without removal of excess reagents

We have identified novel CE conditions for the separation of 7‐amino‐4‐methylcoumarin‐labeled monosaccharides and oligosaccharides from glycoproteins. Using a neutrally coated capillary and alkaline borate buffer containing hydroxypropylcellulose and ACN, saccharide derivatives form anionic borate complexes, which move from the cathode to the anode in an electric field and are detected near the anodic end. Excess labeling reagents and other fluorescent products remain at the cathodic end. Fluorimetric detection using an LED as a light source enables determination of monosaccharide derivatives with good linearity between at least 0.4 and 400 μM, may correspond to 140 amol to 140 fmol. The lower LOD (S/N = 5) is only 80 nM in the sample solution (ca. 28 amol). The results were comparable to reported values using fluorometric detection LC. The method was also applied to the analysis of oligosaccharides that were enzymatically released from glycoproteins. Fine resolution enables profiling of glycans in glycoproteins. The applicability of the method was examined by applying it to other derivatives labeled with nonacidic tags such as ethyl p‐aminobenzoate‐ and 2‐aminoacridone‐labeled saccharides.