Controlled vinyl-addition-type polymerization of norbornene initiated by several cobalt complexes having substituted terpyridine ligands

A series of cobalt(II) complexes having terpyridine derivatives such as 2,2^′:6^′,2″-terpyridine (1), 4,4^′,4″-^tBu₃-2,2^′:6^′,2″-terpyridine (2), 5,5″-Me₂-2,2^′:6^′,2″-terpyridine (3), 6,6″-Me₂-2,2^′:6^′,2″-terpyridine (4) and 6,6″-(3,5-Me₂C₆H₃)₂-2,2^′:6^′,2″-terpyridine (5) was synthesized. The structures of 1, 3, and 4 were confirmed by X-ray crystallography. The coordination sphere around the cobalt center in 1 can be described as pseudo square pyramidal. On the other hand, complex 4 has pseudo trigonal bipyramidal structure. Upon activation with d-MAO (dried-methylaluminoxane), these complexes showed high activities for the polymerization of norbornene (NBE). In particular, polymerization of NBE with 4/d-MAO system at room temperature resulted in quantitative yield within several hours to give the polymers with relatively narrow molecular weight distributions and controlled molecular weight. The polymerizations of NBE with these cobalt catalyst systems proceeded in vinyl addition polymerization, which was confirmed by ¹H NMR spectra of the resulting polymers.     

Study of solid-state reactions in Sm(Co,Fe, Cu,Zr)z 2:17-type alloys by means of in situ electrical resistivity measurements

In the present work, solid-state reactions in Sm₂(Co, Fe, Cu, Zr)₁₇-type alloys have been investigated by means of in situ electrical resistivity measurements. Changes in the electrical resistivity of a Sm(Co_0.74Fe_0.1Cu_0.12Zr_0.04)_8.5 alloy after solid solution treatment at 1190 °C, quenching to room temperature, and during isothermal ageing at temperatures between 400 and 900 °C, have indicated microstructural/phase changes occurring at temperatures below those commonly used for the development of high coercivity in Sm(Co, Fe, Cu, Zr)_z-type materials. Subsequent crystallographic and magnetic transition measurements have shown a high degree of correlation with respect to the changes observed in the electrical resistivity during isothermal ageing.     

Three-dimensional photofabrication with femtosecond lasers for applications in photonics and biomedicine

A status report on rapidly advancing femtosecond laser technology, three-dimensional (3D) microstructuring by multiphoton illumination technique, is given. Taking its origin from multiphoton microscopy, this technique is now becoming an important microfabrication tool. In our work we apply near-infrared Ti:sapphire femtosecond laser pulses (at 800/780 nm) for 3D material processing. When tightly focused into the volume of a photosensitive material (or photoresist), they initiate 2PP process by, for example, transferring liquid into the solid state. This allows the fabrication of any computer generated 3D structure by direct laser “recording” into the volume of photosensitive material. 2PP of photosensitive materials irradiated by femtosecond laser pulses is now considered as enabling technology for the fabrication of 3D photonic crystals and photonic crystal templates. In particular, 2PP allows one to introduce defects at any desired locations, which is crucial for the practical applications. Recently, we studied possible applications of 2PP technique in biomedicine. 2PP is a very interesting technique for the fabrication of drug delivery systems, scaffolds for tissue engineering, and medical implants. These and other biomedical applications of 2PP will be reviewed.     

Infrared investigation of benzene to 30 GPa transformation to a polymer

Abstract

After a pressure cycle to 30 GPa, benzene transforms to a white solid which can be recovered at ambient. Results obtained from infrared spectroscopy and other physico-chemical methods show that the recovered solid is a highly cross-linked polymer. The molecular structure of benzene is very likely completely altered by the transformation.     

Engineering of a two-step purification strategy for a panel of monoclonal immunoglobulin M directed against undifferentiated human embryonic stem cells

A two-step purification strategy comprising of polyethylene glycol (PEG) precipitation and anion-exchange chromatography was developed for a panel of monoclonal immunoglobulin M (IgM) (pI 5.5–7.7) produced from hybridoma cultures. PEG precipitation was optimized with regards to concentration, pH and mixing. For anion-exchange chromatography, different resins were screened of which Fractogel EMD, a polymer grafted porous resin had the highest capacity. Despite its significantly slower mass transfer, the binding capacity was still higher compared to a convection driven resin (monolith). This purification strategy was successfully demonstrated for all 9 IgMs in the panel. In small scale most antibodies could be purified to >95% purity with the exception of two which gave a lower final purity (46% and 85%). The yield was dependent on the different antibodies ranging from 28% to 84%. Further improvement of recovery and purity was obtained by the digestion of DNA present in the hybridoma supernatant using an endonuclease, benzonase. So far this strategy has been applied for the purification of up to 2 l hybridoma supernatants.     

嵌段共聚物在乳液聚合和分散聚合中的应用

综述了嵌段共聚物在乳液聚合和分散聚合中作为稳定剂应用的进展，主要讨论了共聚物化学组成，比例，分子量，浓度以及胶束形成等因素对聚合体系的影响。     

Polymerization of 4-Dimethylamino-N-propargylpyridinium Bromide by Transition Metal Catalysts

The polymerization of an ionic propargyl derivative, 4-dimethylamino-N-propargylpyridinium bromide (DMAPPB), was carried out by palladium, platinum, and ruthenium chlorides. The polymerization of DMAPPB by these transition metal catalysts proceeded well to give a relatively high polymer yield. The chemical structure of the resulting polymer was characterized by such instrumental methods as elemental analysis, infrared, NMR, UV–visible spectroscopies to have conjugated polymer backbone system bearing 4-dimethylamino-N-methylenepyridinium bromide. The polymer was soluble in DMF, DMSO, and formic acid, and found to be less hygroscopic than those of similar homologues having more smaller substituents. The resulting polymers were mostly black powders and showed the amorphous morphology.     

A 15-year record of seasonal variation in the isotopic composition of precipitation water over continental Portugal

The Nuclear and Technological Institute (Instituto Tecnológico e Nuclear—ITN) in cooperation with the International Atomic Energy Agency (IAEA) has been conducting a nationwide survey of hydrogen (²H/¹H) and oxygen (¹⁸O/¹⁶O) isotopic composition of monthly precipitation since 1988. This paper focuses on basic features of spatial and temporal distribution of δ¹⁸O and δ²H in the precipitation over Continental Portugal derived from ITN database. Phenomenological relationships between stable isotopes composition of precipitation and various climate-related parameters (local air temperature, distance to the Atlantic coast, altitude, amount of precipitation) are established and discussed.     

An effective route for the synthesis of cationic palladium complexes of general formula [(Acac)PdLL]A

A series of palladium complexes of general formula [(Acac)PdL¹L²]⁺A⁻, where L¹, L² = phosphines and A = BF₄, CF₃SO₃, were synthesized. Preliminary studies show that the complexes are active in selective dimerization of styrene and addition polymerization of norbornene.     

Nitroxide-mediated precipitation polymerization of styrene in supercritical carbon dioxide: Effects of monomer loading and nitroxide partitioning on control

Nitroxide-mediated solution and precipitation polymerizations of styrene in toluene and supercritical carbon dioxide (scCO₂), respectively, using the nitroxides N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)]nitroxide (SG1) and 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) are presented. Solution polymerizations are compared with simulations using PREDICI software, revealing that differences in the polymerization behaviours between the SG1- and TIPNO-mediated systems cannot be rationalized based on literature rate coefficients and the ideal mechanism for nitroxide-mediated polymerization. Nitroxide and monomer partitioning between the polymer particles and the continuous phase play important roles in the precipitation polymerizations in scCO₂. Loss of control (broader molecular weight distributions) as a result of nitroxide partitioning is accentuated at low monomer loading, and is significantly more pronounced for TIPNO than SG1. However, at higher monomer loading the level of control was superior in scCO₂ compared to in the corresponding solution polymerizations for both nitroxides, most likely caused by an increase in the number of activation-deactivation cycles experienced by any given chain during its growth.