Olefin polymerization on immobilized zirconocene catalysts containing alkylaluminoxanes synthesized on the support surface

Ethylene and propylene polymerization on immobilized catalysts of composition MMT-H₂O/AlR₃/Zr-cene (MMT = montmorillonite) and on the corresponding homogeneous catalysts of composition Zr-cene-MAO (Zr-cene = rac-Et(Ind)₂ZrCl₂, rac-Me₂Si(Ind)₂ZrCl₂, rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂, rac-1-(9-η⁵-Flu)2-(5,6-Cp2-Me-1-η⁵-Ind)Et]ZrCl₂) is considered. Here, the activating support for the zirconocenes is montmorillonite containing methylaluminoxane or isobutylaluminoxane synthesized directly on the monmorillonite surface by the partial hydrolysis of an alkylaluminum (AlMe₃, Al(i-Bu)₃, Al(i-Bu)₂H) with the mobile water of the support (MMT-H₂O/AlR₃). The MMT-H₂O/AlR₃ supports are demonstrated to be effective activators for ansa-zirconocenes. The catalytic properties of the immobilized systems (process kinetics and efficiency, the molar mass of the resulting polymer, and the structure of the macromolecules) depend on the activating support and the zirconocene precatalyst. The complexes of the MMT-H₂O/Al(i-Bu)₃ support with all zirconocene precatalysts are more active in propylene polymerization than the same complexes of MMT-H₂O/AlMe₃. The zirconcenes immobilized on MMT-H₂O/AlR₃ afford polyethylene and polypropylene with a higher molar mass than the corresponding homogeneous systems. Furthermore, immobilization causes activesite heterogeneity. As compared to the homogeneous single-site catalysts of composition Zr-cene-MAO, the corresponding catalysts immobilized on MMT-H₂O/AlR₃/Zr-cene are more stereospecific in the case of rac-Me₂Si(Ind)₂ZrCl₂ (C ₂ symmetry) and are less stereospecific in the case of rac-[1-(9-η⁵-Flu)2-(5,6-Cp-2-Me-1-η⁵-Ind)Et]ZrCl₂ (C _s symmetry).     

Synthetically Tuning the 2‐Position of Halogenated Quinolines: Optimizing Antibacterial and Biofilm Eradication Activities via Alkylation and Reductive Amination Pathways

Agents capable of eradicating bacterial biofilms are of great importance to human health as biofilm‐associated infections are tolerant to our current antibiotic therapies. We have recently discovered that halogenated quinoline (HQ) small molecules are: 1) capable of eradicating methicillin‐resistant Staphylococcus aureus (MRSA), methicillin‐resistant Staphylococcus epidermidis (MRSE) and vancomycin‐resistant Enterococcus faecium (VRE) biofilms, and 2) synthetic tuning of the 2‐position of the HQ scaffold has a significant impact on antibacterial and antibiofilm activities. Here, we report the chemical synthesis and biological evaluation of 39 HQ analogues that have a high degree of structural diversity at the 2‐position. We identified diverse analogues that are alkylated and aminated at the 2‐position of the HQ scaffold and demonstrate potent antibacterial (MIC≤0.39 μm ) and biofilm eradication (MBEC 1.0–93.8 μm ) activities against drug‐resistant Staphylococcus aureus, Staphylococcus epidermidis and Enterococcus faecium strains while demonstrating <5 % haemolysis activity against human red blood cells (RBCs) at 200 μm . In addition, these HQs demonstrated low cytotoxicity against HeLa cells. Halogenated quinolines are a promising class of antibiofilm agents against Gram‐positive pathogens that could lead to useful treatments against persistent bacterial infections.     

Capillary zone electrophoresis tandem mass spectrometry detects low concentration host cell impurities in monoclonal antibodies

We have evaluated CZE‐ESI‐MS/MS for detection of trace amounts of host cell protein impurities in recombinant therapeutics. Compared to previously published procedures, we have optimized the buffer pH used in the formation of a pH junction to increase injection volume. We also prepared a 5‐point calibration curve by spiking 12 standard proteins into a solution of a human mAb. A custom CZE‐MS/MS system was used to analyze the tryptic digest of this mixture without depletion of the antibody. CZE generated a ～70‐min separation window (～90‐min total analysis duration) and ～300‐peak capacity. We also analyzed the sample using ultra‐performance LC‐MS/MS. CZE‐MS/MS generated approximately five times higher base peak intensity and more peptide identifications for low‐level spiked proteins. Both methods detected all proteins spiked at ～100 ppm level with respect to the antibody.     

Investigation of stereoisomers of 4-alkenyl-trans-decahydroquinol-4-ols in mixtures by the method of reaction chromato-mass spectrometry

The mass spectra of the appropriate 4-ethyl derivatives, which provide the determination of the configuration of the 4 position in the initial alcohols, are registered in the chromato-mass spectrometric investigation of mixtures of the stereoisomeric 4-vinyl-trans-decahydroquinol-4-ols using a microreactor for hydrogenation; the microreactor is placed before or after the chromatographic column.Communication 13 of the series Reaction chromato-mass spectrometry. For Communication 12, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1215–1217, September, 1986     

Synthesis of optically active analogs of α-tocopherol based on (S)-(+)-dihydromyrcene

New optically active analogs of α-tocopherol (vitamin E) were synthesized starting from enantiomerically enriched (ee≈50%) (S)-(+)-dihydromyrcene. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1631–1634, September, 2000.     

The effect of anions in the coordination spherè of Mg complexes ofN-acetyldehydrophenylalanyl-(S)-valine on the diastereoselectivity of hydrogenation

Diastereoselective hydrogenation in ethanol over Pd/C ofN-acetyldehydrophenylalanyl-(S)-valine (1) as complexes with Mg salts of strong acids gives predominantlyN-acetyl-(S)-phenylalanyl-(S)-valine (de up to 60%). In the case of complexes of1 with Mg salts of weak acids, the sign of asymmetric induction changes. Data of¹⁹F NMR spectroscopy ofN-acetyldehydro(p-fluorophenylalanyl)-(S)-valine indicate that in the former case, the anion of a strong acid does not enter the coordination sphere of the complex, whereas in the larter case, the anion of the weak acid does. The nature of the solvent also influences the reaction stereoselectivity. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1704–1706, September, 1999.     

N-Methyl-N-(2-phenylethenyl)trifluoromethanesulfonamide

Russian Journal of Organic Chemistry -     

Measurement of the luminescence decay times of PbS quantum dots in the near-IR spectral range

Methods for recording luminescence decay times of semiconductor PbS quantum dots (QDs) with optical transitions in the near-IR spectral range have been analyzed. A measuring complex for spectral and kinetic analysis in the near-IR range (0.8?C2.0 ??m) in the time interval from several tens of nanoseconds to several tens of microseconds is described. In this complex, a semiconductor picosecond laser is used as an excitation source; luminescence decay times are recorded by a fast InGaAs photodiode, a high-speed amplifier, and a high-frequency oscilloscope; and the measurement results are multiply averaged (up to a million times) by a program. The technical features of this method are discussed and compared with the characteristics of techniques based on photon counting or application of more powerful radiation sources, and the limitations on sensitivity are analyzed. The results of measuring the luminescence decay kinetics of PbS QDs 2.7?C7.6 nm in size prepared in the form of solutions and incorporated into matrices are reported.     

Estimate of stability of reconstruction of the exponential type

The problem of estimation of stability of reconstruction of the multiplicative exponential type is investigated. Some estimates of the stability are derived. Proceedings of the Seminar on Stability Problems for Stochastic Models, Hajdúszoboszló, Hungary, 1997, Part I.