Time-resolved fluorescence studies of ribonuclease T1 in reversed micelles

Time-resolved fluorescence intensity and anisotropy decay data were obtained for ribonuclease T₁ entrapped in bis(2-ethylhexyl) sodium sulfosuccinate/heptane reverse micelles, as a function of the size of the inner water pool at neutral pH. Data have been presented previously to show that this protein retains its native structure and undergoes reversible thermal unfolding in these reverse micelles (Shastry and Eftink,Biochemistry 36, in press). The fluorescence decay of entrapped protein is similar to that for the protein in buffer. The rotational correlation time of entrapped ribonuclease T₁ is found to be longer than that in buffer; this rotational correlation time decreases with increasing size of the water pool but is still over twice the value for the protein in buffer for the largest size of water pool investigated, indicating an increased microviscosity within the reverse micelle. Thermal unfolding of the protein results in a significant decrease in the rotational correlation time of the entrapped proteins, consistent with the protein being unfolded but not interacting with the inner surfactant wall of the reverse micelle.Nomenclature _i Amplitude of component i associated with fluorescence decay _i - _i Fractional intensity associated with fluorescence decay time _i - Rotational correlation time g_i Amplitude of component i associated with anisotropy decay _i - _max Fluorescence emission maximum - r_o Fundamental anisotropy of an immobilized fluorophore - _i Fluorescence lifetime of component i - W_o Ratio of water molecules per detergent molecules in a reverse micelle     

Interaction of isomeric forms of xanthophyll pigment zeaxanthin with dipalmitoylphosphatidylcholine studied in monomolecular layers

Two-component monomolecular layers were formed with DPPC and two stereoisomers of zeaxanthin 9-cis and 13-cis at the argon-water interface. Very distinct over-additivity which represents affection of a lipid arrangement in the membrane has been observed in the case of zeaxanthin 9-cis (maximum at 20 mol%) but not in the case of zeaxanthin 13-cis. The differences in the organization of the isomers of zeaxanthin-DPPC monolayers are interpreted in terms of the different orientation of both xanthophylls at the interface observed at relatively high surface pressures (>25 mN/m) comparable to the surface pressures of biomembranes. The results are consistent with the model according to which zeaxanthin 9-cis adopts a vertical orientation at the polar-nonpolar interface in contrast to zeaxanthin 13-cis, which is oriented horizontally owing to the fact that it interacts by two hydroxyl groups with the same hydrophobic-hydrophilic interface in the monolayer. The findings are discussed in comparison with the behavior of zeaxanthin in the conformation all-trans in the same system. Zeaxanthin all-trans forms efficiently molecular aggregates in the mixed monolayers in contrast to cis isomers. Circular dichroism measurements show the formation of molecular structures by zeaxanthin 13-cis that are interpreted as dimers. FTIR measurements show that these dimers are stabilized by van der Waals interactions unlike aggregated structures formed by all-trans zeaxanthin that are stabilized by hydrogen bonding. Physiological importance of the differences in aggregation and orientation of stereoisomers of zeaxanthin in lipid environment is discussed.     

A systematic SAR study of C10 modified paclitaxel analogues using a combinatorial approach

A library with 63 paclitaxel analogues modified at the C10 position of paclitaxel has been prepared using parallel solution phase synthesis. Most of the C10 analogues were slightly less active than paclitaxel in the tubulin assembly assay and had reduced potency in the B16 melanoma and MCF-7 cell line cytotoxicity assays. These modifications at C10, however, did not lead to the total loss of activity, indicating that the C10 moiety of paclitaxel may not be directly involved in the drug-microtubule interactions, but could influence its binding affinity to P-glycoprotein. Approximately 50% of the analogues demonstrated better activity against the drug resistant cell line MCF7-ADR. However, the increase in activity was 10-fold at most. This result demonstrates that the cytotoxicity against this drug resistant cancer cell line is sensitive to structural changes at the C10 position of paclitaxel. It was also found that the presence of a nitrogen atom in the C10 substituent might play a role in the interaction of analogues with microtubules.     

Inspecting the structure-activity relationship of protein kinase CK2 inhibitors derived from tetrabromo-benzimidazole

CK2 is a very pleiotropic protein kinase whose high constitutive activity is suspected to cooperate to neoplasia. Here, the crystal structure of the complexes between CK2 and three selective tetrabromo-benzimidazole derivatives inhibiting CK2 with Ki values between 40 and 400 nM are presented. The ligands bind to the CK2 active site in a different way with respect to the parent compound TBB. They enter more deeply into the cavity, establishing halogen bonds with the backbone of Glu114 and Val116 in the hinge region. A detailed analysis of the interactions highlights a major role of the hydrophobic effect in establishing the rank of potency within this class of inhibitors and shows that polar interactions are responsible for the different orientation of the molecules in the active site.     

射线理论下的浅海环境噪声场空间相干性分析及海底声学参数反演

基于射线理论,以简化海底模型为基础,获得了浅海噪声场空间相干性在频域上的表示方法,并用于海底声学参数反演。将风关海洋噪声看作分布在无限大平面上的点源,通过计算噪声场垂直方向上的能量分布,进一步获得空间两点噪声场频域相干性表达式。利用数值仿真验证了模型对于不同海底类型的敏感性。并结合噪声场空间两点的频域相干性海上实验数据,反演得到该处海域的底质类型,进一步获得海底声速、密度和声衰减系数。结果表明,反演得到的海底参数与实际情况符合较好,文中提出采用的这种计算方法能够有效的反映海底反射对于噪声场空间相干性的影响,并且可在一定程度上提高反演海底声学参数效率。     

Crystal and molecular structure of 2-(p-tolyl)-2-dehydrosparteine

The formula of the title compound is C₂₂H₃₀N₂,M _T =322.5; monoclinic:P2₁,a=7.569(3),b=9.381(1),c=13.684(4) Å,=105.81(2)°,Z=2,V _c =933.7 ų,D _x =1.15 g cm^–3,(CuK)=5.1 cm^–1. The sparteine skeleton (bis-quinolizidine system) has atrans-trans configuration. RingA has an intermediate form between the sofa and half-chair conformations, ringsB andD-chair, and ringC-boat conformations, respectively. The double bond C(2)=C(3) is equal to 1.343(9) Å. The phenyl ring is planar and makes an angle with a plane through N(1), C(2), C(3), and C(4) atoms equal to 43.9°.     

Orbit algebras that are invariant under stable equivalences of Morita type

In this note we show that there are a lot of orbit algebras that are invariant under stable equivalences of Morita type between self-injective algebras. There are also indicated some links between Auslander-Reiten periodicity of bimodules and noetherianity of their orbit algebras.     

The chloro-substituent enhances performance of 2,4-bis (imino)pyridylchromium catalysts yielding highly linear polyethylene

The five unsymmetrical 2-[1-(2,4-dibenzhydryl-6-chlorophenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridine compounds (aryl: 2,6-Me₂Ph L1 , 2,6-Et₂Ph L2 , 2,6-ⁱPr₂Ph L3 , 2,4,6-Me₃Ph L4 and 2,6-Et₂–4-MePh L5 ) were prepared and characterized with FT-IR and ¹H/¹³C NMR spectroscopy as well as elemental analysis. The treatment of L1 – L5 with CrCl₃·3THF affords the corresponding chromium chloride complexes ( Cr1 – Cr5 ) in excellent yields. The molecular structures of Cr2 and Cr3 characterized by X-ray diffraction show a distorted octahedral geometry with three nitrogen atoms and three chlorine atoms around the metal center. On activation with either MAO or MMAO, Cr1 – Cr5 collectively display high activity (up to 14.96 × 10⁶ g (PE) mol⁻¹ (Cr) h⁻¹ at 60 °C) affording highly linear polyethylene with low molecular weight distribution (M_w/M_n) ranging from 1.06 to 2.81. An in-depth catalytic evaluation of Cr1 was conducted in order to investigate how the cocatalyst type and its amount, reaction temperature and polymerization time affect the catalytic activities and polymer properties.