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Hydrophobic Segment (hydrophobic + segment)
Selected AbstractsA hydrophobic segment within the C-terminal domain is essential for both client-binding and dimer formation of the HSP90-family molecular chaperoneFEBS JOURNAL, Issue 1 2003Shin-ichi Yamada The , isoform of human 90-kDa heat shock protein (HSP90,) is composed of three domains: the N-terminal (residues 1,400); middle (residues 401,615) and C-terminal (residues 621,732). The middle domain is simultaneously associated with the N- and C-terminal domains, and the interaction with the latter mediates the dimeric configuration of HSP90. Besides one in the N-terminal domain, an additional client-binding site exists in the C-terminal domain of HSP90. The aim of the present study is to elucidate the regions within the C-terminal domain responsible for the bindings to the middle domain and to a client protein, and to define the relationship between the two functions. A bacterial two-hybrid system revealed that residues 650,697 of HSP90, were essential for the binding to the middle domain. An almost identical region (residues 657,720) was required for the suppression of heat-induced aggregation of citrate synthase, a model client protein. Replacement of either Leu665-Leu666 or Leu671-Leu672 to Ser-Ser within the hydrophobic segment (residues 662,678) of the C-terminal domain caused the loss of bindings to both the middle domain and the client protein. The interaction between the middle and C-terminal domains was also found in human 94-kDa glucose-regulated protein. Moreover, Escherichia coli HtpG, a bacterial HSP90 homologue, formed heterodimeric complexes with HSP90, and the 94-kDa glucose-regulated protein through their middle-C-terminal domains. Taken together, it is concluded that the identical region including the hydrophobic segment of the C-terminal domain is essential for both the client binding and dimer formation of the HSP90-family molecular chaperone and that the dimeric configuration appears to be similar in the HSP90-family proteins. [source] SMAP-29 has two LPS-binding sites and a central hingeFEBS JOURNAL, Issue 4 2002Brian F. Tack The CD spectra of SMAP-29, an antimicrobial peptide from sheep, showed disordered structure in aqueous buffers, and significant helicity in membrane-like environments, including SDS micelles, lipopolysaccharide (LPS) dispersions, and trifluoroethanol buffer systems. A structure determined by NMR in 40% perdeuterated trifluoroethanol indicated that residues 8,17 were helical, residues 18,19 formed a hinge, and residues 20,28 formed an ordered, hydrophobic segment. SMAP-29 was flexible in 40% trifluoroethanol, forming two sets of conformers that differed in the relative orientation of the N-terminal domain. We used a chromogenic Limulus assay to determine the EC50 of the peptide (the concentration that bound 50% of the added LPS). Studies with full-length and truncated SMAP-29 molecules revealed that each end of the holopeptide contained an LPS-binding domain. The higher affinity LPS-binding domain was situated in the flexible N-terminal portion. LPS binding to full-length SMAP-29 showed positive cooperativity, so the EC50 of the peptide (2.6 µm) was considerably lower than that of the individual LPS-binding domains. LPS-binding studies with a mixture of truncated peptides revealed that this cooperativity was primarily intramolecular (i.e. involving the N- and C-terminal LPS-binding sites of the same peptide molecule). CAP-18[106,142], an antimicrobial cathelicidin peptide of rabbits, resembled SMAP-29 in that it contained N- and C-terminal LPS-binding domains, had an EC50 of 2.5 µm, and bound LPS with positive cooperativity. We conclude that the presence of multiple binding sites that function cooperatively allow peptides such as SMAP-29 and CAP-18 to bind LPS with high affinity. [source] Ideal tetrafunctional amphiphilic PEG/PDMS conetworks by a dual-purpose extender/crosslinker.JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2005Abstract The synthesis of a new type of amphiphilic conetwork (APCN) consisting of well-defined hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments is described. The conetwork is ideal (the lengths of each PEG and PDMS chain segments, respectively, are identical) and tetrafunctional (exactly four chains emanate from each crosslink site). The synthesis of the conetworks was achieved by the use of a novel dual-purpose extender/crosslinker Y (bis [(dimethylsilyl)oxy]-[(etoxydimethylsilyl)oxy]phenylsilane, (SiPh(SiH)2OEt)), in two steps: (1) Synthesis of a new linear random multiblock copolymer (MBC) (AY)n(BY)m, where A is the hydrophilic PEG and B is the hydrophobic segment, and (2) Crosslinking the multiblocks by catalytic condensation of the SiOEt groups in the Y units. The extender/crosslinker fulfills two totally different functions: First, it extends two incompatible hydrophilic and hydrophobic prepolymers (PEG and PDMS) to a random MBC, and, subsequently, it cross-links the multiblocks to the target APCN. The synthesis and characterization of the extender/crosslinker is also presented. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4953,4964, 2005 [source] Structures and Chiroptical Properties of Thermoresponsive Block Copolymers Containing L -Proline MoietiesMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 17 2007Hideharu Mori Abstract Amino acid-based block copolymers containing poly(A-Pro-OMe) have been synthesized by RAFT polymerization using the dithioester-terminated poly(DMA) as a macro-CTA. An amphiphilic block copolymer composed of polystyrene as a hydrophobic segment and poly(A-Pro-OMe) as a hydrophilic segment was also prepared using polystyrene as the macro-CTA. The chiroptical properties of the block copolymer, poly(DMA)- block -poly(A-Pro-OMe), was evaluated by specific rotation, CD, and UV-vis spectroscopy. The assembled structure of the block copolymer on a mica surface was characterized by SFM. Thermally induced phase separations of the random and block copolymers were also studied in aqueous solution. [source] Synthesis of CdS Nanoparticles Dispersed Within Poly(urethane acrylate- co -styrene) Films Using an Amphiphilic Urethane Acrylate NonionomerMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 11 2006Ju-Young Kim Abstract Summary: CdS nanoparticles dispersed within poly(urethane acrylate- co -styrene) (PUCS) films were prepared using amphiphilic urethane acrylate nonionomer (UAN) precursor chains, which had a poly(propylene oxide)-based hydrophobic segment and a hydrophilic poly(ethylene oxide) segment. CdS nanoparticles were first prepared and dispersed in UAN/styrene mixtures, and then these nano-colloid solutions could be directly converted to CdS/PUCS nanocomposite films via radical bulk polymerization process. Formation of CdS nanoparticles was confirmed by UV absorption spectra, PL emission spectra and TEM images. The size of the CdS nanoparticles was varied from 10.2 to 14.5 nm, in correlation with the increase of amount of cadmium salt in the preparation composition, which was also confirmed by a red shift in the UV and PL emission spectra. In the course of the formation of the CdS nanoparticles within the UAN/styrene mixtures, the PEO segments of UAN are microphase-separated from the hydrophobic segments of UAN and styrene to make a complex with the cadmium cations and stabilize the CdS nanoparticles. This was also confirmed by TEM images and DMA measurements. TEM micrograph of the polyurethane acrylate films containing CdS nanoparticles, prepared using a weight fraction of cadmium acetate of 0.125 wt.-%. [source] Pyrethroid and DDT cross-resistance in Aedes aegypti is correlated with novel mutations in the voltage-gated sodium channel geneMEDICAL AND VETERINARY ENTOMOLOGY, Issue 1 2003C. Brengues Abstract. Samples of the dengue vector mosquito Aedes aegypti (L.) (Diptera: Culicidae) were collected from 13 localities between 1995 and 1998. Two laboratory strains, Bora (French Polynesia) and AEAE, were both susceptible to DDT and permethrin; all other strains, except Larentuka (Indonesia) and Bouaké (Ivory Coast), contained individual fourth-instar larvae resistant to permethrin. Ten strains were subjected to a range of biochemical assays. Many strains had elevated carboxylesterase activity compared to the Bora strain; this was particularly high in the Indonesian strains Salatiga and Semarang, and in the Guyane strain (Cayenne). Monooxygenase levels were increased in the Salatiga and Paea (Polynesia) strains, and reduced in the two Thai strains (Mae Kaza, Mae Kud) and the Larentuka strain. Glutathione S-transferase activity was elevated in the Guyane strain. All other enzyme profiles were similar to the susceptible strain. The presence of both DDT and pyrethroid resistance in the Semarang, Belem (Brazil) and Long Hoa (Vietnam) strains suggested the presence of a knock-down resistant (kdr)-type resistance mechanism. Part of the S6 hydrophobic segment of domain II of the voltage-gated sodium channel gene was obtained by RT-PCR and sequenced from several insects from all 13 field strains. Four novel mutations were identified. Three strains contained identical amino acid substitutions at two positions, two strains shared a different substitution, and one strain was homozygous for a fourth alteration. The leucine to phenylalanine substitution that confers nerve insensitivity to pyrethroids in a range of other resistant insects was absent. Direct neurophysiological assays on individual larvae from three strains with these mutations demonstrated reduced nerve sensitivity to permethrin or lambda cyhalothrin inhibition compared to the susceptible strains. [source] Perfluorocyclobutyl-containing Amphiphilic Block Copolymers Synthesized by RAFT PolymerizationCHINESE JOURNAL OF CHEMISTRY, Issue 11 2009Yongjun Chen Abstract Amphiphilic block copolymers containing hydrophobic perfluorocyclobutyl-based (PFCB) polyacrylate and hydrophilic poly(ethylene glycol) (PEG) segments were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The PFCB-containing acrylate monomer, p -(2-(p -tolyloxy)perfluorocyclobutoxy)-phenyl acrylate, was first synthesized from commercially available compounds in good yields, and this kind of acrylate monomer can be homopolymerized by free radical polymerization or RAFT polymerization. Kinetic study showed the 2,2,-azobis(isobutyronitrile) (AIBN) initiated and cumyl dithiobenzoate (CDB) mediated RAFT polymerization was in a living fashion, as suggested by the fact that the number-average molecular weights (Mn) increased linearly with the conversions of the monomer, while the polydispersity indices kept less than 1.10. The block polymers with narrow molecular weight distributions (Mw/Mn,1.21) were prepared through RAFT polymerization using PEG monomethyl ether capped with 4-cyanopentanoic acid dithiobenzoate end group as the macro chain transfer agent (mPEG-CTA). The length of the hydrophobic segment can be tuned by the feed ratio of the PFCB-based acrylate monomer and the extending of the polymerization time. The micellization behavior of the block copolymers in aqueous media was investigated by the fluorescence probe technique. [source] Synthesis and characterization of core,shell-type polymeric micelles from diblock copolymers via reversible addition,fragmentation chain transferJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2006Ping Zhang Abstract A method was developed to enable the formation of nanoparticles by reversible addition,fragmentation chain transfer polymerization. The thermoresponsive behavior of polymeric micelles was modified by means of micellar inner cores and an outer shell. Polymeric micelles comprising AB block copolymers of poly(N -isopropylacrylamide) (PIPAAm) and poly(2-hydroxyethylacrylate) (PHEA) or polystyrene (PSt) were prepared. PIPAAm- b -PHEA and PIPAAm- b -PSt block copolymers formed a core,shell micellar structure after the dialysis of the block copolymer solutions in organic solvents against water at 20 °C. Upon heating above the lower critical solution temperature (LCST), PIPAAm- b -PHEA micelles exhibited an abrupt increase in polarity and an abrupt decrease in rigidity sensed by pyrene. In contrast, PIPAAm- b -PSt micelles maintained constant values with lower polarity and higher rigidity than those of PIPAAm- b -PHEA micelles over the temperature range of 20,40 °C. Structural deformations produced by the change in the outer polymer shell with temperature cycles through the LCST were proposed for the PHEA core, which possessed a lower glass-transition temperature (ca. 20 °C) than the LCST of the PIPAAm outer shell (ca. 32.5 °C), whereas the PSt core with a much higher glass-transition temperature (ca. 100 °C) retained its structure. The nature of the hydrophobic segments composing the micelle inner core offered an important control point for thermoresponsive drug release and the drug activity of the thermoresponsive polymeric micelles. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3312,3320, 2006 [source] Synthesis of CdS Nanoparticles Dispersed Within Poly(urethane acrylate- co -styrene) Films Using an Amphiphilic Urethane Acrylate NonionomerMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 11 2006Ju-Young Kim Abstract Summary: CdS nanoparticles dispersed within poly(urethane acrylate- co -styrene) (PUCS) films were prepared using amphiphilic urethane acrylate nonionomer (UAN) precursor chains, which had a poly(propylene oxide)-based hydrophobic segment and a hydrophilic poly(ethylene oxide) segment. CdS nanoparticles were first prepared and dispersed in UAN/styrene mixtures, and then these nano-colloid solutions could be directly converted to CdS/PUCS nanocomposite films via radical bulk polymerization process. Formation of CdS nanoparticles was confirmed by UV absorption spectra, PL emission spectra and TEM images. The size of the CdS nanoparticles was varied from 10.2 to 14.5 nm, in correlation with the increase of amount of cadmium salt in the preparation composition, which was also confirmed by a red shift in the UV and PL emission spectra. In the course of the formation of the CdS nanoparticles within the UAN/styrene mixtures, the PEO segments of UAN are microphase-separated from the hydrophobic segments of UAN and styrene to make a complex with the cadmium cations and stabilize the CdS nanoparticles. This was also confirmed by TEM images and DMA measurements. TEM micrograph of the polyurethane acrylate films containing CdS nanoparticles, prepared using a weight fraction of cadmium acetate of 0.125 wt.-%. [source] Synthesis and morphology transformation of amphiphilic diblock polyurethane copolymers in aqueous solutionPOLYMER INTERNATIONAL, Issue 8 2010Qing Miao Abstract Amphiphilic block copolymers possess both hydrophobic and hydrophilic properties and can form versatile micellar structures in aqueous solution. The aim of the research presented was to prepare a series of non-ionic amphiphilic diblock polyurethane copolymers (PUn) based on isophorone diisocyanate, monoallyl-end-capped poly(ethylene oxide) and poly(propylene oxide) (PPO), followed by an investigation of their micellization properties and morphology transformation in aqueous solution. The PUn samples were synthesized by condensation polymerization. These polyurethanes exhibit surface tension as low as 33.7,37.0 mN m,1. There is an obvious decrease in critical micelle concentration as the hydrophobic PPO molecular weight increases. According to transmission electron microscopy, the morphology of aggregates of the copolymers can be tuned by varying the concentration in aqueous solution rather than organic solvent. For example, for PU7, large compound micelles are produced instead of vesicles. For PU17, the concentration can be used to control the size and thickness of vesicles. Vesicle size increases from 60 to 500 nm and vesicle thickness from 40 to 60 nm with concentration ranging from 0.003 to 0.03 wt%. The study shows that the copolymers in aqueous solution have excellent surface activities. In addition, they can self-assemble into large compound micelles or vesicles at certain concentrations. Moreover, the synthesis method described allows one to obtain a desired morphology of aggregates by adjusting the composition of hydrophilic and hydrophobic segments, which provides a novel and simple way to obtain particles on the nanometer scale. Copyright © 2010 Society of Chemical Industry [source] | |||||||||||||