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1.
Supramolecular fibrous materials in biological systems play important structural and functional roles, and therefore, there is a growing interest in synthetic materials that mimic such fibrils, especially those bearing enzymatic reactivity. In this study, we investigated the self-assembly and enzymatic post-modification of short aromatic peptide amphiphiles (PAs), Fmoc-LnQG (n = 2 or 3), which contain an LQG recognition unit for microbial transglutaminase (MTG). These aromatic PAs self-assemble into fibrous structures via π-π stacking interactions between the Fmoc groups and hydrogen bonds between the peptides. The intermolecular interactions and morphologies of the assemblies were influenced by the solution pH because of the change in the ionization states of the C-terminal carboxy group of the peptides. Moreover, MTG-catalyzed post-modification of a small fluorescent molecule bearing an amine group also showed pH dependency, where the enzymatic reaction rate was increased at higher pH, which may be because of the higher nucleophilicity of the amine group and the electrostatic interaction between MTG and the self-assembled Fmoc-LnQG. Finally, the accumulation of the fluorescent molecule on these assembled materials was directly observed by confocal fluorescence images. Our study provides a method to accumulate functional molecules on supramolecular structures enzymatically with the morphology control.  相似文献   

2.
Preparation of Pt-loaded TiO2 nanofibers and their catalytic performance for water gas shift (WGS) reactions have been explained in this work. The Pt-loaded TiO2 nanofibers were obtained by electrospinning poly-ethylene oxide (PEO) aqueous solutions containing Ti(OH)n slurry and Pt nanoparticles at room temperature, followed by calcination at 773 K for 4 h. The calcined nanofibers were rougher than the nanofibers of PEO/Ti(OH)n/Pt due to the PEO degradation and oxidation of Ti(OH)n to TiO2. Diameters of the Pt-loaded TiO2 nanofibers ranged between 200 and 900 nm. Catalytic activity of the Pt-loaded TiO2 nanofibers for water gas shift (WGS) reactions was evaluated and it was observed that their activity was 5–7 times higher than that of a bulk catalyst. Such improvement is attributed to the larger surface area of the nanofiber catalyst compared to that of the bulk catalyst. To the best of our knowledge, this is the first demonstration of a synthesis of Pt-loaded TiO2 nanofibers from a Ti(OH)n nanoparticle slurry using electrospinning and its application to WGS reactions.  相似文献   

3.
Bronchopulmonary dysplasia (BPD) is one of the most common complications of prematurity, occurring in 30% of very low birth weight infants. The benefits of dietary intake of polyunsaturated fatty acids ω-3 (PUFA ω-3) during pregnancy or the perinatal period have been reported. The aim of this study was to assess the effects of maternal PUFA ω-3 supplementation on lung injuries in newborn rats exposed to prolonged hyperoxia. Pregnant female Wistar rats (n = 14) were fed a control diet (n = 2), a PUFA ω-6 diet (n = 6), or a PUFA ω-3 diet (n = 6), starting with the 14th gestation day. At Day 1, female and newborn rats (10 per female) were exposed to hyperoxia (O2, n = 70) or to the ambient air (Air, n = 70). Six groups of newborns rats were obtained: PUFA ω-6/O2 (n = 30), PUFA ω-6/air (n = 30), PUFA ω-3/O2 (n = 30), PUFA ω-3/air (n = 30), control/O2 (n = 10), and control/air (n = 10). After 10 days, lungs were removed for analysis of alveolarization and pulmonary vascular development. Survival rate was 100%. Hyperoxia reduced alveolarization and increased pulmonary vascular wall thickness in both control (n = 20) and PUFA ω-6 groups (n = 60). Maternal PUFA ω-3 supplementation prevented the decrease in alveolarization caused by hyperoxia (n = 30) compared to PUFA ω-6/O2 (n = 30) or to the control/O2 (n = 10), but did not significantly increase the thickness of the lung vascular wall. Therefore, maternal PUFA ω-3 supplementation may protect newborn rats from lung injuries induced by hyperoxia. In clinical settings, maternal PUFA ω-3 supplementation during pregnancy and during lactation may prevent BPD development after premature birth.  相似文献   

4.
Article describes the synthesis of fifteen β-hydroxy-β-arylalkanoic acids by Reformatsky reaction using the 1-ethoxyethyl-2-bromoalkanoates, aromatic or cycloalkyl ketones or aromatic aldehydes. The short survey of previously reported synthetic procedures for title compounds, is given. The majority of obtained compounds exert antiproliferative activity in vitro toward human: HeLa, Fem-X cells, K562, and LS174 cells, having IC50 values from 62.20 to 205 μM. The most active compound is 3-OH-2,2-di-Me-3-(4- biphenylyl)-butanoic acid, having the IC50 value 62.20 μM toward HeLa cells. Seven examined compounds did not affect proliferation of healthy human blood peripheral mononuclear cells (PBMC and PBMC+ PHA), IC50 > 300 μM. The preliminary QSAR results show that estimated lipophilicity of compounds influences their antiproliferative activity in the first place. The ability of dehydration, and the spatial arrangement of hydrophobic portion, HBD and HBA in molecules are has almost equal importance as lipophilicity.  相似文献   

5.
Inhibition of the molecular chaperone heat shock protein 90 (Hsp90) represents a promising approach for cancer treatment. BIIB021 is a highly potent Hsp90 inhibitor with remarkable anticancer activity; however, its clinical application is limited by lack of potency and response. In this study, we aimed to investigate the impact of replacing the hydrophobic moiety of BIIB021, 4-methoxy-3,5-dimethylpyridine, with various five-membered ring structures on the binding to Hsp90. A focused array of N7/N9-substituted purines, featuring aromatic and non-aromatic rings, was designed, considering the size of hydrophobic pocket B in Hsp90 to obtain insights into their binding modes within the ATP binding site of Hsp90 in terms of π–π stacking interactions in pocket B as well as outer α-helix 4 configurations. The target molecules were synthesized and evaluated for their Hsp90α inhibitory activity in cell-free assays. Among the tested compounds, the isoxazole derivatives 6b and 6c, and the sole six-membered derivative 14 showed favorable Hsp90α inhibitory activity, with IC50 values of 1.76 µM, 0.203 µM, and 1.00 µM, respectively. Furthermore, compound 14 elicited promising anticancer activity against MCF-7, SK-BR-3, and HCT116 cell lines. The X-ray structures of compounds 4b, 6b, 6c, 8, and 14 bound to the N-terminal domain of Hsp90 were determined in order to understand the obtained results and to acquire additional structural insights, which might enable further optimization of BIIB021.  相似文献   

6.
To date, conjugated microporous polymers (CMPs) have been developed into multifaceted photocatalysts. Here, two CMPs based on pyrene with the linkages of thiazolo[5,4-d]thiazole (TzTz) are prepared for visible light photocatalysis. The dimension of the molecular building block’s symmetry on the property and activity of CMPs is systematically investigated. Py(4)-TzTz-CMP with a pyrene building block of D2h symmetry gives rise to better optoelectronic property than Py(2)-TzTz-CMP with a pyrene building block of C2 symmetry. Therefore, Py(4)-TzTz-CMP photocatalyst is endowed with superior conversions for the green light-promoted oxygenation of sulfides with O2. Intriguingly, mechanistic explorations disclose that both superoxide and singlet oxygen are responsible for the production of the target sulfoxides. This work gives insight into the rational design of highly active CMP photocatalysts for selective chemical transformations.  相似文献   

7.
We report on the self-assembly, in water and in bulk, of amphiphilic liquid crystal block copolymers consisting of a cholesterol-based smectic LC polymer block (PAChol) and poly(ethylene glycol) (PEG) block. Two series of block copolymers, PEG45-b-PAChol and PEG114-b-PAChol (45 and 114 are the degree of polymerization of PEG blocks) with different hydrophilic/hydrophobic weight ratios were synthesized and characterized in detail. Depending on the diblock composition, smectic polymer vesicles and/or nanofibers were formed by adding water into a dilute solution of copolymers in dioxane. If THF is used instead of dioxane as solvent, solid spherical aggregates were obtained upon water addition for PEG45-b-PAChol series, while macroscopic precipitation occurred for PEG114-b-PAChol series. The mesomorphic and microphase segregation structures of the block copolymers in bulk were studied by X-ray scattering, DSC and POM. The interdigital smectic A (SmAd) phase with a lamellar period of 4.25 nm was detected in all block copolymers. For PEG114-b-PAChol5 (PEG/PAChol weight ratio = 66/34) and PEG114-b-PAChol12 (45/55), lamellar type of microphase segregation was observed.  相似文献   

8.
Recent studies have shown that the surfactants bearing an ultra-long hydrophobic chain (>C18) exhibit unique self-assembly properties. However, their synthesis and surface activities have been less documented. In this work, monounsaturated alkyl dimethyl amidopropyl betaines, UCnDAB (n?=?18, 22, and 24), were prepared by the reaction of the corresponding fatty acids with N,N-dimethyl-1,3-propanediamine, followed by quaternization with sodium choloroacetate of the obtained intermediates. The intermediates and final surfactants were characterized by 1H NMR and ESI-HRMS, respectively. Krafft temperature (T K) and surface activities of the surfactants were also examined. It was found that T K of all these surfactants is lower than 0?°C, and their critical micellar concentration (CMC) is within the range of 10?3?mmol/L. In addition, the linear relationship between lg CMC and n is still in evidence.  相似文献   

9.
Recent progress in the de novo design of self-assembling peptides has enabled the construction of peptide-based viral capsids. Previously, we demonstrated that 24-mer β-annulus peptides from tomato bushy stunt virus spontaneously self-assemble into an artificial viral capsid. Here we propose to use the artificial viral capsid through the self-assembly of β-annulus peptide as a simple model to analyze the effect of molecular crowding environment on the formation process of viral capsid. Artificial viral capsids formed by co-assembly of fluorescent-labelled and unmodified β-annulus peptides in dilute aqueous solutions and under molecular crowding conditions were analyzed using fluorescence correlation spectroscopy (FCS). The apparent particle size and the dissociation constant (Kd) of the assemblies decreased with increasing concentration of the molecular crowding agent, i.e., polyethylene glycol (PEG). This is the first successful in situ analysis of self-assembling process of artificial viral capsid under molecular crowding conditions.  相似文献   

10.
New head-to-head type polythiophenes with acetylenic -CCR side groups, HH-P3(CCR)Th (R=n-C10H21, n-C6H13, n-C4H9), were prepared by palladium-catalyzed polycondensation of the corresponding dibromo-monomers by using Me3SnSnMe3 as the polycondensing agent. The single crystal structure of the monomer revealed high coplanarity of the bithiophene unit, and the derived polymer showed a UV-vis absorption peak at approximately 520 nm. The λmax position was red-shifted from those of regioregular poly(3-alkylthiophene)s (385 and 430 nm for HH- and HT-type polymers, respectively). These data indicate that the newly synthesized polythiophene with the -CCR group has a highly coplanar structure with a large effective π-conjugation system.  相似文献   

11.
The inhibition of the enzyme dipeptidyl-peptidase IV (DPP-IV) is an effective pharmacotherapeutic approach for the management of type 2 diabetes. Recent findings have suggested that dietary proteins, including bovine α-lactalbumin, could be precursors of peptides able to inhibit DPP-IV. However, information on the location of active peptide sequences within the proteins is far from being comprehensive. Moreover, the traditional approach to identify bioactive peptides from foods can be tedious and long. Therefore, the objective of this study was to use peptide arrays to screen α-lactalbumin-derived peptides for their interaction with DPP-IV. Deca-peptides spanning the entire α-lactalbumin sequence, with a frame shift of 1 amino acid between successive sequences, were synthesized on cellulose membranes using “SPOT” technology, and their binding to and inhibition of DPP-IV was studied. Among the 114 α-lactalbumin-derived decamers investigated, the peptides 60WCKDDQNPHS69Ki = 76 µM), 105LAHKALCSEK114 (Ki = 217 µM) and 110LCSEKLDQWL119 (Ki = 217 µM) were among the strongest DPP-IV inhibitors. While the SPOT- and traditionally-synthesized peptides showed consistent trends in DPP-IV inhibitory activity, the cellulose-bound peptides’ binding behavior was not correlated to their ability to inhibit the enzyme. This research showed, for the first time, that peptide arrays are useful screening tools to identify DPP-IV inhibitory peptides from dietary proteins.  相似文献   

12.
Fullerene-Nafion composite membranes have been fabricated through a new solution casting for the first time. The fullerenes used for the composites included C60 and polyhydroxy fullerene (PHF), C60(OH)n (n ∼ 12). The dispersion of the fullerene in the composite membrane was much more refined with smaller agglomeration particles, relative to the previously prepared fullerene-Nafion composites in which the fullerene was introduced through doping. The miscibility of the hydrophobic fullerene, C60, in the Nafion matrix was further improved by a new fullerene dispersant, poly[tri(ethylene oxide)benzyl]fullerene, C60[CH2C6H4(OCH2CH2O)3OCH3]n (n ∼ 5), synthesized in this work. The solution-cast fullerene composites also demonstrated a significant improvement in the physical stability relative to the fullerene-doped Nafion composites through a better integration of the fullerene into the Nafion matrix. Furthermore, increased loadings of the fullerene in Nafion were made possible through the new solution-casting method, compared to the previous doping method. The water characteristics in the fullerene composites have been examined by TGA and 1H pulse NMR measurements. The interactions between the fullerene and the Nafion have been studied through ATR FT-IR and molecular dynamics simulations which suggested PHF resides primarily in the hydrophobic domain of Nafion when the loading was low. The voltammetric measurements also have shown that the fullerene composites have the reduced limiting current density, compared to Nafion membranes without fullerenes.  相似文献   

13.
Multiwalled carbon nanotube/nylon-6 nanocomposites (MWNT/nylon-6) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and pristine MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced aromatic amine (COC6H4-NH2) groups onto the side wall. Scanning electron microscopy (SEM) images obtained from the fractured surfaces of the nanocomposites showed that the F-MWNTs in the nylon-6 matrix were well dispersed as compared to those of the P-MWNTs. Both nanocomposites could be electrospun into nanofibers in which the MWNTs were embedded and oriented along the nanofiber axis, as confirmed by transmission electron microscopy. The specific strength and modulus of the MWNTs-reinforced nanofibers increased as compared to those of the neat nylon-6 nanofibers. The crystal structure of the nylon-6 in the MWNT/nylon-6 nanofibers was mostly γ-phase, although that of the MWNT/nylon-6 films, which were prepared by hot-pressing the pellets between two aluminum plates and then quenching them in icy water, was mostly α-phase, indicating that the shear force during electrospinning might favor the γ-phase, similarly to the conventional fiber spinning.  相似文献   

14.
Multiwalled carbon nanotube/polycaprolactone nanocomposites (MWNT/PCL) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and unfunctionalized MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced the aromatic amine (COC6H4-NH2) groups on the side wall. The F-MWNTs were chemically bonded with the PCL chains in the F-MWNT/PCL, as indicated by the appearance of the amide II group in the FT-IR spectrum. The TGA thermograms showed that the F-MWNT/PCL had better thermal stability than PCL and P-MWNT/PCL. The PCL and the nanocomposite nanofibers were prepared by an electrospinning technique. The nanocomposites that contain more than 2 wt% of MWNTs were not able to be electrospun. The bead of the F-MWNT/PCL nanofiber was formed less than that of the P-MWNT/PCL. The nanocomposite nanofibers showed a relatively broader diameter than the pure PCL nanofibers. The MWNTs were embedded within the nanofibers and were well oriented along the axes of the electrospun nanofibers, as confirmed by transmission electron microscopy.  相似文献   

15.
Multiwalled carbon nanotube/Polyacrylonitrile (MWNT/PAN) composite nanofibers were prepared by electrospinning technique, whereby functionalized MWNTs (F-MWNTs) and pristine MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced aromatic amine (COC6H4-NH2) groups onto the sidewall. The diameter range of the PAN nanofibers was 400-100 ± 50 nm. The beads formation was also observed when the amounts of MWNTs were increased in the PAN solution. The bead formation in F-MWNT/PAN composite nanofibers was less as compared to P-MWNT/PAN. The MWNTs were embedded within nanofibers and were well oriented along the nanofiber axis, as confirmed by transmission electron microscopy. The mechanical and thermal properties of the PAN nanofibers were improved by the incorporation of MWNTs.  相似文献   

16.
Liang Tong  Dong Yang  Yongjun Li  Guolin Lu 《Polymer》2009,50(11):2341-2348
We present the synthesis and self-assembly behavior of a new semi-fluorinated amphiphilic triblock copolymer. A series of perfluorocyclobutyl aryl ether-based amphiphilic ABA triblock copolymer containing hydrophilic poly(ethylene glycol) segment as the middle block were synthesized by atom transfer radical polymerization (ATRP). ATRP of 4-(4′-p-tolyloxyperfluorocyclobutoxy)benzyl methacrylate was initiated by PEG-based bifunctional macroinitiators with different molecular weights to obtain the desired copolymers with narrow molecular weight distributions (Mw/Mn ≤ 1.30) and the number of perfluorocyclobutyl linkage can be tuned by the feed ratio and the conversion of the fluorine-containing methacrylic monomer. The critical micelle concentrations of these amphiphilic ABA triblock copolymers in aqueous media were determined by fluorescence probe technique. They could aggregate to form spherical and cylindrical micelles visualized by TEM with varying the content of hydrophobic segment.  相似文献   

17.
The reaction of a pyridinium-containing ligand precursor with manganese(II) chloride and sodium azide yielded a Mn(II) coordination polymer, [MnLN3]n·1.5nH2O, where L is 1-(tetrazolato-5-methyl)pyridinium-4-carboxylate, a bifunctional zwitterionic ligand generated in situ from a non-coordinative precursor via two organic reactions (cyano-to-azide cycloaddition and ester hydrolysis). In the compound, metal ions are connected into uniform chains by the triple bridges consisting of μ-1,1-azide, μ-2,3-tetrazolate and μ-1,3-carboxylate, and the formally anionic chains are charge compensated and interlinked into 2D layers by the cationic 1-methylenepyridinium backbone of the L ligand. The compound displays typical 1D antiferromagnetism with J =  2.37 cm 1 through the triple bridges. Magneto-structural analysis indicates the antiferromagnetic interaction increases as the Mn–N–Mn angle of the azide bridge decreases.  相似文献   

18.
Poly(l-lactide) (PLLA) polymers having terminal n-alkyl groups with a wide variety of lengths (C0–C22) were synthesized by ring-opening polymerization of l-lactide in the presence of coinitiators of l-lactic acid (C0), 1-hexanol (C6), 1-dodecanol (C12), and 1-docosanol (C22) and their segmental mobility and non-isothermal and isothermal crystallization behavior were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffractometry (WAXD). Glass transition and cold crystallization temperatures of melt-quenched samples during heating decreased with an increase in the length of terminal n-alkyl groups. The enhanced PLLA segmental mobility and hydrophobic interaction-based accelerated PLLA nucleation by the presence of terminal long n-alkyl groups should have caused the accelerated non-isothermal and isothermal crystallization of PLLA segments traced by cold crystallization temperature during heating and by radial growth rate of spherulites, respectively. The crystallization accelerating effect became higher with the length of terminal n-alkyl groups. The effects of the length of terminal n-alkyl group on the crystalline growth mechanism of PLLA at the lowest crystallizable temperature was insignificant, whereas the effects of the length of terminal n-alkyl group on the nucleation mechanism of PLLA chains were significant and insignificant for PLLA having Mn of 6–7 × 103 of 2 × 104 g mol−1, respectively. WAXD measurements revealed that the transition crystallization temperature at which crystalline modification changes from δ-form to α-form was affected by the length of terminal n-alkyl group for PLLA having Mn of 6–7 × 103 g mol−1, but was not altered by the length of terminal n-alkyl group for PLLA having Mn of 2 × 104 g mol−1.  相似文献   

19.
In this paper, in terms of the concentration of an aqueous solution of a surfactant, we investigate the self-assembly behavior of a porphyrin, 5, 10, 15, 20-tetra(4-pyridyl)-21H, 23H-porphine [H2TPyP], by using an oil/water system as the medium. We find that when a chloroform solution of H2TPyP is dropwise added into an aqueous solution of cetyltrimethylammonium bromide [CTAB] with a lower concentration, a large amount of irregular nanoarchitectures, together with a small amount of well-defined shuttle-like nanostructures, hollow nanospheres, and nanotubes, could be produced. While a moderate amount of shuttle-like nanostructures accompanied by a few irregular nanoarchitectures, solid nanospheres, and nanorods are produced when a CTAB aqueous solution in moderate concentration is employed, in contrast, a great quantity of shuttle-like nanostructures together with a negligible amount of solid nanospheres, nanofibers, and irregular nanostructures are manufactured when a high-concentration CTAB aqueous solution is involved. An explanation on the basis of the molecular geometry of H2TPyP and in terms of the intermolecular π-π interactions between H2TPyP units, and hydrophobic interactions between CTAB and H2TPyP has been proposed. The investigation gives deep insights into the self-assembly behavior of porphyrins in an oil/water system and provides important clues concerning the design of appropriate porphyrins when related subjects are addressed. Our investigation suggests that an oil/aqueous system might be an efficient medium for producing unique organic-based nanostructures.  相似文献   

20.
The amphiphilic gels based on hydrophobically modified dimethylaminoethyl methacrylate with different 1-bromoalkanes (1-CnH2n+1Br, n = 2, 4, 6, 8, 12) were synthesized by radiation-induced polymerization and crosslinking. The length of alkyl side chains had significant influence on the swelling behavior of the resulting gels. The swelling degree of the gels decreased with the increase of side chain length, and the gel hardly swelled when n = 12. The effect of temperature and ionic strength on the swelling behavior of the resulting gels revealed that (1) the gels with longer side chains (n ≥ 8) had upper critical solution temperature, while other gels were not thermo-sensitive. (2) Antipolyelectrolyte effect was observed when immersing the gels (n ≥ 8) in NaCl solutions in certain concentration range. The dramatic difference in swelling behavior was attributed to the different gel structures. The gels with short side chains (n ≤ 6) had cellular structure of normal polyelectrolyte gels. The gels (n ≥ 8) had an aggregation gel structure caused by the hydrophobic interaction among alkyl groups and the formation of ion-cluster between tetra-alkyl ammonium cation and Br, which had been analyzed with the aid of SEM, Br-selective electrode and fluorescence molecular probe.  相似文献   

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