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1.
The new copolymers from different feed compositions of glycidyl methacrylate (GMA) and tetrahydrofurfuryl acrylate (THFA) were synthesized using free radical polymerization in toluene at 70±1 °C using benzoyl peroxide (BPO) as initiator. The polymers were characterized by 1H NMR, 13C NMR and FTIR spectroscopic techniques. The polydispersities of the copolymers suggest a strong tendency for chain termination by disproportionation. The glass transition temperature of the copolymers increases with increase in GMA content. The thermal stability of the copolymers increases with increase in THFA content. The copolymer compositions were determined using 1H NMR analysis. Reactivity ratios for GMA and THFA as determined by the Mao-Huglin method were r1=0.379 and r2=0.266. The results showed that all these copolymerizations are strictly linear systems describable by the Mayo-Lewis equation based on the terminal model and that accurate reactivity ratio data can be obtained.  相似文献   

2.
The domain-structure of samples containing a series of starch/poly(sodium acrylate)-grafted superabsorbents, pure starch, pure poly(sodium acrylate), and blend of starch/poly(sodium acrylate) has been studied by high-resolution solid-state 13C NMR spectroscopy at room temperature. The result shows that the crystallinity of starch decreases greatly in the grafted and blended samples. The values of 1H spin-lattice relaxation time in rotating frame T 1ρ and 1H spin-lattice relaxation time T 1 shows that starch and poly(sodium acrylate) components in both grafted and blended samples have good compatibility in nanometer scale. In the 13C cross-polarization/magic-angle-spinning (CP/MAS) spectra, the chemical shift of the carbonyl group of poly(sodium acrylate) depends on the composition of the grafting samples, which indicates that the starch and the poly(sodium acrylate) components of the grafting samples exhibit better compatibility with each other than that of blended samples at molecular level.  相似文献   

3.
The free radical solution polymerization of acrylonitrile (AN) with itaconic acid (IA) or methyl acrylate (MA) was carried out in dimethylsulfoxide (DMSO) using 2 2'-azobisisobutyronitrile (AIBN) as the initiator. Based on the monomer conversion versus time data, the copolymerization rate was retarded by IA but promoted by MA. The monomer sequence distribution was characterized by 13C NMR to explain the significant difference in the copolymerization kinetics of the ANIA and AN-MA copolymers. The results of the copolymer composition curves and 13C NMR spectral analysis illustrated that the penultimate model was suitable for describing the copolymerization behavior of AN-IA, and the terminal and penultimate models were adequate for AN-MA. The penultimate reactivity ratios, r MA , were ~2 times higher than r IA , indicating that the reactivity of AN-terminated radical having MA as the preceding group was higher than that with IA. Then, the corresponding content of triads sequence AN-AN-AN (AAA) in the AN-MA copolymers was higher than those in the AN-IA copolymers. The appearance of new resonance signals of the quaternary and methyl carbon indicated a higher content of IA in copolymers. The higher IA concentrations the lower viscosity-average molecular weight of the polymers. The decrease in the molecular weight was correlated to the formation of the oligomers.  相似文献   

4.
We have synthesized a series of copolymers with different compositions of acrylonitrile (AN, 80–100 wt%), methyl acrylate (MA, 4–20 wt%) and itaconic acid (IA, 0–3 wt%) by using an efficient aqueous suspension polymerization, and have investigated the molecular structure and thermal stabilization behavior of PAN homopolymer, AN/MA-based bipolymers, and AN/MA/IA-based terpolymers by adopting 1H/13C-NMR and thermal FT-IR analyses. The viscosity-average molecular weight of the synthesized polymers were measured to be ~263,000 g/mol. The reactivity ratios of AN and MA for all the copolymers were evaluated to be 0.99 and 1.05, respectively. Accordingly, the output compositions of the synthesized copolymers were quite consistent with the input monomer compositions. The 13C NMR analysis revealed that all the synthesized polymers have an atactic chain configuration, regardless of the feed composition. The structural evolutions during the thermal stabilization process of the copolymers in air environment were characterized by monitoring the temperature-dependent changes of characteristic absorbance bands at 2240 cm-1 (C≡N), 1595 cm-1 (C=N) and 1660 cm-1 (C=O) with aid of thermal FT-IR spectroscopy. It was found that the IA unit in the terpolymers accelerated the oxidation and cyclization reactions, unlike the retarding effect of MA unit, and that the onset temperatures of the oxidation reaction of the copolymers with IA unit was lower than that of the cyclization reaction.  相似文献   

5.
Core-shell fluorinated acrylate copolymers emulsion was thus synthesized via the core-shell emulsion polymerization with the fluorinated monomers and acrylic monomers as the main raw materials and its properties were studied. PFMA, the fluorinated acrylate monomers, was synthesized by the esterification of perfluorooctanoyl chloride (PFOC) and hydroxypropyl methacrylate (HPMA). Then the core-shell fluorinated acrylate copolymers emulsion with a poly(MMA/BA/St) core and a poly(PFMA/MMA/BA) shell was synthesized via a starved semi-continuous core-shell emulsion polymerization method by using KPS and sodium bicarbonate as the initiator/buffer system and SDS/Twain 80 as the commixture emulsifier. Lastly, the synthesized copolymers was applied as textile finishing agent for cotton textile. The results of FT-IR and NMR indicated that PFMA had been synthesized as expected and effectively combined in the emulsion copolymerization. The GPC, zeta potential, TEM and DSC showed that the particles had uniform spherical core-shell structure with a diameter of 65-150 nm, and the distribution and emulsion stability was satisfactory. As XPS, FESEM and AFM shown, a hydrophobic structure which was similar to the structure of the lotus leaf were formed and the surface hydrophobicity of the films can be improved. Based on the analysis of DSC, thermal stabilities of the films were enhanced with the increase of fluorine content. Besides, FESEM of textiles showed that the surface of treated textiles were smooth and the edges were clear and visible, indicating significant improvement of the performance on water and oil repellent.  相似文献   

6.
A new chrysolaminarin, named CL2, with a molecular mass of 7.75 kDa, was purified from the marine diatom, Odontella aurita, using DEAE-52 cellulose anion-exchange chromatography and Sephadex G-200 gel-filtration chromatography. The monosaccharide and structural analysis revealed that CL2 was a glucan mainly composed of glucose, which was linked by the β-d-(1→3) (main chain) and β-d-(1→6) (side chain) glycosidic bond, demonstrated by infrared spectroscopy (IR) and nuclear magnetic resonance (NMR). The antioxidant activity tests revealed that the CL2 presented stronger hydroxyl radical scavenging activity with increasing concentrations, but less was effective on reducing power analysis and scavenging 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. The influences of nitrogen concentration and light intensity on chrysolaminarin production of O. aurita were further investigated in a glass column photobioreactor, and a record high chrysolaminarin productivity of 306 mg L−1 day−1 was achieved. In conclusion, the chrysolaminarin CL2 from O. aurita may be explored as a natural antioxidant agent for application in aquaculture, food and pharmaceutical areas.  相似文献   

7.
From the dichloromethane/methanol extract of the crinoid Colobometra perspinosa, collected south east of Richards Island (Bedara), Family Islands, Central Great Barrier Reef, Australia, 3-(1′-hydroxypropyl)-1,6,8-trihydroxy-9,10-anthraquinone [one of the two stereoisomers of rhodoptilometrin, (1)], 3-propyl-1,6,8-trihydroxy-9,10-anthraquinone (3), 2-[(phenylacetyl)amino]ethanesulfonic acid (4), and 4-hydroxybutanoic acid (5) were isolated. Comparison of 1H- and 13C-NMR data for rhodoptilometrin (1) with those reported in the literature showed significant differences for some resonances associated with rings A and C. In an attempt to provide accurately assigned 1H- and 13C-NMR data, as well as to confirm the structure of 1, a thorough NMR investigation of this compound was undertaken. Measurements included: concentration dependent 13C, 1D selective NOE, HSQC, HMBC and 1,1-ADEQUATE. The NMR data for 4 and 5 are reported here for the first time, as is their occurrence from the marine environment. The in vitro anticancer activity of the original extract was found to be associated with 1, 3 and 5.  相似文献   

8.
The first total synthesis of marine-derived penicimonoterpene (±)-1 has been achieved in four steps from 6-methylhept-5-en-2-one using a Reformatsky reaction as the key step to construct the basic carbon skeleton. A total of 24 new derivatives of 1 have also been designed and synthesized. Their structures were characterized by analysis of their 1H NMR, 13C NMR and HRESIMS data. Some of them showed significant antibacterial activity against Aeromonas hydrophila, Escherichia coli, Micrococcus luteus, Staphylococcus aureus, Vibrio anguillarum, V. harveyi and/or V. parahaemolyticus, and some showed activity against plant-pathogenic fungi (Alternaria brassicae, Colletotrichum gloeosporioides and/or Fusarium graminearum). Some of the derivatives exhibited antimicrobial MIC values ranging from 0.25 to 4 μg/mL, which were stronger than those of the positive control. Notably, Compounds 3b and 10 showed extremely high selectively against plant-pathogenic fungus F. graminearum (MIC 0.25 μg/mL) and pathogenic bacteria E. coli (MIC 1 μg/mL), implying their potential as antimicrobial agents. SAR analysis of 1 and its derivatives indicated that modification of the carbon-carbon double bond at C-6/7, of groups on the allylic methylene unit and of the carbonyl group at C-1, effectively enhanced the antimicrobial activity.  相似文献   

9.
Plant-derived nematicides are being increasingly used while select synthetic nematicides are phased out for environmental concerns. This is the first report on the in vitro nematicidal activity of cis- and trans-protopinium isolated from roots of Fumaria parviflora and its in vivo effect on the southern root-knot nematode Meloidogyne incognita. Cis- and trans-protopinium was isolated from the methanolic fraction FM2.1, and its structure elucidated using 13C and 1H nuclear magnetic resonance (NMR). The NMR spectra were characterized using deuterated dimethyl sulfoxide (DMSO) at temperatures of 25 and 80 °C. In an in vitro study, over 120 h of incubation, the area under cumulative percent hatch inhibition and mortality of cis- and trans-protopinium reached 100% at a concentration of 200 μg mL−1. In the greenhouse and field settings, cis- and trans-protopinium was evaluated against M. incognita on tomato at a concentration of 100, 200, and 300 μg mL−1 for two consecutive seasons, that is, spring and autumn, in 2010. At a concentration of 300 μg mL−1 in the greenhouse and field trials during spring and autumn, cis- and trans-protopinium significantly reduced the nematode galling index, the number of females per gram of root, and the reproduction factor, as well as increased plant height, fresh and dry shoot weights, and root length. Therefore, cis- and trans-protopinium can be used as an effective and safe nematicide against M. incognita on tomato in an organic and sustainable agricultural production system. Phytochemicals have various agricultural applications, especially to control economically important nematode pests.  相似文献   

10.
1-Hydroxy-10-methoxy-dibenz[b, e]oxepin-6,11-dione (1) was obtained from the culture broth of a marine-derived fungus, Beauveria bassiana TPU942, isolated from a marine sponge collected at Iriomote Island in Okinawa, together with two known compounds, chrysazin (2) and globosuxanthone A (3). The structure of 1 was elucidated on the basis of its spectroscopic data (HREIMS, 1D and 2D NMR experiments including 1H–1H COSY, HMQC and HMBC spectra). Dibenz[b, e]oxepines are rare in nature, and only six natural products have been reported. Therefore, compound 1 is the seventh natural product in this class. Compounds 2 and 3 showed an antifungal activity against Candida albicans, and 3 inhibited the cell growth against two human cancer cell lines, HCT-15 (colon) and Jurkat (T-cell lymphoma). Compound 1 did not show an apparent activity in the same bioassays.  相似文献   

11.
Triumfetta pilosa contain malvalic acid (2.4%) and sterculic acid (6.6%) along with the other normal fatty acids like palmitic (16.7%), stearic (10.8%), oleic (20.1%) and linoleic (43.4%). The cyclopropenoid (malvalic and sterculic) and other normal fatty acids have been determined by FTIR, 1H NMR, gas liquid chromatographic-techniques and chemical degradations.  相似文献   

12.
RAFT-mediated silk graft copolymerizations with DMAAm (N,N-Dimethylacrylamide) were studied. Three types of macromolecular RAFT agents which released different R group radicals, namely, polyacrylic acid-b-polystyrene radical (PAA-b-PSt?), polyacrylic acid-b-polybutyl acrylate radical (PAA-b-PBA?) and polystyrene-b-polyacrylic acid radical (PSt-b-PAA?), were chosen as the transfer agents. During the graft copolymerizations, the newly born PAA-b-PSt? in the aqueous phase enhanced the formation of silk macroradicals, consequently accelerated the copolymerization rate and improved monomer grafting efficiency (Ge) greatly. The Ge was less improved when the RAFT agent capable of producing PAA-b-PBA? were substituted for the one producing PAA-b-PSt?. In addition, Ge also benefited from an increase in the chain length of PSt block in PAA-b-PSt?, as well as PBA block in PAA-b-PBA?. However, the addition of RAFT agent giving rise to PSt-b-PAA? had negligible effects on Ge. The reasons were ascribed to both the radical reactivity and capacity of radical adsorption onto silk fibers.  相似文献   

13.
The zoanthids Palythoa caribaeorum and Protopalythoa variabilis are among the most abundant marine species along the Brazilian coast. We now report the isolation and structure elucidation of two unprecedented sulfonylated ceramides, palyosulfonoceramide A (1) and palyosulfonoceramide B (2) from specimens collected off Brazil’s northeastern coast. The structures of 1 and 2 were established using a combination of NMR analyses, including: evaluation of 1H, 13C, 1H–1H COSY, 1H–13C HSQC, 1H–13C HMBC, and 1H–15N HMBC NMR spectra, high-resolution mass spectrometry and chemical degradation. In addition, we also isolated the corresponding known ceramides, N-((2S,3R,4E,8E)-1,3-dihydroxyoctadeca-4,8-dien-2-yl)-hexadecanamide (3) and N-((2S,3R,4E)-1,3-dihydroxyoctadeca-4-en-2-yl)-hexadecanamide (4), which provided further support for the assignments of 1 and 2.  相似文献   

14.
Cellulose from flax, hemp, kenaf and sorghum was investigated by solid state NMR and vibrational spectroscopy, and the structural differences found were validated by X-ray diffractometry. All three techniques indicate a notable region of order in the cellulose of both flax and hemp, but the absolute crystallinity values are not directly comparable. CP-MAS 13C-NMR and FTIR spectroscopy revealed the presence of Iα and Iβ forms in all the samples. On passing from flax and hemp to kenaf and sorghum the progressive loss in the crystalline phase is evidenced by 13C-CPMAS T1 measurements; 1H-CPMAS T1ρ measurement revealed an analogous loss in phase dimension for the ordered phase, but similar dimension values for the paracrystalline and amorphous phases. The FTIR and FTRaman spectra of all the cellulose samples reveal the same chain conformation but a different hydrogen bond pattern, and this accounts for the NMR and X-ray results.  相似文献   

15.
To study the kinetics of the bread baking process, transverse relaxation (T2) of protons was measured during a baking process performed inside the magnet of a pulsed low field1H nuclear magnetic resonance (NMR) instrument. Experimental NMR relaxation data were analysed both by chemometric data analysis and by multi-exponential curve-fitting. Throughout the entire baking process from dough to bread three T2-components were determined. During the NMR-baking process significant shifts were observed in the characteristic time constants at c. 55 °C (gelatinisation of starch) and at c. 85 °C. In a second experiment staling of white bread crumb aged 0–8 days was investigated by texture analysis and NMR relaxation. High correlations (r>0·9) between texture parameters and NMR relaxation data of bread crumb were found by partial least squares regression (PLSR) models. Firmness and elasticity as measured by a Texture Analyser were predicted with an estimated error (RMSECV) of 150 (range 200–2200) and 0·032 (range 0·4–0·7), respectively. Future texture of the bread samples was also predictable by use of NMR relaxation data from the early storage period (day 0 to day 3).  相似文献   

16.
The subzero properties of wheat doughs were measured by dynamic mechanical thermal analysis (DMTA) and dielectric thermal analysis (DETA) over the temperature range −90 to +40 °C and by1H-nuclear magnetic resonance (NMR) T2relaxation over the range −45 to 0 °C. The experiments revealed two transitions in the dough: one independent of frequency at −10 °C (attributed to ice melting) and one dependent on frequency at −30 °C (attributed to a glass transition). The glass transition temperatures measured by DMTA moved to higher temperatures during frozen storage when the optimal water content of dough was used. A reduction in the water content eliminated this phenomenon. A similar effect of water reduction was observed by NMR studies, in which amplitude ratios and decay times were used to calculate the phase transitions. However, the glass transition recorded by NMR was independent of frozen storage with optimal water content. The changes of water state in frozen doughs were studied by ultracentrifugation (the amount of liquid phase) and NMR (freezable water based on liquid amplitude ratios). Frozen storage increased the liquid phase in dough with optimal water content. Thus, ice crystals are growing during frozen storage resulting in the concentration of polymers and a higher glass transition observed by DMTA. The increase of liquid phase during storage was substantially lower when the water content of dough was decreased. Ice crystals» growth can be minimised by reducing water content. The experiments were carried out with four different flours. The measurement of glass transition temperature by DMTA, DETA or NMR did not reveal great differences in doughs made from different flours. The amount of liquid phase was strongly flour dependent.  相似文献   

17.
Background:Bioactive glasses 58S, are silicate-based materials containing calcium and phosphate, which dissolved in body fluid and bond to the bone tissue. This type of bioactive glass is highly biocompatible and has a wide range of clinical applications. Methods:The 58S glass powders were synthesized via sol-gel methods, using tetraethyl orthosilicate, triethyl phosphate, and calcium nitrate, as precursors. Upon the analyses of phase and chemical structures of bioactive glass in different gelation times (12, 48, and 100 h), the appropriate heat treatment (at 525, 575, and 625 °C) was performed to eliminate nitrate compounds and stabilize the glass powder samples. The in vitro assay in SBF solution revealed the bioactivity of the synthesized 58S glass through the morphological (SEM), chemical structure (FTIR), release of calcium, phosphorous and silicon elements, pH variations, and weight loss measurements. The behavior of MSCs in the presence of bioactive glass powders was studied by MTT cytotoxicity, cell staining, ALP activity and biomineralization tests, as well as by the evaluation of ALP, osteocalcin, osteonectin, collagen I, and RUNX2 gene expression. Results: The results confirmed a gelation time of 100 h and a calcination temperature of 575 °C at optimal conditions for the synthesis of nitrate-free bioactive glass powders. Conclusion:The glass spherical nanoparticles in the range of 20-30 nm possess the improved bioactivity and osteogenic properties as demanded for bone tissue engineering. Key Words: Bioactive glass 58S, Gene expression, Mesenchymal stem cells  相似文献   

18.
Two new water-soluble phenanthroperylene quinones, gymnochrome H (2) and monosulfated gymnochrome A (3), as well as the known compounds gymnochrome A (4) and monosulfated gymnochrome D (5) were isolated from the deep-sea crinoid Hypalocrinus naresianus, which had been collected in the deep sea of Japan. The structures of the compounds were elucidated by spectroscopic analysis including HRMS, 1D 1H and 13C NMR, and 2D NMR. The absolute configuration was determined by ECD spectroscopy, analysis of J-couplings and ROE contacts, and DFT calculations. The configuration of the axial chirality of all isolated phenanthroperylene quinones (2–5) was determined to be (P). For gymnochrome H (2) and monosulfated gymnochrome A (3), a (2′S,2″R) configuration was determined, whereas for monosulfated gymnochrome D (5) a (2′R,2″R), configuration was determined. Acetylated quinones are unusual among natural products from an echinoderm and gymnochrome H (2) together with the recently reported gymnochrome G (1) represent the first isolated acetylated phenanthroperylene quinones.  相似文献   

19.
Poly(ethylene terephthalate) (PET) fibers were grafted with glycidyl methacrylate (GMA) using benzoyl peroxide as initiator. 1,6-diaminohexane (HMDA) was then covalently attached to this GMA grafted PET fibers. Variations of time, temperature, initiator and monomer concentrations were investigated. HMDA-GMA-g-PET fibers were used as a new sorbent for removal of Cr(VI) ions from aqueous solutions through batch adsorption method. Effects of various parameters such as pH, treatment time, and initial ions concentration on the adsorption amount of ions onto reactive fibers were investigated. The adsorption rates of Cr(VI) ions were much higher on the HMDA-GMA-g-PET fiber than on GMA-g-PET and ungrafted PET fiber. Within 60 min, at pH 3, Cr(VI) was removed by 98 % while the initial concentration of ions was at 25 mg/l and by 94 % at 400 mg/l. The Cr(VI) ions adsorbed were easily desorbed by treating with 1M KOH within 10 min.  相似文献   

20.
The marine-derived filamentous fungus Asteromyces cruciatus 763, obtained off the coast of La Jolla, San Diego, USA, yielded the new pentapeptide lajollamide A (1), along with the known compounds regiolone (2), hyalodendrin (3), gliovictin (4), 1N-norgliovicitin (5), and bis-N-norgliovictin (6). The planar structure of lajollamide A (1) was determined by Nuclear Magnetic Resonance (NMR) spectroscopy in combination with mass spectrometry. The absolute configuration of lajollamide A (1) was unambiguously solved by total synthesis which provided three additional diastereomers of 1 and also revealed that an unexpected acid-mediated partial racemization (2:1) of the L-leucine and L-N-Me-leucine residues occurred during the chemical degradation process. The biological activities of the isolated metabolites, in particular their antimicrobial properties, were investigated in a series of assay systems.  相似文献   

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