Novel random copolymers of 1,4‐dioxane‐2‐one (DON) and 2,2‐ethylenedioxy‐1,3‐propanediol carbonate (EOPDC) are synthesized in bulk at 120 °C using Sn(Oct)2 as a catalyst. The effects of different molar feed ratios of EOPDC/DON on the yield and molecular weight of the copolymers are investigated. The copolymers are obtained with a yield of 55.4–98%. The number‐average molecular weight of the copolymer is 0.49–4.18 × 104 g mol?1 with a polydispersity of 1.52–1.68. The poly(DON‐co‐EOPDC)s obtained are characterized by FTIR, 1H NMR, and 13C NMR spectroscopy, gel‐permeation chromatography (GPC), and DSC. The hydrolytic degradation of the copolymer in phosphate buffered saline (PBS) is also investigated. The results show that both the hydrophilicity and the degradation rate of the copolymers increase with increasing copolymer DON content. 相似文献
Coffee drinking has been associated with reduced incidence of colorectal cancer, possibly via chemoprotection/modification of the metabolism of dietary heterocyclic amine carcinogens such as 2-amino-1-methyl-6-phenylimidazo-[4,5-b]pyridine (PhIP) by kahweol and cafestol palmitates (K/C), two components of unfiltered coffee. Using the PhIP-exposed male Fisher F344 rat as a model, K/C have been shown to reduce colonic PhIP-DNA adducts by > 50%. We have used the male F344 rat to investigate the effects of dietary K/C (0.02-0.2% as a 1:1 mixture) on the metabolism of PhIP by N-acetyltransferase- (NAT), sulfotransferase- (SULT), and glutathione-dependent pathways. K/C decreased hepatic NAT-dependent PhIP activation by up to 80% in a dose-dependent manner. Conversely, hepatic glutathione S-transferase (GST) activity/expression increased, e.g., 3-4 fold toward 1-chloro-2,4-dinitrobenzene (total activity), up to 23-fold toward 4-vinylpyridine (rGSTP1), and approximately 7-fold for rGSTA2 protein. These effects had fully developed after 5 days of the test diet and persisted for at least 5 days after withdrawal of K/C. Hepatic glutathione increased two- to threefold and this increase was more short-lived than other changes. K/C did not modify hepatic SULT activity or colon NAT and GST activities. Benzylisothiocyanate and black tea, which have also been shown to reduce the formation of PhIP-DNA adducts in this model, had little effect on hepatic NAT, SULT, GST, or GSH. In primary culture of rat hepatocytes, both kahweol and cafestol palmitates reduced NAT activity by 80%. In summary, the unique potential of K/C to convert rapid acetylators to a slow acetylator phenotype, accompanied by GST induction, might contribute to chemoprevention against cancers associated with heterocyclic amines. 相似文献
Some species of mycobacteria have been modified to transform sterols to valuable steroid synthons. The unique cell wall of mycobacteria has been recognized as an important organelle to absorb sterols. Some cell wall inhibitors (e.g., vancomycin and glycine) have been validated to enhance sterol conversion by interfering with transpeptidation in peptidoglycan biosynthesis. Therefore, two transpeptidase genes, pbpA and pbpB, were selected to rationally modify the cell wall to simulate the enhancement effect of vancomycin and glycine on sterol conversion in a 22‐hydroxy‐23,24‐bisnorchol‐4‐ene‐3‐one (4‐HBC) producing strain (WIII). Unexpectedly, the pbpA or pbpB gene augmentation was conducive to the utilization of sterols. The pbpB augmentation strain WIII‐pbpB was further investigated for its better performance. Compared to WIII, the morphology of WIII‐pbpB was markedly changed from oval to spindle, indicating alterations of the cell wall. Biochemical analysis indicated that the altered cell wall properties of WIII‐pbpB might contribute to the positive effect on sterol utilization. The productivity of 4‐HBC was enhanced by 28% in the WIII‐pbpB strain compared to that of WIII. These results demonstrated that the modification of peptidoglycan synthesis can improve the conversion of sterols to steroid synthons in mycobacteria. 相似文献
Ring‐opening metathesis polymerization (ROMP) of N‐(1‐adamantyl)‐exo‐norbornene‐5,6‐dicarboximide (AdNDI) ( 3a ) and N‐cyclohexyl‐exo‐norbornene‐5,6‐dicarboximide (ChNDI) ( 3b ) was performed using well‐defined vinylidene ruthenium (II) catalysts Cl2(PR3)2RuCCH(t‐Bu) (R = Ph and Cy). The homopolymer of 3a showed a Tg of 271 °C while poly‐ChNDI of 3b had a Tg of 129 °C. Copolymers of these monomers with norbornene (NB) demonstrated significant Tg increases compared to unsubstituted poly‐NB. Analysis of copolymers of 3a and NB isolated at the initial stages of copolymerization showed that both monomers were incorporated randomly and displayed very similar reactivity.
Fluorene‐based single‐chain copolymers with a white light emitter consisting of a blue and an orange chromophore have been synthesized and their photophysical and electroluminescent properties are investigated. The experimental results suggest that only a relatively small fraction of the orange‐emitting units incorporated into the fluorene is needed to achieve efficient white light emission by controlled incomplete energy transfer. A device from a copolymer with 0.02% DDQ content showed the highest external quantum efficiency of 2.64% with a luminance efficiency of 4.06 cd · A?1 with CIE coordinates (0.28, 0.24). The EL emissions are extremely stable over a wide range of current densities.
One hundred patients with breast carcinoma followed for 7-11 years were included in the present study of EGFR family members, using immunohistochemistry and RT-PCR. By immunohistochemistry, 36%, 27%, 26%, and 82% of the tumours were positive for EGFR, c-erbB-2, c-erbB-3, and c-erbB-4. All the immunoreactive tumours were confirmed positive by RT-PCR. Tumour size, histological grade, lymph node status, S-phase fraction, and stage were confirmed to be significantly associated with both disease-free and cancer-specific survival in the present study. Methods of treatment, histological type, and ploidy had no significant effect on survival. Statistical analysis of EGFR family members in these tumours showed a significant association between c-erbB-2 expression and reduced disease-free and cancer-specific survival. c-erbB-4 expression was associated with a more favourable outcome. Co-expression of c-erbB-2 and EGFR was associated with a worse prognosis. c-erbB-4 expression, however, showed an antagonistic effect on the clinical influence of c-erbB-2 expression. In conclusion, c-erbB-2 expression in breast carcinomas is associated with an unfavourable clinical course and EGFR expression has a synergistic effect. However, c-erbB-4 antagonizes the c-erbB-2 effect on clinical course in breast carcinomas. To achieve best results with immunotherapy against the c-erbB-2 receptor, clarifying the status of c-erbB-4 expression may be of significance. 相似文献
Summary: Novel readily soluble random low‐band‐gap conjugated copolymers (PFO–DTTP, Eg ≈ 1.77–2.00 eV) derived from 9,9‐dioctylfluorene (DOF) and 2,3‐dimethyl‐5,7‐dithien‐2‐yl‐thieno[3,4‐b]pyrazine (DTTP) were prepared. The solutions and the solid thin films of the copolymers absorbed light from 300–690 nm. Prototype photovoltaic cells from solid state composite films with the copolymer PFO–DTTP30 and [6,6]‐phenyl C61 butyric acid methyl ester (PCBM) showed power conversion efficiencies up to 0.83% under an AM1.5 solar simulator (100 mW · cm−2). For electroluminescent devices, the emission peaks were around 734–780 nm. This indicates that the low band gap copolymers are promising materials for polymeric solar cells and deep red/near infrared light‐emitting diodes.
Synthesis of novel low‐band‐gap fluorene‐based copolymer. 相似文献
A novel nitrogen‐containing electroluminescent copolymer, PQV‐alt‐MOPPV has been designed and synthesized by Wittig‐Horner polymerization. Structure, thermal stability, and optical and electrochemical properties of the resulting copolymer were characterized by FT‐IR, 1H NMR, elemental analysis, GPC, DSC, TGA, UV‐vis, PL, EL, and CV. The copolymer possesses excellent solubility in common organic solvents and good thermal stability. The absorption maxima of the copolymer in solution and a thin film are 490 and 516 nm, and the photoluminescence maxima in solution and thin film are 571 and 629 nm, respectively. The PLED (ITO/PEDOT: PSS (40 nm)/PQV‐alt‐MOPPV (80 nm)/Ca (30 nm)/Al (150 nm) shows a very pure red light emission with maximum peaks around 618 nm.
The phase behavior of PCH‐b‐PtBA‐b‐PCH triblock copolymers has been studied. Measurements in the wide‐angle region probed the existence of microphase segregation through variation of block mobility and thermal expansion coefficients. SAXS experiments pointed out that most copolymers present ordered nanostructures, mostly hexagonally packed cylinders, the morphology being confirmed by AFM. An unusual disorder‐to‐order transition is observed in one copolymer synthesized from a macroinitiator with intermediate length and the highest outer‐block molecular weight, whereas none of the copolymers shows an order‐to‐disorder transition upon heating over the temperature range analyzed.
Summary: Blends of high molecular weight poly(R‐3‐hydroxybutyrate) (PHB) ( = 352 000 g · mol?1), comprising of either low molecular weight poly(R‐3‐hydroxybutyrate) (D‐PHB) ( = 3 900 g · mol?1) or poly[(R‐3‐hydroxybutyrate)‐co‐(R‐3‐hydroxyvalerate)] (PHBV) ( = 238 000 g · mol?1) with 12 mol‐% hydroxyvalerate (HV) content as a second constituent, were investigated along with the thermal properties and morphologies. After isothermal crystallization, a lowering of the melting temperature of PHB can be observed with increasing content of the second component in the blends. This behavior points towards miscibility of the constituents both in the liquid and the solid state. Crystallization kinetics was studied under isothermal and non‐isothermal conditions. The overall kinetics of isothermal crystallization was analyzed in terms of the Avrami equation. Only one crystallization peak is observed in all cases for the PHB/D‐PHB and PHB/PHBV blends under the conditions studied. This demonstrates co‐crystallization of the constituents. The addition of D‐PHB or PHBV to PHB reduces the rate of crystallization of the blends compared to that of neat PHB. The corresponding activation energies of crystallization also decrease with an increasing concentration of the second constituent. Non‐isothermal crystallization, carried out with different cooling rates held constant, is discussed in terms of a quasi‐isothermal approach. The corresponding rate constants as functions of reciprocal undercooling show Arrhenius‐like behavior in a certain range of temperatures. At sufficiently high undercooling, the rate constants of crystallization for the isothermal process exceed those reflecting non‐isothermal conditions, whereas in the limit of low undercoolings, the rate constants become similar. Ring‐banded morphologies are observed when PHB is in excess. When the respective second component is the major component, fibrous textures of the spherulites develop.
Coke-oven workers (COWs) are occupationally exposed to high concentrations of polycyclic aromatic hydrocarbons (PAH). Urinary 8-hydroxy-2-deoxyguanosine (8-OH-dG) and 1-hydroxypyrene (1-OHP) are biological markers of oxidative DNA damage and PAH metabolism, respectively. We investigated the relationship between urinary 8-OH-dG and 1-OHP in 217 Taiwanese COWs, 55 topside-oven, and 162 sideoven workers. For topside-oven workers, mean 8-OH-dG and 1-OHP concentrations (ng/ml +/- SD) were 13.8 +/- 12.0 and 93.5 +/- 104.4, respectively. These levels were significantly higher than those for sideoven workers: 10.2 +/- 7.9 ng/ml (P = 0.04) and 19.8 +/- 28.6 ng/ml (P < 0.001), respectively. Individual urinary 8-OH-dG concentrations were directly correlated with urinary 1-OHP concentrations: the higher the 1-OHP level, the higher the 8-OH-dG level (Spearman correlation coefficients: r = 0.43, P < 0.0001, n = 217). Multiple regression analysis indicated that a 10-fold increase in 1-OHP was associated with a 1.91-fold increase in 8-OH-dG. Compared to no vitamin intake, intake of at least one multiple vitamin pill per week reduced 8-OH-dG excretion (P = 0.02). Our findings suggest that urinary 1-OHP and 8-OH-dG reflect occupational PAH exposure and oxidative DNA damage in COWs. In addition, multiple vitamins may reduce oxidative stress caused by PAH exposure. 相似文献
Three medium‐bandgap polymers based on a 4,5‐ethylene‐2,7‐dithienyl carbazole as the electron‐donating unit and different 5,6‐dialkoxy‐2,1,3‐benzothiadiazoles as the electron‐accepting units, are synthesized as polymer donors for photovoltaic applications. The three copolymers possess highest occupied molecular oribital (HOMO) levels around ?5.47 eV and medium bandgaps of about 1.94 eV. The solar cells with polymer:[6,6]‐phenyl C71‐butyric acid methyl ester (PC71BM) = 1:4 as the active layer, show an especially high open‐circuit voltage (Voc) of 0.95 V and attain good power conversion efficiency up to 5.91%. The hole mobilities of the active layer films, measured by space‐charge‐limited current (SCLC), are up to 3.5 × 10?4 cm2 V?1 s?1. Given the favorable medium bandgaps, low‐lying HOMO levels, and good hole mobilities, these copolymers are promising candidates for the construction of a highly efficient front cell to harvest the shorter wavelength band of the solar radiation in a tandem solar cell with high Voc.