Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechan...Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechanism. When compared to the crystal thickness (d(c)), the volume occupied by the chain in the melts i.e., the radius of gyration (R-g), plays a very important role in polymer crystallization. When d(c) less than or equal to R-g, crystallization does not necessitate a chain disentangling. The entanglements are just shifted into the amorphous regions. However, as d(c)>R-g, i.e., as the crystal thickness gets larger than the radius of gyration of the chain in the melt, it becomes necessary for a chain to disentangle. Then a change of crystallization mechanism occurs. Such change has been experimentally observed in the crystallization of poly(I-butene). A change in the crystal morphologies from spherulite to quadrangle, is seen via PLM, as crystallization temperatures increase. Even more, such a change is molecular weight dependent, and shifts to lower temperature as molecular weight decreases. There exists a jump of crystal thickness and crystallinity associated with morphological change, as seen via SAXS. A change of crystallization kinetics and crystallinity is further evidenced via dilatometry. The unique feature of P1b crystallization has been discussed based on the radius of gyration of chain in the melt (R-g), and very good agreement is obtained.展开更多
The crystallization and crystalline structure of syndiotactic-polypropylene (sPP) and syndiotactic-poly(1-butene) (sPB) blend containing 10 (Bl-10), 25 (Bl-25), 50 (Bl-50), 75 (Bl-75), and 90 (Bl-90) wt% of sPB, have ...The crystallization and crystalline structure of syndiotactic-polypropylene (sPP) and syndiotactic-poly(1-butene) (sPB) blend containing 10 (Bl-10), 25 (Bl-25), 50 (Bl-50), 75 (Bl-75), and 90 (Bl-90) wt% of sPB, have been investigated by means of differential scanning calorimetry (DSC), FT-IR, and wide-angle X-ray diffraction (WAXD) analyses. The melt-crystallization behavior of the blend samples was studied by DSC on the cooling process at constant rates. Bl-50, Bl-75, and Bl-90 showed lower crystallization temperatures than the neat sPP. sPP in Bl-75 showed the lowest crystallization rate among the blend samples. Bl-90 showed a two-phase molten state, and sPP in Bl-90 crystallized via two-stepprocess. Time evolution of FT-IR spectroscopy at room temperature detected conformational transformation of the sPP polymer chain in the blend samples of Bl-50 and Bl-75. The absorption peaks intensity in the FT-IR spectra derived from the helical conformations in the crystalline phase decreased, and the planar zigzag conformations in the amorphous and mesophase phases decreased over the crystallization time. The time evolution of the WAXD profile of Bl-90 indicated that sPP in the blend accelerated the crystallization of sPB. The crystallized Bl-10, Bl-25, and Bl-50 samples showed diffraction peaks in WAXD profiles and melting endothermic peak in DSC profiles derived from only the sPP crystal. The crystallinity and melting temperature of sPP in the crystallized Bl-10, Bl-25, and Bl-50 samples were almost independent of the sPB content. Both the crystalline structure of sPP and sPB were detected in Bl-75 and Bl-90. Bl-75 showed the lowest crystallinity and melting temperature of sPP among the blend samples.展开更多
A series of phosphorus-modified PITQ-13 catalysts was prepared by wet impregnation of NH4H2PO4 solution into an HITQ-13 parent. The catalysts were characterized using XRD, N2 adsorption, MAS NMR and NH3-TPD. Their cat...A series of phosphorus-modified PITQ-13 catalysts was prepared by wet impregnation of NH4H2PO4 solution into an HITQ-13 parent. The catalysts were characterized using XRD, N2 adsorption, MAS NMR and NH3-TPD. Their catalytic performance in 1-butene catalytic cracking was evaluated in a fixed fluidized bed reactor. The results showed that the crystallinity, surface area and pore volume of P-modified PITQ-13 catalysts decreased with the increasing amounts of P. The number of weak acid sites increased, whereas that of strong acidity decreased. The selectivity to propylene in 1-butene cracking reactions increased because of the decrease in strong acidity. The yield of propylene achieved 41.6% over PITQ-13-2 catalyst with a P content of 1.0 wt%, which was 5.1% greater than that achieved over HITQ-13 catalyst.展开更多
Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the...Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the catalytic performance results, induction period and objective product were closely related to the reaction conditions. Lower space velocity led to longer induction period and higher propene yield. The optimal reaction temperature for propene production is around 150 ~C and it shifted to 100 ~C for ethene production. 1-Butene auto-metathesis predominated in the reaction network if the support with lower degree of sodium exchanged. And propene gradually became the dominant product upon increasing the support sodium exchange degree. 6Mo/H100Na0M-30A1 catalyst with a support of full sodium exchange degree exhibited the highest propene yield.展开更多
A new propene production route from 1-butene metathesis has been developed on heterogeneous 10WO3/Al2O3-HY catalysts with different HY contents. It is found that the catalysts play bi-functionally first for the isomer...A new propene production route from 1-butene metathesis has been developed on heterogeneous 10WO3/Al2O3-HY catalysts with different HY contents. It is found that the catalysts play bi-functionally first for the isomerization of 1-butene to 2-butene and then for the cross-metathesis between 1-butene and 2-butene to propene and 2-pentene. The combination of HY zeolite and Al2O3 is prerequisite for the production of propene. The propene yield keeps increasing with the HY content in the range of 10-70 wt%, where 10WO3/Al2O3-70HY exhibits the highest propene yield. The MS-H2-TPR and MS-O2-TPO characterizations indicate that the increase of HY content in the catalysts weakens the interaction between W species and supports, whereas enhance the probability of coking on the metal species and acid sites.展开更多
Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impac...Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impact on the adsorption properties. In this study, a novel acidic ionic liquid, 1-butyl-3-(triethoxysilylpropyl)imidazolium hydrogen sulfate(i.e., [BTPIm][HSO_4]), was synthesized and subsequently grafted onto the MCM-36 zeolite for the regulation of its adsorption properties towards isobutane and 1-butene. The resultant [BTPIm][HSO_4]-immobilized MCM-36(i.e., MCM-36-IL) was characterized by FT-IR, XPS, XRD, SEM, TG/DTG and N_2 adsorption–desorption measurement. It was found that the specific surface area, micropore volume and mesopore volume of the MCM-36 support underwent a reduction upon the immobilization of ionic liquid,while the surface density of acid increased from 0.0014 to 0.0035 mmol·m^(-2). The adsorption capacity of isobutane and 1-butene on the MCM-36-IL was determined by a static volumetric method. Results demonstrated that the interaction between isobutane and MCM-36-IL was enhanced and the interaction between 1-butene and MCM-36-IL was reduced. As a result, a tunable adsorption ratio of isobutane/1-butene on MCM-36 was achieved.With the increase in surface density of acid and the tunable adsorption ratio of isobutane and 1-butene on the functionalized MCM-36, the acidic ionic liquid-immobilized zeolites are beneficial to obtain an improved reaction yield and a prolonged catalyst life in the reactions catalyzed by solid acid.展开更多
Four monodentate P-ligands and their mixtures(six groups of double-ligand systems,four groups of triple-ligand systems and one group of tetra-ligand system)were used with Rh(acac)(CO)2(acac=acetylacetonate)or...Four monodentate P-ligands and their mixtures(six groups of double-ligand systems,four groups of triple-ligand systems and one group of tetra-ligand system)were used with Rh(acac)(CO)2(acac=acetylacetonate)or Rh(acac)CO(PPh3)as the catalyst in the hydroformylation reaction of 1-butene.It was found that different Rh catalysts showed little difference in the catalysis performance.The general order of catalysis performance is doubleligand system 〉 single-ligand system〉triple-ligand system 〉 tetra-ligand system.Some synergistic effect in the double-ligand system was detected which needs a further investigation.展开更多
The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid ca...The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid (i.e., IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22 (i.e., MCM-22-IL) was characterized by FT1R, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to l-butene (I/O) were investigated to correlate with surface features of MCM-22-IL Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene (I/O) was significantly im- proved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length oflLs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.展开更多
The interfacial instability of the poly(ethylene oxide)(PEO)-based electrolytes impedes the long-term cycling and further application of all-solid-state lithium metal batter-ies.In this work,we have shown an effective...The interfacial instability of the poly(ethylene oxide)(PEO)-based electrolytes impedes the long-term cycling and further application of all-solid-state lithium metal batter-ies.In this work,we have shown an effective additive 1-adaman-tanecarbonitrile,which con-tributes to the excellent per-formance of the poly(ethylene oxide)-based electrolytes.Owing to the strong interaction of the 1-Adamantanecarboni-trile to the polymer matrix and anions,the coordination of the Li^(+)-EO is weakened,and the binding effect of anions is strengthened,thereby improving the Li^(+)conductivity and the electrochemical stability.The diamond building block on the surface of the lithium anode can sup-press the growth of lithium dendrites.Importantly,the 1-Adamantanecarbonitrile also regulates the formation of LiF in the solid electrolyte interface and cathode electrolyte interface,which contributes to the interfacial stability(especially at high voltages)and protects the electrodes,enabling all-solid-state batteries to cycle at high voltages for long periods of time.Therefore,the Li/Li symmetric cell undergoes long-term lithium plating/stripping for more than 2000 h.1-Adamantanecarbonitrile-poly(ethylene oxide)-based LFP/Li and 4.3 V Ni_(0.8)Mn_(0.1)Co_(0.1)O_(2)/Li all-solid-state batteries achieved stable cycles for 1000 times,with capacity retention rates reaching 85%and 80%,respectively.展开更多
BACKGROUND Poly(ADP-ribose)polymerase inhibitors(PARPis)are approved as first-line therapies for breast cancer gene(BRCA)-positive,human epidermal growth factor receptor 2-negative locally advanced or metastatic breas...BACKGROUND Poly(ADP-ribose)polymerase inhibitors(PARPis)are approved as first-line therapies for breast cancer gene(BRCA)-positive,human epidermal growth factor receptor 2-negative locally advanced or metastatic breast cancer.They are also effective for new and recurrent ovarian cancers that are BRCA-or homologous recombination deficiency(HRD)-positive.However,data on these mutations and PARPi use in the Middle East are limited.AIM To assess BRCA/HRD prevalence and PARPi use in patients in the Middle East with breast/ovarian cancer.METHODS This was a single-center retrospective study of 57 of 472 breast cancer patients tested for BRCA mutations,and 25 of 65 ovarian cancer patients tested for HRD.These adult patients participated in at least four visits to the oncology service at our center between August 2021 and May 2023.Data were summarized using descriptive statistics and compared using counts and percentages.Response to treatment was assessed using Response Evaluation Criteria in Solid Tumors criteria.RESULTS Among the 472 breast cancer patients,12.1%underwent BRCA testing,and 38.5%of 65 ovarian cancer patients received HRD testing.Pathogenic mutations were found in 25.6%of the tested patients:26.3%breast cancers had germline BRCA(gBRCA)mutations and 24.0%ovarian cancers showed HRD.Notably,40.0%of gBRCA-positive breast cancers and 66.0%of HRD-positive ovarian cancers were Middle Eastern and Asian patients,respectively.PARPi treatment was used in 5(33.3%)gBRCA-positive breast cancer patients as first-line therapy(n=1;7-months progression-free),for maintenance(n=2;>15-months progression-free),or at later stages due to compliance issues(n=2).Four patients(66.6%)with HRD-positive ovarian cancer received PARPi and all remained progression-free.CONCLUSION Lower testing rates but higher BRCA mutations in breast cancer were found.Ethnicity reflected United Arab Emirates demographics,with breast cancer in Middle Eastern and ovarian cancer in Asian patients.展开更多
While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410× 10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are ca...While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410× 10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).展开更多
Poly(4-methyl-1-pentene) (PMP) hollow fiber membranes were prepared by the melt-spun and cold-stretch(MSCS) method. Scanning electronic microscopy (SEM) was used to characterize the section and surface structures of t...Poly(4-methyl-1-pentene) (PMP) hollow fiber membranes were prepared by the melt-spun and cold-stretch(MSCS) method. Scanning electronic microscopy (SEM) was used to characterize the section and surface structures of themembranes with special asymmetric structure. The preliminary results of gas permeation measurements indicated that the resultant hollow fiber membranes have the potential ability for oxygen/nitrogen separation.展开更多
Poly-α-olefin(PAO) synthetic oil is the base oil of high-quality lubricants, and has a huge market potential.We illustrate PAO synthesis by catalytic polymerization of 1-decene with a boron trifluoride(BF_3)/alcohol ...Poly-α-olefin(PAO) synthetic oil is the base oil of high-quality lubricants, and has a huge market potential.We illustrate PAO synthesis by catalytic polymerization of 1-decene with a boron trifluoride(BF_3)/alcohol system. Gas chromatography–mass spectrometry, proton nuclear magnetic resonance and ^(13) C nuclear magnetic resonance analysis confirmed dimer, trimer and tetramer structures of PAO. Each component contained branched chains with a 1,2 insertion of a head-to-tail link; a 2,1 insertion of a tail-to-tail link and a methyl-containing linked structure. At a low conversion rate, the reaction rate was related directly with the reaction temperature and the catalyst/1-decene concentration. An apparent kinetic equation for PAO formation was determined during 1-decene polymerization.展开更多
The highly conserved abundant nuclear protein poly (ADP-ribose) polymerase-1 (PARP-1) is activated by DNA damage. PARP-1 activation is associated in DNA repair, cell death and inflammation. Since oxidative stress ...The highly conserved abundant nuclear protein poly (ADP-ribose) polymerase-1 (PARP-1) is activated by DNA damage. PARP-1 activation is associated in DNA repair, cell death and inflammation. Since oxidative stress induced robust DNA damage and wide spread inflamma- tory responses are common pathologies of various CNS diseases, the attention towards PARP-1 as a therapeutic target has been amplifying. This review highlights the multiple roles of PARP- 1 in neurological diseases and po- tential of PARP- 1 inhibitors to enter clinical translation.展开更多
基金This work was supported by the Deutsche Forschungsgemeinschall and der Chemischen Industrierate, Alexander von Humboldt Stiffeng and the China National Distinguished Young Investigator Fund (No. 29925413).
文摘Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechanism. When compared to the crystal thickness (d(c)), the volume occupied by the chain in the melts i.e., the radius of gyration (R-g), plays a very important role in polymer crystallization. When d(c) less than or equal to R-g, crystallization does not necessitate a chain disentangling. The entanglements are just shifted into the amorphous regions. However, as d(c)>R-g, i.e., as the crystal thickness gets larger than the radius of gyration of the chain in the melt, it becomes necessary for a chain to disentangle. Then a change of crystallization mechanism occurs. Such change has been experimentally observed in the crystallization of poly(I-butene). A change in the crystal morphologies from spherulite to quadrangle, is seen via PLM, as crystallization temperatures increase. Even more, such a change is molecular weight dependent, and shifts to lower temperature as molecular weight decreases. There exists a jump of crystal thickness and crystallinity associated with morphological change, as seen via SAXS. A change of crystallization kinetics and crystallinity is further evidenced via dilatometry. The unique feature of P1b crystallization has been discussed based on the radius of gyration of chain in the melt (R-g), and very good agreement is obtained.
文摘The crystallization and crystalline structure of syndiotactic-polypropylene (sPP) and syndiotactic-poly(1-butene) (sPB) blend containing 10 (Bl-10), 25 (Bl-25), 50 (Bl-50), 75 (Bl-75), and 90 (Bl-90) wt% of sPB, have been investigated by means of differential scanning calorimetry (DSC), FT-IR, and wide-angle X-ray diffraction (WAXD) analyses. The melt-crystallization behavior of the blend samples was studied by DSC on the cooling process at constant rates. Bl-50, Bl-75, and Bl-90 showed lower crystallization temperatures than the neat sPP. sPP in Bl-75 showed the lowest crystallization rate among the blend samples. Bl-90 showed a two-phase molten state, and sPP in Bl-90 crystallized via two-stepprocess. Time evolution of FT-IR spectroscopy at room temperature detected conformational transformation of the sPP polymer chain in the blend samples of Bl-50 and Bl-75. The absorption peaks intensity in the FT-IR spectra derived from the helical conformations in the crystalline phase decreased, and the planar zigzag conformations in the amorphous and mesophase phases decreased over the crystallization time. The time evolution of the WAXD profile of Bl-90 indicated that sPP in the blend accelerated the crystallization of sPB. The crystallized Bl-10, Bl-25, and Bl-50 samples showed diffraction peaks in WAXD profiles and melting endothermic peak in DSC profiles derived from only the sPP crystal. The crystallinity and melting temperature of sPP in the crystallized Bl-10, Bl-25, and Bl-50 samples were almost independent of the sPB content. Both the crystalline structure of sPP and sPB were detected in Bl-75 and Bl-90. Bl-75 showed the lowest crystallinity and melting temperature of sPP among the blend samples.
基金supported by PetroChina Company Limited(12-09-01-01)the National Basic Research Program of China(973 Program,2012CB215001)
文摘A series of phosphorus-modified PITQ-13 catalysts was prepared by wet impregnation of NH4H2PO4 solution into an HITQ-13 parent. The catalysts were characterized using XRD, N2 adsorption, MAS NMR and NH3-TPD. Their catalytic performance in 1-butene catalytic cracking was evaluated in a fixed fluidized bed reactor. The results showed that the crystallinity, surface area and pore volume of P-modified PITQ-13 catalysts decreased with the increasing amounts of P. The number of weak acid sites increased, whereas that of strong acidity decreased. The selectivity to propylene in 1-butene cracking reactions increased because of the decrease in strong acidity. The yield of propylene achieved 41.6% over PITQ-13-2 catalyst with a P content of 1.0 wt%, which was 5.1% greater than that achieved over HITQ-13 catalyst.
基金the National Natural Science Foundation of China(Grant No.20903088 and 21006104)
文摘Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the catalytic performance results, induction period and objective product were closely related to the reaction conditions. Lower space velocity led to longer induction period and higher propene yield. The optimal reaction temperature for propene production is around 150 ~C and it shifted to 100 ~C for ethene production. 1-Butene auto-metathesis predominated in the reaction network if the support with lower degree of sodium exchanged. And propene gradually became the dominant product upon increasing the support sodium exchange degree. 6Mo/H100Na0M-30A1 catalyst with a support of full sodium exchange degree exhibited the highest propene yield.
基金supported by the National Natural Science Foundation of China (No.20773120)National 973 Project of China (No.2005CB221403)
文摘A new propene production route from 1-butene metathesis has been developed on heterogeneous 10WO3/Al2O3-HY catalysts with different HY contents. It is found that the catalysts play bi-functionally first for the isomerization of 1-butene to 2-butene and then for the cross-metathesis between 1-butene and 2-butene to propene and 2-pentene. The combination of HY zeolite and Al2O3 is prerequisite for the production of propene. The propene yield keeps increasing with the HY content in the range of 10-70 wt%, where 10WO3/Al2O3-70HY exhibits the highest propene yield. The MS-H2-TPR and MS-O2-TPO characterizations indicate that the increase of HY content in the catalysts weakens the interaction between W species and supports, whereas enhance the probability of coking on the metal species and acid sites.
基金Supported by the National Natural Science Foundation of China(No.21276163,and No.21576168)
文摘Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impact on the adsorption properties. In this study, a novel acidic ionic liquid, 1-butyl-3-(triethoxysilylpropyl)imidazolium hydrogen sulfate(i.e., [BTPIm][HSO_4]), was synthesized and subsequently grafted onto the MCM-36 zeolite for the regulation of its adsorption properties towards isobutane and 1-butene. The resultant [BTPIm][HSO_4]-immobilized MCM-36(i.e., MCM-36-IL) was characterized by FT-IR, XPS, XRD, SEM, TG/DTG and N_2 adsorption–desorption measurement. It was found that the specific surface area, micropore volume and mesopore volume of the MCM-36 support underwent a reduction upon the immobilization of ionic liquid,while the surface density of acid increased from 0.0014 to 0.0035 mmol·m^(-2). The adsorption capacity of isobutane and 1-butene on the MCM-36-IL was determined by a static volumetric method. Results demonstrated that the interaction between isobutane and MCM-36-IL was enhanced and the interaction between 1-butene and MCM-36-IL was reduced. As a result, a tunable adsorption ratio of isobutane/1-butene on MCM-36 was achieved.With the increase in surface density of acid and the tunable adsorption ratio of isobutane and 1-butene on the functionalized MCM-36, the acidic ionic liquid-immobilized zeolites are beneficial to obtain an improved reaction yield and a prolonged catalyst life in the reactions catalyzed by solid acid.
基金Supported by the National Natural Science Foundation of China(21306227)the Science Foundation of China University of Petroleum,Beijing(C201604)
文摘Four monodentate P-ligands and their mixtures(six groups of double-ligand systems,four groups of triple-ligand systems and one group of tetra-ligand system)were used with Rh(acac)(CO)2(acac=acetylacetonate)or Rh(acac)CO(PPh3)as the catalyst in the hydroformylation reaction of 1-butene.It was found that different Rh catalysts showed little difference in the catalysis performance.The general order of catalysis performance is doubleligand system 〉 single-ligand system〉triple-ligand system 〉 tetra-ligand system.Some synergistic effect in the double-ligand system was detected which needs a further investigation.
基金Supported by the National Natural Science Foundation of China(21576168,21276163)
文摘The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid (i.e., IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22 (i.e., MCM-22-IL) was characterized by FT1R, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to l-butene (I/O) were investigated to correlate with surface features of MCM-22-IL Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene (I/O) was significantly im- proved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length oflLs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.
基金supported by National Natural Science Foundation of China(Grant No.22209012).
文摘The interfacial instability of the poly(ethylene oxide)(PEO)-based electrolytes impedes the long-term cycling and further application of all-solid-state lithium metal batter-ies.In this work,we have shown an effective additive 1-adaman-tanecarbonitrile,which con-tributes to the excellent per-formance of the poly(ethylene oxide)-based electrolytes.Owing to the strong interaction of the 1-Adamantanecarboni-trile to the polymer matrix and anions,the coordination of the Li^(+)-EO is weakened,and the binding effect of anions is strengthened,thereby improving the Li^(+)conductivity and the electrochemical stability.The diamond building block on the surface of the lithium anode can sup-press the growth of lithium dendrites.Importantly,the 1-Adamantanecarbonitrile also regulates the formation of LiF in the solid electrolyte interface and cathode electrolyte interface,which contributes to the interfacial stability(especially at high voltages)and protects the electrodes,enabling all-solid-state batteries to cycle at high voltages for long periods of time.Therefore,the Li/Li symmetric cell undergoes long-term lithium plating/stripping for more than 2000 h.1-Adamantanecarbonitrile-poly(ethylene oxide)-based LFP/Li and 4.3 V Ni_(0.8)Mn_(0.1)Co_(0.1)O_(2)/Li all-solid-state batteries achieved stable cycles for 1000 times,with capacity retention rates reaching 85%and 80%,respectively.
文摘BACKGROUND Poly(ADP-ribose)polymerase inhibitors(PARPis)are approved as first-line therapies for breast cancer gene(BRCA)-positive,human epidermal growth factor receptor 2-negative locally advanced or metastatic breast cancer.They are also effective for new and recurrent ovarian cancers that are BRCA-or homologous recombination deficiency(HRD)-positive.However,data on these mutations and PARPi use in the Middle East are limited.AIM To assess BRCA/HRD prevalence and PARPi use in patients in the Middle East with breast/ovarian cancer.METHODS This was a single-center retrospective study of 57 of 472 breast cancer patients tested for BRCA mutations,and 25 of 65 ovarian cancer patients tested for HRD.These adult patients participated in at least four visits to the oncology service at our center between August 2021 and May 2023.Data were summarized using descriptive statistics and compared using counts and percentages.Response to treatment was assessed using Response Evaluation Criteria in Solid Tumors criteria.RESULTS Among the 472 breast cancer patients,12.1%underwent BRCA testing,and 38.5%of 65 ovarian cancer patients received HRD testing.Pathogenic mutations were found in 25.6%of the tested patients:26.3%breast cancers had germline BRCA(gBRCA)mutations and 24.0%ovarian cancers showed HRD.Notably,40.0%of gBRCA-positive breast cancers and 66.0%of HRD-positive ovarian cancers were Middle Eastern and Asian patients,respectively.PARPi treatment was used in 5(33.3%)gBRCA-positive breast cancer patients as first-line therapy(n=1;7-months progression-free),for maintenance(n=2;>15-months progression-free),or at later stages due to compliance issues(n=2).Four patients(66.6%)with HRD-positive ovarian cancer received PARPi and all remained progression-free.CONCLUSION Lower testing rates but higher BRCA mutations in breast cancer were found.Ethnicity reflected United Arab Emirates demographics,with breast cancer in Middle Eastern and ovarian cancer in Asian patients.
基金This work was in part supported by the Hong Kong Research Grants Council(HKUST6062/98P and DAG96/97 SC11).
文摘While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410× 10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).
基金This work was supported by the National Natural Science Foundation of China (Grant No. 59833120).
文摘Poly(4-methyl-1-pentene) (PMP) hollow fiber membranes were prepared by the melt-spun and cold-stretch(MSCS) method. Scanning electronic microscopy (SEM) was used to characterize the section and surface structures of themembranes with special asymmetric structure. The preliminary results of gas permeation measurements indicated that the resultant hollow fiber membranes have the potential ability for oxygen/nitrogen separation.
基金supported by the Natural Science Foundation of China(21576048)the PetroChina Innovation Foundation(2014D-5006-0503)
文摘Poly-α-olefin(PAO) synthetic oil is the base oil of high-quality lubricants, and has a huge market potential.We illustrate PAO synthesis by catalytic polymerization of 1-decene with a boron trifluoride(BF_3)/alcohol system. Gas chromatography–mass spectrometry, proton nuclear magnetic resonance and ^(13) C nuclear magnetic resonance analysis confirmed dimer, trimer and tetramer structures of PAO. Each component contained branched chains with a 1,2 insertion of a head-to-tail link; a 2,1 insertion of a tail-to-tail link and a methyl-containing linked structure. At a low conversion rate, the reaction rate was related directly with the reaction temperature and the catalyst/1-decene concentration. An apparent kinetic equation for PAO formation was determined during 1-decene polymerization.
文摘The highly conserved abundant nuclear protein poly (ADP-ribose) polymerase-1 (PARP-1) is activated by DNA damage. PARP-1 activation is associated in DNA repair, cell death and inflammation. Since oxidative stress induced robust DNA damage and wide spread inflamma- tory responses are common pathologies of various CNS diseases, the attention towards PARP-1 as a therapeutic target has been amplifying. This review highlights the multiple roles of PARP- 1 in neurological diseases and po- tential of PARP- 1 inhibitors to enter clinical translation.