Objective: Flexible ureteroscopy (fURS) has become a widely accepted and effective technique for treating kidney stones. With the development of new laser systems, the fURS approach has evolved significantly. This lit...Objective: Flexible ureteroscopy (fURS) has become a widely accepted and effective technique for treating kidney stones. With the development of new laser systems, the fURS approach has evolved significantly. This literature review aims to examine the current state of knowledge on fURS treatment of kidney stones, with a particular focus on the impact of the latest laser technologies on clinical outcomes and patient safety.Methods: We conducted a search of the PubMed/PMC, Web of Science Core Collection, Scopus, Embase (Ovid), and Cochrane Databases for all randomized controlled trial articles on laser lithotripsy in September 2023 without time restriction.Results: We found a total of 22 relevant pieces of literature. Holmium laser has been used for intracavitary laser lithotripsy for nearly 30 years and has become the golden standard for the treatment of urinary stones. However, the existing holmium laser cannot completely powder the stone, and the retropulsion of the stone after the laser emission and the thermal damage to the tissue have caused many problems for clinicians. The introduction of thulium fiber laser and Moses technology brings highly efficient dusting lithotripsy effect through laser innovation, limiting pulse energy and broadening pulse frequency.Conclusion: While the holmium:yttrium-aluminum-garnet laser remains the primary choice for endoscopic laser lithotripsy, recent technological advancements hint at a potential new gold standard. Parameter range, retropulsion effect, laser fiber adaptability, and overall system performance demand comprehensive attention. The ablation efficacy of high-pulse-frequency devices relies on precise targeting, which may pose practical challenges.展开更多
A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite (molar ratio of SiO2 to Al2O3 being 25) was 2:1. The CuO-ZnO-Al2O3-ZrO2 ...A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite (molar ratio of SiO2 to Al2O3 being 25) was 2:1. The CuO-ZnO-Al2O3-ZrO2 (CuO/ZnO/Al2O3=3/6/1 by weight) component was prepared by a modified 'two-step' co-precipitation method. The effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSMo5 catalyst for dimethyl ether synthesis from CO2 hydrogenation were investigated. It was found that ZrO2 improved the properties of CuO-ZnO-Al2O3/HZSM-5 as a structural promoter.展开更多
Ni/Si O_2 and bimetallic Ni_xGa/SiO_2 catalysts with different Ni/Ga atomic ratios(x = 10~2) were investigated for the selective hydrogenation of acetylene.It was found that Ni_xGa/SiO_2 showed higher selectivity to ...Ni/Si O_2 and bimetallic Ni_xGa/SiO_2 catalysts with different Ni/Ga atomic ratios(x = 10~2) were investigated for the selective hydrogenation of acetylene.It was found that Ni_xGa/SiO_2 showed higher selectivity to ethylene than Ni/Si O_2.This is attributed to the formation Ni-Ga alloy and Ni3 Ga intermetallic compound(IMC) where there was a charge transfer from Ga to Ni,which is favorable for reducing the adsorption strength and amount of ethylene on Ni atoms.As a result,the over-hydrogenation,the C–C bond hydrogenolysis and the polymerization were suppressed,and subsequently the selectivity to ethylene was enhanced.With the decrease of Ni/Ga atomic ratio,the activity and stability of the Ni_xGa/SiO_2 catalysts increased first and then decreased,while the ethylene selectivity tended to increase.Ni_5 Ga/SiO_2 exhibited the best performance.Under the conditions of 180 °C,0.1 MPa,and a reactant(1.0 vol% acetylene,5.0 vol% H_2 and 94 vol% N_2) with the space velocity of 36,000 m L h^(-1) g^(-1),the acetylene conversion maintained at 100% on Ni_5 Ga/SiO_2 during 120 h time on stream and the selectivity to ethylene was 75%~81%after reaction for 68 h.It was also found that the formation of Ni-Ga alloy and Ni_3 Ga IMC suppressed the incorporation of carbon to form NiCx,subsequently enhancing the catalyst stability.Additionally,with increasing the Ga content,the catalyst acid amount and strength tended to increase,which promoted the polymerization and carbon deposition and so the catalyst deactivation.展开更多
NiP/SiOand bimetallic Ni MP/Si O2(M = Co, Fe, Mo, W; Ni/M atomic ratio=5) catalysts were prepared by the temperature-programmed reduction method. The catalysts and their precursors were characterized by means of UV–V...NiP/SiOand bimetallic Ni MP/Si O2(M = Co, Fe, Mo, W; Ni/M atomic ratio=5) catalysts were prepared by the temperature-programmed reduction method. The catalysts and their precursors were characterized by means of UV–Vis DRS, H-TPR, XRD, TEM, CO chemisorption and NH-TPD. Their performance for the deoxygenation of methyl laurate was tested on a fixed-bed reactor. The results show that the main phase was NiP in all catalysts, and M(M = Co, Fe, Mo, W) entered the lattice of NiP forming solid solution. Different from Fe and Co, the introduction of Mo and W into NiP/SiOreduced the phosphide particle size and increased the acid amount. In the deoxygenation reaction, the turnover frequency of methyl laurate increased on the catalysts in the order of NiMoP/SiO, NiP/SiO, Ni WP/Si O2, NiFeP/SiOand NiCoP/SiO, which is influenced by the size of phosphide particles and the interaction between Ni and M(M = Fe, Co, Mo or W). The introduction of the second metal(especially Mo and W) into NiP/SiOpromoted the hydrodeoxygenation pathway. This is mainly attributed to the interaction between Ni and the second metal. Finally, the Ni MoP/SiOcatalyst was tested at 340 oC, 3 MPa, methyl laurate WHSV of 14 h-1and H/methyl laurate molar ratio of 25 for 132 h, and its deactivation took place. We found that the catalyst deactivation mainly resulted from carbonaceous deposit rather than the sintering of metal phosphide crystallites.展开更多
Ni–Ga alloy(Ni/Ga atomic ratio of 8),Ni3Ga and Ni5Ga3 intermetallic compounds(IMCs)catalysts were prepared from Ni–Mg-Al-Ga layered double hydroxides(LDHs)for the deoxygenation of methyl esters to hydrocarbons.In th...Ni–Ga alloy(Ni/Ga atomic ratio of 8),Ni3Ga and Ni5Ga3 intermetallic compounds(IMCs)catalysts were prepared from Ni–Mg-Al-Ga layered double hydroxides(LDHs)for the deoxygenation of methyl esters to hydrocarbons.In the alloy and IMCs,the presence of Ga reduced the surface Ni atom density,and the charge transfer from Ga to Ni increased the electron density of Ni.In the deoxygenation of methyl laurate,the Ni catalyst gave a complete hydrogenolysis of methyl laurate to CH4at 330°C and 3.0 MPa,while the presence of Ga promoted the HDO pathway and suppressed C–C bond hydrogenolysis and methanation.The Ni5Ga3 catalyst exhibited the best desired performance.Even at 400°C,it gave the yield of C11 and C12 hydrocarbons of ~99%,and the selectivity to CH4(SCH4) was only 2.4%.In the deoxygenation of methyl octanoate and methyl palmitate,the Ni5Ga3 catalyst also gave the yield of hydrocarbons above95%.Reactivity evaluation and methyl propionate-TPD and TPSR results indicate that the C–OCH3 bond instead of the O–CH3 one was cleaved on both Ni and bimetallic Ni–Ga catalysts.It is highlighted that methanol,derived from the C–OCH3 bond hydrogenolysis,mainly decomposed to CO and H2 on IMCs,while it was converted to methane on metallic Ni and alloy.It is of great significance that H2 could be yielded from the methyl ester itself.In short,the utilization of Ni–Ga IMCs can effectively reduce carbon loss and H2 consumption,all of which are ascribed to the geometric and electronic effects of Ga.展开更多
SiO2-supported Ni-Mo bimetallic phosphides were prepared by temperature-programmed reduction (TPR) method from the phosphate precur- sors calcined at different temperatures. Their properties were characterized by me...SiO2-supported Ni-Mo bimetallic phosphides were prepared by temperature-programmed reduction (TPR) method from the phosphate precur- sors calcined at different temperatures. Their properties were characterized by means of ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), H2 temperature-programmed reduction (H2-TPR), X-ray diffraction (XRD), transmission electron microscopy (TEM), CO chemisorption, H2 and NH3 temperature-programmed desorptions (H2-TPD and NH3-TPD). Their catalytic performances for the deoxygena- tion of methyl laurate were tested in a fixed-bed reactor. When the precursors were calcined at 400 and 500 ℃, respectively, NiMoP2 phase could be formed apart from Ni2P and MoP phases in the prepared C400 and C500 catalysts. However, when the precursors were calcined at 600, 700 and 800 ℃, respectively, only Ni2P and MoP phases could be detected in the prepared C600, C700 and C800 catalysts. Also, in C400, C500 and C600 catalysts, Mo atoms were found to be entered in the lattice of Ni2P phase, but the entering extent became less with the increase of calcination temperature. As the calcination temperature of the precursor increased, the interaction between Ni and Mo in the prepared catalysts decreased, and the phosphide crystallite size tended to increase, subsequently leading to the decrease in the surface metal site density and the acid amount. C600 catalyst showed the highest activity among the tested ones for the deoxygenation of methyl laurate. As the calcination temperature of the precursor increased, the selectivity to C12 hydrocarbons decreased while the selectivity to C11 hydrocarbons tended to increase. This can be mainly attributed to the decreased Ni-Mo interaction and the increased phosphide particle size. In sum, the structure and performance of Ni-Mo bimetallic phosphide catalyst can be tuned by the calcination temperature of precursor.展开更多
Objective: To examine the trajectory of psychosomatic symptoms and to explore the impact of psychosomatic symptoms on setup error in patients undergoing breast cancer radiotherapy.Methods: A total of 102 patients with...Objective: To examine the trajectory of psychosomatic symptoms and to explore the impact of psychosomatic symptoms on setup error in patients undergoing breast cancer radiotherapy.Methods: A total of 102 patients with early breast cancer who received initial radiotherapy were consecutively recruited. The M.D. Anderson Symptom Inventory(MDASI) and three different anxiety scales, i.e., the Self-Rating Anxiety Scale(SAS), State-Trait Anxiety Inventory(STAI), and Anxiety Sensitivity Index(ASI), were used in this study. The radiotherapy setup errors were measured in millimetres by comparing the real-time isocratic verification film during radiotherapy with the digitally reconstructed radiograph(DRR). Patients completed the assessment at three time points: before the initial radiotherapy(T1), before the middle radiotherapy(T2), and before the last radiotherapy(T3).Results: The SAS and STAI-State scores of breast cancer patients at T1 were significantly higher than those at T2 and T3(F=24.44, P<0.001;F=30.25, P<0.001). The core symptoms of MDASI were positively correlated with anxiety severity. The setup errors of patients with high SAS scores were greater than those of patients with low anxiety levels at T1(Z=-2.01, P=0.044). We also found that higher SAS scores were associated with a higher risk of radiotherapy setup errors at T1(B=0.458, P<0.05).Conclusions: This study seeks to identify treatment-related psychosomatic symptoms and mitigate their impact on patients and treatment. Patients with early breast cancer experienced the highest level of anxiety before the initial radiotherapy, and then, anxiety levels declined. Patients with high somatic symptoms of anxiety may have a higher risk of radiotherapy setup errors.展开更多
Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. He...Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal(Fe, Co, Ni, Mo and W) phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.展开更多
SiO2‐supported monometallic Ni and bimetallic Ni‐In catalysts were prepared and used for hydrodeoxygenation of anisole,which was used as a model bio‐oil compound,for BTX(benzene,toluene,and xylene)production.The ef...SiO2‐supported monometallic Ni and bimetallic Ni‐In catalysts were prepared and used for hydrodeoxygenation of anisole,which was used as a model bio‐oil compound,for BTX(benzene,toluene,and xylene)production.The effects of the Ni/In ratio and Ni content on the structures and performances of the catalysts were investigated.The results show that In atoms were incorporated into the Ni metal lattice.Although the Ni‐In bimetallic crystallites were similar in size to those of monometallic Ni at the same Ni content,H2uptake by the bimetallic Ni‐In catalyst was much lower than that by monometallic Ni because of dilution of Ni atoms by In atoms.Charge transfer from In to Ni was observed for the bimetallic Ni‐In catalysts.All the results indicate intimate contact between Ni and In atoms,and the In atoms geometrically and electronically modified the Ni atoms.In the hydrodeoxygenation of anisole,although the activities of the Ni‐In bimetallic catalysts in the conversion of anisole were lower than that of the monometallic Ni catalyst,they gave higher selectivities for BTX and cyclohexane as a result of suppression of benzene ring hydrogenation and C–C bond hydrogenolysis.They also showed lower methanation activity.These results will be useful for enhancing carbon yields and reducing H2consumption.In addition,the lower the Ni/In ratio was,the greater was the effect of In on the catalytic performance.The selectivity for BTX was primarily determined by the Ni/In ratio and was little affected by the Ni content.We suggest that the performance of the Ni‐In bimetallic catalyst can be ascribed to the geometric and electronic effects of In.展开更多
Objective: To investigate the expression of vascular endothelial growth factor D (VEGF-D) in gastric cancer and its relationship with lymph node metastasis. Methods: 100 cases of gastric carcinoma tissues (50 cases wi...Objective: To investigate the expression of vascular endothelial growth factor D (VEGF-D) in gastric cancer and its relationship with lymph node metastasis. Methods: 100 cases of gastric carcinoma tissues (50 cases with lymph node metastasis, 50 cases negative) and 30 cases of normal gastric tissues were gathered to detect the expressions of VEGF-C and D proteins by immunohistochemistry. Results: VEGF-C and D were revealed in cytoplasm of gastric carcinoma tissues and normal gastric tissues. The positive rates of VEGF-C and D expressions were significantly higher in gastric cancer tissues than those in the normal ones (51%, 60% vs 10%, 20% respectively; both P < 0.05). There were significant correlations be- tween the positive expression of VEGF-D and lymph node metastasis, lymphatic invasion, positive expression of VEGF-C, but not with tumour size, tissue differentiation, and venous invasion. Conclusion: The expression of VEGF-D is closely related to lymph node metastasis in gastric carcinoma.展开更多
Porous carbon-encapsulated Ni and Ni-Sn intermetallic compound catalysts were prepared by the one-pot extended Stöber method followed by carbonization and tested for in-situ hydrothermal deoxygenation of methyl p...Porous carbon-encapsulated Ni and Ni-Sn intermetallic compound catalysts were prepared by the one-pot extended Stöber method followed by carbonization and tested for in-situ hydrothermal deoxygenation of methyl palmitate with methanol as the hydrogen donor.During the catalyst preparation,Sn doping reduces the size of carbon spheres,and the formation of Ni-Sn intermetallic compounds restrain the graphitization,contributing to larger pore volume and pore diameter.Consequently,a more facile mass transfer occurs in carbon-encapsulated Ni-Sn intermetallic compound catalysts than in carbonencapsulated Ni catalysts.During the in-situ hydrothermal deoxygenation,the synergism between Ni and Sn favors palmitic acid hydrogenation to a highly reactive hexadecanal that easily either decarbonylate to n-pentadecane or is hydrogenated to hexadecanol.At high reaction temperature,hexadecanol undergoes dehydrogenation-decarbonylation,generating n-pentadecane.Also,the C-C bond hydrolysis and methanation are suppressed on Ni-Sn intermetallic compounds,favorable for increasing the carbon yield and reducing the H_(2) consumption.The npentadecane and n-hexadecane yields reached 88.1%and 92.8%on carbon-encapsulated Ni_(3) Sn_(2) intermetallic compound at 330℃.After washing and H_(2) reduction,the carbon-encapsulated Ni_(3) Sn_(2) intermetallic compound remains stable during three recycling cycles.This is ascribed to the carbon confinement that effectively suppresses the sintering and loss of metal particles under harsh hydrothermal conditions.展开更多
Despite exciting achievements with some malignancies,immunotherapy for hypoimmunogenic cancers,especially glioblastoma(GBM),remains a formidable clinical challenge.Poor immunogenicity and deficient immune infiltrates ...Despite exciting achievements with some malignancies,immunotherapy for hypoimmunogenic cancers,especially glioblastoma(GBM),remains a formidable clinical challenge.Poor immunogenicity and deficient immune infiltrates are two major limitations to an effective cancer-specific immune response.Herein,we propose that an injectable signal-amplifying nanocomposite/hydrogel system consisting of granulocyte-macrophage colony-stimulating factor and imiquimod-loaded antigen-capturing nanoparticles can simultaneously amplify the chemotactic signal of antigen-presenting cells and the"danger"signal of GBM.We demonstrated the feasibility of this strategy in two scenarios of GBM.In the first scenario,we showed that this simultaneous amplification system,in conjunction with local chemotherapy,enhanced both the immunogenicity and immune infiltrates in a recurrent GBM model;thus,ultimately making a cold GBM hot and suppressing postoperative relapse.Encouraged by excellent efficacy,we further exploited this signal-amplifying system to improve the efficiency of vaccine lysate in the treatment of refractory multiple GBM,a disease with limited clinical treatment options.In general,this biomaterial-based immune signal amplification system represents a unique approach to restore GBM-specific immunity and may provide a beneficial preliminary treatment for other clinically refractorymalignancies.展开更多
Forty one novel 1,3,4-oxadiazole/thiadiazole thioether derivatives containing phenoxy moiety were designed and synthesized. Bioassay demonstrated that some of them showed remarkable activities against Tylenchufus semi...Forty one novel 1,3,4-oxadiazole/thiadiazole thioether derivatives containing phenoxy moiety were designed and synthesized. Bioassay demonstrated that some of them showed remarkable activities against Tylenchufus semipenetruns in vitro and in vivo. Compounds 20, 21, 35 and 39 showed excellent lethal activities after treatment for 48 h in vitro, with LC50 values of 13.4±1.8, 11.7±2.5, 13.7±2.4 and 13.31.1 mg.L-1, respectively, which were obviously superior to fosthiazate (49.1±2.8 mg.L-1) and avermectin (26.6±2.3 mg.L-1). Compound 23. can effectively control the citrus nema- tode disease caused by T. semipenetruns at 200 mg.L-1 in vivo with (68±3)% inhibitory effect, which was even better than that of avermectin ((63±2)%). The CoMFA and CoMSIA models of three-dimensional quantitative structure-activity relationships (3D-QSARs) were established. The compound 33 was designed based on the 3D-QSAR models with more vigorous nematicidal activities in vitro (LC50:9.8±1.4 mg.L-1) and in vivo ((70±5)%). These results demonstrated that compound 33 can be considered as a potential nematicide.展开更多
Culturing has been the cornerstone of microbiology since Robert Koch first successfully cultured bacteria in the late nineteenth century. However, even today, the majority of microorganisms in the marine environment r...Culturing has been the cornerstone of microbiology since Robert Koch first successfully cultured bacteria in the late nineteenth century. However, even today, the majority of microorganisms in the marine environment remain uncultivated. There are various explanations for the inability to culture bacteria in the laboratory, including lack of essential nutrients, osmotic support or incubation conditions, low growth rate, development of micro-colonies, and the presence of senescent or viable but nonculturable (VBNC) cells. In the marine environment, many bacteria have been associated with dormancy, as typified by the VBNC state. VBNC refers to a state where bacteria are metabolically active, but are no longer culturable on routine growth media. It is apparently a unique survival strategy that has been adopted by many microorganisms in response to harsh environmental conditions and the bacterial cells in the VBNC state may regain culturability under favorable conditions. The resuscitation of VBNC cells may well be an important way to cultivate the otherwise uncultured microorganisms in marine environments. Many resuscitation stimuli that promote the restoration of culturability have so far been identified;these include sodium pyruvate, quorum sensing autoinducers, resuscitation-promoting factors Rpfs and YeaZ, and catalase. In this review, we focus on the issues associated with bacterial culturability, the diversity of bacteria entering the VBNC state, mechanisms of induction into the VBNC state, resuscitation factors of VBNC cells and implications of VBNC resuscitation stimuli for cultivating these otherwise uncultured microorganisms. Bringing important microorganisms into culture is still important in the era of high-throughput sequencing as their ecological functions in the marine environment can often only be known through isolation and cultivation.展开更多
Carbon-coated Ni,Co and Ni-Co alloy catalysts were prepared by the carbonization of the metal doped resorcinol-formaldehyde resins synthesized by the one-pot extended Stöber method.It was found that the introduct...Carbon-coated Ni,Co and Ni-Co alloy catalysts were prepared by the carbonization of the metal doped resorcinol-formaldehyde resins synthesized by the one-pot extended Stöber method.It was found that the introduction of Co remarkably reduced the carbon microsphere size.The metallic Ni,Co,and Ni-Co alloy particles(mainly 10-12 nm)were uniformly distributed in carbon microspheres.A charge transfer from Ni to Co appeared in the Ni-Co alloy.Compared with those of metallic Ni and Co,the d-band center of the Ni-Co alloy shifted away from and toward the Fermi level,respectively.In the in-situ aqueous phase hydrodeoxygenation of methyl palmitate with methanol as the hydrogen donor at 330℃,the decarbonylation/decarboxylation pathway dominated on all catalysts.The Ni-Co@C catalysts gave higher activity than the Ni@C and Co@C catalysts,and the yields of n-pentadecane and n-C6-n-C16 reached 71.6%and 92.6%,respectively.The excellent performance of Ni-Co@C is attributed to the electronic interactions between Ni and Co and the small carbon microspheres.Due to the confinement effect of carbon,the metal particles showed high resistance to sintering under harsh hydrothermal conditions.Catalyst deactivation is due to the carbonaceous deposition,and the regeneration with CO_(2) recovered the catalyst reactivity.展开更多
基金supported by the 1.3.5 Project for Disciplines of Excellence,West China Hospital,Sichuan University(Grant No.ZYGD18011 and No.ZYJC18015 to Wang K).
文摘Objective: Flexible ureteroscopy (fURS) has become a widely accepted and effective technique for treating kidney stones. With the development of new laser systems, the fURS approach has evolved significantly. This literature review aims to examine the current state of knowledge on fURS treatment of kidney stones, with a particular focus on the impact of the latest laser technologies on clinical outcomes and patient safety.Methods: We conducted a search of the PubMed/PMC, Web of Science Core Collection, Scopus, Embase (Ovid), and Cochrane Databases for all randomized controlled trial articles on laser lithotripsy in September 2023 without time restriction.Results: We found a total of 22 relevant pieces of literature. Holmium laser has been used for intracavitary laser lithotripsy for nearly 30 years and has become the golden standard for the treatment of urinary stones. However, the existing holmium laser cannot completely powder the stone, and the retropulsion of the stone after the laser emission and the thermal damage to the tissue have caused many problems for clinicians. The introduction of thulium fiber laser and Moses technology brings highly efficient dusting lithotripsy effect through laser innovation, limiting pulse energy and broadening pulse frequency.Conclusion: While the holmium:yttrium-aluminum-garnet laser remains the primary choice for endoscopic laser lithotripsy, recent technological advancements hint at a potential new gold standard. Parameter range, retropulsion effect, laser fiber adaptability, and overall system performance demand comprehensive attention. The ablation efficacy of high-pulse-frequency devices relies on precise targeting, which may pose practical challenges.
文摘A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite (molar ratio of SiO2 to Al2O3 being 25) was 2:1. The CuO-ZnO-Al2O3-ZrO2 (CuO/ZnO/Al2O3=3/6/1 by weight) component was prepared by a modified 'two-step' co-precipitation method. The effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSMo5 catalyst for dimethyl ether synthesis from CO2 hydrogenation were investigated. It was found that ZrO2 improved the properties of CuO-ZnO-Al2O3/HZSM-5 as a structural promoter.
基金supported by the National Natural Science Foundation of China (21576193)
文摘Ni/Si O_2 and bimetallic Ni_xGa/SiO_2 catalysts with different Ni/Ga atomic ratios(x = 10~2) were investigated for the selective hydrogenation of acetylene.It was found that Ni_xGa/SiO_2 showed higher selectivity to ethylene than Ni/Si O_2.This is attributed to the formation Ni-Ga alloy and Ni3 Ga intermetallic compound(IMC) where there was a charge transfer from Ga to Ni,which is favorable for reducing the adsorption strength and amount of ethylene on Ni atoms.As a result,the over-hydrogenation,the C–C bond hydrogenolysis and the polymerization were suppressed,and subsequently the selectivity to ethylene was enhanced.With the decrease of Ni/Ga atomic ratio,the activity and stability of the Ni_xGa/SiO_2 catalysts increased first and then decreased,while the ethylene selectivity tended to increase.Ni_5 Ga/SiO_2 exhibited the best performance.Under the conditions of 180 °C,0.1 MPa,and a reactant(1.0 vol% acetylene,5.0 vol% H_2 and 94 vol% N_2) with the space velocity of 36,000 m L h^(-1) g^(-1),the acetylene conversion maintained at 100% on Ni_5 Ga/SiO_2 during 120 h time on stream and the selectivity to ethylene was 75%~81%after reaction for 68 h.It was also found that the formation of Ni-Ga alloy and Ni_3 Ga IMC suppressed the incorporation of carbon to form NiCx,subsequently enhancing the catalyst stability.Additionally,with increasing the Ga content,the catalyst acid amount and strength tended to increase,which promoted the polymerization and carbon deposition and so the catalyst deactivation.
基金financially supported by the National Natural Science Foundation of China(No.21176177)the Natural Science Foundation of Tianjin(No.12JCYBJC13200)
文摘NiP/SiOand bimetallic Ni MP/Si O2(M = Co, Fe, Mo, W; Ni/M atomic ratio=5) catalysts were prepared by the temperature-programmed reduction method. The catalysts and their precursors were characterized by means of UV–Vis DRS, H-TPR, XRD, TEM, CO chemisorption and NH-TPD. Their performance for the deoxygenation of methyl laurate was tested on a fixed-bed reactor. The results show that the main phase was NiP in all catalysts, and M(M = Co, Fe, Mo, W) entered the lattice of NiP forming solid solution. Different from Fe and Co, the introduction of Mo and W into NiP/SiOreduced the phosphide particle size and increased the acid amount. In the deoxygenation reaction, the turnover frequency of methyl laurate increased on the catalysts in the order of NiMoP/SiO, NiP/SiO, Ni WP/Si O2, NiFeP/SiOand NiCoP/SiO, which is influenced by the size of phosphide particles and the interaction between Ni and M(M = Fe, Co, Mo or W). The introduction of the second metal(especially Mo and W) into NiP/SiOpromoted the hydrodeoxygenation pathway. This is mainly attributed to the interaction between Ni and the second metal. Finally, the Ni MoP/SiOcatalyst was tested at 340 oC, 3 MPa, methyl laurate WHSV of 14 h-1and H/methyl laurate molar ratio of 25 for 132 h, and its deactivation took place. We found that the catalyst deactivation mainly resulted from carbonaceous deposit rather than the sintering of metal phosphide crystallites.
基金support from the National Natural Science Foundation of China(Nos.21576193 and 21176177)。
文摘Ni–Ga alloy(Ni/Ga atomic ratio of 8),Ni3Ga and Ni5Ga3 intermetallic compounds(IMCs)catalysts were prepared from Ni–Mg-Al-Ga layered double hydroxides(LDHs)for the deoxygenation of methyl esters to hydrocarbons.In the alloy and IMCs,the presence of Ga reduced the surface Ni atom density,and the charge transfer from Ga to Ni increased the electron density of Ni.In the deoxygenation of methyl laurate,the Ni catalyst gave a complete hydrogenolysis of methyl laurate to CH4at 330°C and 3.0 MPa,while the presence of Ga promoted the HDO pathway and suppressed C–C bond hydrogenolysis and methanation.The Ni5Ga3 catalyst exhibited the best desired performance.Even at 400°C,it gave the yield of C11 and C12 hydrocarbons of ~99%,and the selectivity to CH4(SCH4) was only 2.4%.In the deoxygenation of methyl octanoate and methyl palmitate,the Ni5Ga3 catalyst also gave the yield of hydrocarbons above95%.Reactivity evaluation and methyl propionate-TPD and TPSR results indicate that the C–OCH3 bond instead of the O–CH3 one was cleaved on both Ni and bimetallic Ni–Ga catalysts.It is highlighted that methanol,derived from the C–OCH3 bond hydrogenolysis,mainly decomposed to CO and H2 on IMCs,while it was converted to methane on metallic Ni and alloy.It is of great significance that H2 could be yielded from the methyl ester itself.In short,the utilization of Ni–Ga IMCs can effectively reduce carbon loss and H2 consumption,all of which are ascribed to the geometric and electronic effects of Ga.
基金supported by the National Natural Science Foundation of China(No.21176177)the Natural Science Foundation of Tianjin(No.12JCYBJC13200)State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)
文摘SiO2-supported Ni-Mo bimetallic phosphides were prepared by temperature-programmed reduction (TPR) method from the phosphate precur- sors calcined at different temperatures. Their properties were characterized by means of ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), H2 temperature-programmed reduction (H2-TPR), X-ray diffraction (XRD), transmission electron microscopy (TEM), CO chemisorption, H2 and NH3 temperature-programmed desorptions (H2-TPD and NH3-TPD). Their catalytic performances for the deoxygena- tion of methyl laurate were tested in a fixed-bed reactor. When the precursors were calcined at 400 and 500 ℃, respectively, NiMoP2 phase could be formed apart from Ni2P and MoP phases in the prepared C400 and C500 catalysts. However, when the precursors were calcined at 600, 700 and 800 ℃, respectively, only Ni2P and MoP phases could be detected in the prepared C600, C700 and C800 catalysts. Also, in C400, C500 and C600 catalysts, Mo atoms were found to be entered in the lattice of Ni2P phase, but the entering extent became less with the increase of calcination temperature. As the calcination temperature of the precursor increased, the interaction between Ni and Mo in the prepared catalysts decreased, and the phosphide crystallite size tended to increase, subsequently leading to the decrease in the surface metal site density and the acid amount. C600 catalyst showed the highest activity among the tested ones for the deoxygenation of methyl laurate. As the calcination temperature of the precursor increased, the selectivity to C12 hydrocarbons decreased while the selectivity to C11 hydrocarbons tended to increase. This can be mainly attributed to the decreased Ni-Mo interaction and the increased phosphide particle size. In sum, the structure and performance of Ni-Mo bimetallic phosphide catalyst can be tuned by the calcination temperature of precursor.
文摘Objective: To examine the trajectory of psychosomatic symptoms and to explore the impact of psychosomatic symptoms on setup error in patients undergoing breast cancer radiotherapy.Methods: A total of 102 patients with early breast cancer who received initial radiotherapy were consecutively recruited. The M.D. Anderson Symptom Inventory(MDASI) and three different anxiety scales, i.e., the Self-Rating Anxiety Scale(SAS), State-Trait Anxiety Inventory(STAI), and Anxiety Sensitivity Index(ASI), were used in this study. The radiotherapy setup errors were measured in millimetres by comparing the real-time isocratic verification film during radiotherapy with the digitally reconstructed radiograph(DRR). Patients completed the assessment at three time points: before the initial radiotherapy(T1), before the middle radiotherapy(T2), and before the last radiotherapy(T3).Results: The SAS and STAI-State scores of breast cancer patients at T1 were significantly higher than those at T2 and T3(F=24.44, P<0.001;F=30.25, P<0.001). The core symptoms of MDASI were positively correlated with anxiety severity. The setup errors of patients with high SAS scores were greater than those of patients with low anxiety levels at T1(Z=-2.01, P=0.044). We also found that higher SAS scores were associated with a higher risk of radiotherapy setup errors at T1(B=0.458, P<0.05).Conclusions: This study seeks to identify treatment-related psychosomatic symptoms and mitigate their impact on patients and treatment. Patients with early breast cancer experienced the highest level of anxiety before the initial radiotherapy, and then, anxiety levels declined. Patients with high somatic symptoms of anxiety may have a higher risk of radiotherapy setup errors.
基金supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)
文摘Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal(Fe, Co, Ni, Mo and W) phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.
基金supported by the National Natural Science Foundation of China(21576193,21176177)~~
文摘SiO2‐supported monometallic Ni and bimetallic Ni‐In catalysts were prepared and used for hydrodeoxygenation of anisole,which was used as a model bio‐oil compound,for BTX(benzene,toluene,and xylene)production.The effects of the Ni/In ratio and Ni content on the structures and performances of the catalysts were investigated.The results show that In atoms were incorporated into the Ni metal lattice.Although the Ni‐In bimetallic crystallites were similar in size to those of monometallic Ni at the same Ni content,H2uptake by the bimetallic Ni‐In catalyst was much lower than that by monometallic Ni because of dilution of Ni atoms by In atoms.Charge transfer from In to Ni was observed for the bimetallic Ni‐In catalysts.All the results indicate intimate contact between Ni and In atoms,and the In atoms geometrically and electronically modified the Ni atoms.In the hydrodeoxygenation of anisole,although the activities of the Ni‐In bimetallic catalysts in the conversion of anisole were lower than that of the monometallic Ni catalyst,they gave higher selectivities for BTX and cyclohexane as a result of suppression of benzene ring hydrogenation and C–C bond hydrogenolysis.They also showed lower methanation activity.These results will be useful for enhancing carbon yields and reducing H2consumption.In addition,the lower the Ni/In ratio was,the greater was the effect of In on the catalytic performance.The selectivity for BTX was primarily determined by the Ni/In ratio and was little affected by the Ni content.We suggest that the performance of the Ni‐In bimetallic catalyst can be ascribed to the geometric and electronic effects of In.
基金Supported by a grant from Importance Introduction Person with Ability Startup Fund of Jiangsu University Affiliated Hospital (Number: p-67).
文摘Objective: To investigate the expression of vascular endothelial growth factor D (VEGF-D) in gastric cancer and its relationship with lymph node metastasis. Methods: 100 cases of gastric carcinoma tissues (50 cases with lymph node metastasis, 50 cases negative) and 30 cases of normal gastric tissues were gathered to detect the expressions of VEGF-C and D proteins by immunohistochemistry. Results: VEGF-C and D were revealed in cytoplasm of gastric carcinoma tissues and normal gastric tissues. The positive rates of VEGF-C and D expressions were significantly higher in gastric cancer tissues than those in the normal ones (51%, 60% vs 10%, 20% respectively; both P < 0.05). There were significant correlations be- tween the positive expression of VEGF-D and lymph node metastasis, lymphatic invasion, positive expression of VEGF-C, but not with tumour size, tissue differentiation, and venous invasion. Conclusion: The expression of VEGF-D is closely related to lymph node metastasis in gastric carcinoma.
文摘Porous carbon-encapsulated Ni and Ni-Sn intermetallic compound catalysts were prepared by the one-pot extended Stöber method followed by carbonization and tested for in-situ hydrothermal deoxygenation of methyl palmitate with methanol as the hydrogen donor.During the catalyst preparation,Sn doping reduces the size of carbon spheres,and the formation of Ni-Sn intermetallic compounds restrain the graphitization,contributing to larger pore volume and pore diameter.Consequently,a more facile mass transfer occurs in carbon-encapsulated Ni-Sn intermetallic compound catalysts than in carbonencapsulated Ni catalysts.During the in-situ hydrothermal deoxygenation,the synergism between Ni and Sn favors palmitic acid hydrogenation to a highly reactive hexadecanal that easily either decarbonylate to n-pentadecane or is hydrogenated to hexadecanol.At high reaction temperature,hexadecanol undergoes dehydrogenation-decarbonylation,generating n-pentadecane.Also,the C-C bond hydrolysis and methanation are suppressed on Ni-Sn intermetallic compounds,favorable for increasing the carbon yield and reducing the H_(2) consumption.The npentadecane and n-hexadecane yields reached 88.1%and 92.8%on carbon-encapsulated Ni_(3) Sn_(2) intermetallic compound at 330℃.After washing and H_(2) reduction,the carbon-encapsulated Ni_(3) Sn_(2) intermetallic compound remains stable during three recycling cycles.This is ascribed to the carbon confinement that effectively suppresses the sintering and loss of metal particles under harsh hydrothermal conditions.
基金supported by the National Natural Science Foundation of China(No.81773911,81690263,and 81573616)the Development Project of Shanghai Peak Disciplines-Integrated Medicine(No.20180101).
文摘Despite exciting achievements with some malignancies,immunotherapy for hypoimmunogenic cancers,especially glioblastoma(GBM),remains a formidable clinical challenge.Poor immunogenicity and deficient immune infiltrates are two major limitations to an effective cancer-specific immune response.Herein,we propose that an injectable signal-amplifying nanocomposite/hydrogel system consisting of granulocyte-macrophage colony-stimulating factor and imiquimod-loaded antigen-capturing nanoparticles can simultaneously amplify the chemotactic signal of antigen-presenting cells and the"danger"signal of GBM.We demonstrated the feasibility of this strategy in two scenarios of GBM.In the first scenario,we showed that this simultaneous amplification system,in conjunction with local chemotherapy,enhanced both the immunogenicity and immune infiltrates in a recurrent GBM model;thus,ultimately making a cold GBM hot and suppressing postoperative relapse.Encouraged by excellent efficacy,we further exploited this signal-amplifying system to improve the efficiency of vaccine lysate in the treatment of refractory multiple GBM,a disease with limited clinical treatment options.In general,this biomaterial-based immune signal amplification system represents a unique approach to restore GBM-specific immunity and may provide a beneficial preliminary treatment for other clinically refractorymalignancies.
基金This work was financially supported by the National Key Re- search Development Program of China (2018YFD0200100) and the National Natural Science Foundation of China (No. 21672044) and Subsidy Project for Outstanding Key Laboratory of Guizhou Prov- ince in China (20154004).
文摘Forty one novel 1,3,4-oxadiazole/thiadiazole thioether derivatives containing phenoxy moiety were designed and synthesized. Bioassay demonstrated that some of them showed remarkable activities against Tylenchufus semipenetruns in vitro and in vivo. Compounds 20, 21, 35 and 39 showed excellent lethal activities after treatment for 48 h in vitro, with LC50 values of 13.4±1.8, 11.7±2.5, 13.7±2.4 and 13.31.1 mg.L-1, respectively, which were obviously superior to fosthiazate (49.1±2.8 mg.L-1) and avermectin (26.6±2.3 mg.L-1). Compound 23. can effectively control the citrus nema- tode disease caused by T. semipenetruns at 200 mg.L-1 in vivo with (68±3)% inhibitory effect, which was even better than that of avermectin ((63±2)%). The CoMFA and CoMSIA models of three-dimensional quantitative structure-activity relationships (3D-QSARs) were established. The compound 33 was designed based on the 3D-QSAR models with more vigorous nematicidal activities in vitro (LC50:9.8±1.4 mg.L-1) and in vivo ((70±5)%). These results demonstrated that compound 33 can be considered as a potential nematicide.
基金The work was supported by National Key Research and Development Program of China(No.2018YFE0124100)National Natural Science Foundation of China(Nos.41730530 and 91751202)Marine S&T Fund of Shandong Province for Pilot National Laboratory for Marine Science and Technology(Qingdao)(No.2018SDKJ0406-4).
文摘Culturing has been the cornerstone of microbiology since Robert Koch first successfully cultured bacteria in the late nineteenth century. However, even today, the majority of microorganisms in the marine environment remain uncultivated. There are various explanations for the inability to culture bacteria in the laboratory, including lack of essential nutrients, osmotic support or incubation conditions, low growth rate, development of micro-colonies, and the presence of senescent or viable but nonculturable (VBNC) cells. In the marine environment, many bacteria have been associated with dormancy, as typified by the VBNC state. VBNC refers to a state where bacteria are metabolically active, but are no longer culturable on routine growth media. It is apparently a unique survival strategy that has been adopted by many microorganisms in response to harsh environmental conditions and the bacterial cells in the VBNC state may regain culturability under favorable conditions. The resuscitation of VBNC cells may well be an important way to cultivate the otherwise uncultured microorganisms in marine environments. Many resuscitation stimuli that promote the restoration of culturability have so far been identified;these include sodium pyruvate, quorum sensing autoinducers, resuscitation-promoting factors Rpfs and YeaZ, and catalase. In this review, we focus on the issues associated with bacterial culturability, the diversity of bacteria entering the VBNC state, mechanisms of induction into the VBNC state, resuscitation factors of VBNC cells and implications of VBNC resuscitation stimuli for cultivating these otherwise uncultured microorganisms. Bringing important microorganisms into culture is still important in the era of high-throughput sequencing as their ecological functions in the marine environment can often only be known through isolation and cultivation.
基金support from the National Natural Science Foundation of China(Grant Nos.21576193,21176177).
文摘Carbon-coated Ni,Co and Ni-Co alloy catalysts were prepared by the carbonization of the metal doped resorcinol-formaldehyde resins synthesized by the one-pot extended Stöber method.It was found that the introduction of Co remarkably reduced the carbon microsphere size.The metallic Ni,Co,and Ni-Co alloy particles(mainly 10-12 nm)were uniformly distributed in carbon microspheres.A charge transfer from Ni to Co appeared in the Ni-Co alloy.Compared with those of metallic Ni and Co,the d-band center of the Ni-Co alloy shifted away from and toward the Fermi level,respectively.In the in-situ aqueous phase hydrodeoxygenation of methyl palmitate with methanol as the hydrogen donor at 330℃,the decarbonylation/decarboxylation pathway dominated on all catalysts.The Ni-Co@C catalysts gave higher activity than the Ni@C and Co@C catalysts,and the yields of n-pentadecane and n-C6-n-C16 reached 71.6%and 92.6%,respectively.The excellent performance of Ni-Co@C is attributed to the electronic interactions between Ni and Co and the small carbon microspheres.Due to the confinement effect of carbon,the metal particles showed high resistance to sintering under harsh hydrothermal conditions.Catalyst deactivation is due to the carbonaceous deposition,and the regeneration with CO_(2) recovered the catalyst reactivity.