This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate(KMnO_(4))derived manganese dioxide(MnO_(2))micro/nano-adjuvants.Addressing the limitations of tr...This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate(KMnO_(4))derived manganese dioxide(MnO_(2))micro/nano-adjuvants.Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment,our research establishes KMnO_(4)as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1(αPD-L1)antibodies.The in situ synthesized MnO_(2)adjuvants in the tumor exhibit direct interactions with biological systems,leading to the reduction of MnO_(2)to Mn^(2+)within the tumor,and thereby improving the microenvironment for immune cell activity.Our in vitro and in vivo models demonstrate KMnO_(4)’s capability to induce concentration-dependent cytotoxicity in tumor cells,triggering DNA damage and apoptosis.It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1(HMGB1)on the cell surface.The combination of KMnO_(4)withαPD-L1 antibodies substantially inhibits tumor growth,promotes dendritic cell maturation,and enhances CD8^(+)T cell infiltration,resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile.Our findings advocate for further research into the long-term efficacy of KMnO_(4)and its application in diverse tumor models,emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.展开更多
SAPO-34 zeolite is considered to be an effective catalyst for methanol or dimethyl ether conversion to olefins. In this study,we developed the in situ synthesis technology to prepare SAPO-34 zeolite in kaolin micro-sp...SAPO-34 zeolite is considered to be an effective catalyst for methanol or dimethyl ether conversion to olefins. In this study,we developed the in situ synthesis technology to prepare SAPO-34 zeolite in kaolin micro-spheres as a catalyst for fluidized methanol or dimethyl ether to olefins process. The silicoaluminophosphate zeolite was first time reported to be synthesized in kaolin microspheres. The SAPO-34 content of synthesized catalyst was about 22% as measured by three different quantitative methods(micropore area,X-ray fluorescence and energy dispersive spectroscopy element analysis) . Most of the SAPO-34 zeolites were in nanoscale size and distributed uniformly inside the spheres. The catalytic performance was evaluated in fixed bed and fluidized bed reactors. Compared with the conventional spray-dry catalyst,SAPO/kaolin catalyst showed superior catalytic activities,bet-ter olefin selectivities(up to 94%,exclusive coke) ,and very good hydrothermal stability. The in situ synthesis of SAPO-34 in kaolin microspheres is a facile and economically feasible way to prepare more effective catalyst for fluidized MTO/DTO(methanol to olefins/dimethyl ether to olefins) process.展开更多
The rational exploitation of non-precious metal catalyst with high activity,strong durability and low cost for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of vital importance for metalair ba...The rational exploitation of non-precious metal catalyst with high activity,strong durability and low cost for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of vital importance for metalair batteries.Herein,a composite of Co_(3)O_(4)nanoparticles confined in three-dimensional(3 D)N-doped porous carbon(Co-NpCs)was prepared by a simple freeze-drying and in situ pyrolysis method.The effect of different dosages of Co(NO_(3))_(2)on the catalytic performance was discussed.The Co-NpC-12%exhibits the best catalytic performance(E_(1/2)=0.78 V,better stability than 20%Pt/C)in ORR and in OER among all the as-synthesized samples.Furthermore,it also exhibits the best bifunctional activity(ΔE=0.849 V).The excellent properties of Co-NpCs are mainly due to the synergy between Co_(3)O_(4)and carbon.Firstly,a high Co_(3)O_(4)loading amount can boost the defect level of the N-doped hierarchical porous carbon and expose more active sites.Secondly,the unique in situ pyrolysis guarantees a largearea contact between Co_(3)O_(4)and carbon as well as a strong C-O-Co bonding,which promotes charge transfer,avoids the peeling of Co_(3)O_(4)nanoparticles and effectively improves the stability of the material.This work is expected to offer a feasible strategy to produce metal oxide/carbon nanocomposite and push forward the development of bifunctional electrocatalyst with high activity and stability.展开更多
Fe-based alloy coatings containing TiB2–TiN –（h-BN） were synthesized in situ on Q235 steel substrates by a plasma cladding process using the powders of Fe901 alloy, Ti, and h-BN as raw materials. The effects of Ti...Fe-based alloy coatings containing TiB2–TiN –（h-BN） were synthesized in situ on Q235 steel substrates by a plasma cladding process using the powders of Fe901 alloy, Ti, and h-BN as raw materials. The effects of Ti/h-BN mass ratio on interfacial bonds between the coating and substrate along with the microstructures and microhardnesses of the coatings were investigated. The results show that the Ti/h-BN mass ratio is a vital factor in the formation of the coatings. Free h-BN can be introduced into the coatings by adding an excess amount of h-BN into the precursor. Decreases in the Ti/h-BN mass ratio improve the microstructural uniformity and compactness and enhance the interfacial bonds of the coatings. At a Ti/h-BN mass ratio of 10/20, the coating is free of cracks and micropores, and mainly consists of Fe-Cr, Fe3B, TiB2, TiN, Ti2N, TiB, FeN, FeB, Fe2B, and h-BN phases. Its average microhardness in the zone between 0.1–2.8 mm from the coating surface is about Hv0.2 551.5.展开更多
In situ surface synthesis of Ca–Mg–Al hydrotalcite(HT) on inorganic ceramic membrane(CM) was investigated with urea as precipitator. The effects of molar ratio of raw materials, crystallization time, and temperature...In situ surface synthesis of Ca–Mg–Al hydrotalcite(HT) on inorganic ceramic membrane(CM) was investigated with urea as precipitator. The effects of molar ratio of raw materials, crystallization time, and temperature on surface synthesis of HT were examined. The as-prepared HT/CM samples were characterized by XRD and SEM and an in situ growth mechanism of HT on CM was proposed. KF/HT/CM obtained by loading potassium fluoride(KF) on the HT layer by impregnation and calcination method was used as catalyst for transesterification between palm oil and methanol. The comparison of KF/HT/CM and pure KF/HT powder under identical reaction conditions shows that the production of fatty acid methyl ester is equivalent, which means that the use of inorganic catalytic membrane in the transesterification is a viable alternative.展开更多
Polypropylene microporous membranes were treated with plasma in a mixture of N2 and H2 (1:2 in volume). Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT1R), X-ray photoelectron spectroscopy...Polypropylene microporous membranes were treated with plasma in a mixture of N2 and H2 (1:2 in volume). Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT1R), X-ray photoelectron spectroscopy (XPS) and ultra-violet (UV) spectra demonstrated the success of grafting amino groups. The density of the polar amino groups on the membrane surface is about 0.59 μmol/cm2. The as-treated membranes were successively applied to the in situ synthesis of oligonucleotides and an average coupling yield was more than 98%. The surface feature of the treated membrane is suggested to be responsible for its advantage over a glass slide.展开更多
Chemodynamic therapy (CDT) has attracted tremendous interest in cancer therapy because it is independent of oxygen and photoirradiation. However, the therapeutic efficacy of CDT is restricted by insufficient H_(2)O_(2...Chemodynamic therapy (CDT) has attracted tremendous interest in cancer therapy because it is independent of oxygen and photoirradiation. However, the therapeutic efficacy of CDT is restricted by insufficient H_(2)O_(2) levels in tumor cells. Herein, employing endogenous GSH as a template and cationic polymeric chitosan (CS) as crosslinker and stabilizer exhibiting easy cell uptake, red luminescent gold nanoclusters (denoted CS-GSH@AuNCs) were successfully synthesized in HeLa cells. The in situ synthesized CS-GSH@AuNCs exhibited both superoxidase dismutase (SOD) and peroxidase (POD)-like activity, which could promote the production of H_(2)O_(2) from superoxide anion radicals (O_(2)^(·-)) and then ^(·)OH. The combination of GSH elimination and H_(2)O_(2) elevation boosted the generation of ^(·)OH, which could trigger cancer cell apoptosis and death. The enzyme-like activity of CS-GSH@AuNCs could be effectively activated under acidic conditions, and showed a high killing effect on tumor cells but minimal toxicity to normal cells. The developed GSH consumption and ^(·)OH promotion theranostic platform is an innovative route for enhanced CDT by the amplification of oxidative stress.展开更多
The porcine microsatellite SW943 was regionally localized on 12p11-(2/3p13) by the two methods: the Primed in situ (PRINS) labelling on the pachytene bivalents of pigs using the Dig-11-dUTP as the report molecule and ...The porcine microsatellite SW943 was regionally localized on 12p11-(2/3p13) by the two methods: the Primed in situ (PRINS) labelling on the pachytene bivalents of pigs using the Dig-11-dUTP as the report molecule and pig X rodent Somatic Cell Hybrid Panel (SCHP) which contains 27 cell lines through PCR amplification. Advantages and disadvantages of the two methods for physical mapping of microsatellites were also discussed.展开更多
A novel substrate for in situ synthesis of oligonucleotide was prepared by hydrolyzing microporous polyamide-6 membranes in a 0.01mol/L NaOH/(H2O-CH3OH) mixture medium. The formation of amines (NH2) on the surface was...A novel substrate for in situ synthesis of oligonucleotide was prepared by hydrolyzing microporous polyamide-6 membranes in a 0.01mol/L NaOH/(H2O-CH3OH) mixture medium. The formation of amines (NH2) on the surface was proved by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The treated membrane was applied for in situ synthesis of oligonucleotide and a single step coupling efficiency determined by ultraviolet (UV) spectra was above 98 %.展开更多
Metal-organic frameworks（MOFs） are important functional materials. MOF-5（IL）（Zn4O（BDC）3（BDC=1,4-benzenedicarboxylate） was in situ synthesized by the electrochemical method using a tunable ionic liquid（IL）, ...Metal-organic frameworks（MOFs） are important functional materials. MOF-5（IL）（Zn4O（BDC）3（BDC=1,4-benzenedicarboxylate） was in situ synthesized by the electrochemical method using a tunable ionic liquid（IL）, 1-butyl-3-methylimidazolium chloride, as template. The crystallization of distinctly spherical MOF-5（IL） synthsized in ionic liquid by the electrochemical method is attributed to π-π stacking effect, ionic bond, and coordination bond. The analysis results show that the product MOF-5（IL） exhibits better crystallinity and higher thermal stability than MOF-5 generated using the solvothermal method. The cyclic voltammetry reveals that the electrosynthesis reaction is irreversible and controlled by the diffusion. The experiments on methylorange degradation show that the unique structure characteristics of MOF-5（IL） can enhance the photocatalytic ability of Bi OBr. Therefore, MOFs can replace noble metals to improve the photocatalytic properties of bismuth oxyhalide.展开更多
A phase-pure NaTi2（PO4）3/reduced graphene oxide （rGO） nanocomposite was prepared using a microwave-assisted one-pot method and subsequent heat treatment. The well-crystallized NaTi2（PO4）3 nanoparticles （30-40 n...A phase-pure NaTi2（PO4）3/reduced graphene oxide （rGO） nanocomposite was prepared using a microwave-assisted one-pot method and subsequent heat treatment. The well-crystallized NaTi2（PO4）3 nanoparticles （30-40 nm） were uniformly precipitated on rGO templates through Ti-O-C bonds. The chemical interactions between the NaTi2（PO4）3 nanoparticles and rGO could immobilize the NaTi2（PO4）3 nanoparticles on the rGO sheets, which might be responsible for the excellent electrochemical performance of the nanocomposite. The NaTi2（PO4）B/rGO nanocomposite exhibited a specific capacity of 128.6 mA-h.g-1 approaching the theoretical value at a 0.1 C-rate with an excellent rate capability （72.9% capacity retention at 50 C-rate） and cycling performance （only 4.5% capacity loss after 1,000 cycles at a high rate of 10 C）. These properties were maintained even when the electrodes were prepared without the use of an additional conducting agent. The excellent sodium storage properties of the NaTi2（PO4）B/rGO nanocomposite could be attributed to the nano-sized NaTi2（PO4）3 particles, which significantly reduced the transport lengths for Na＋ ions, and an intimate contact between the NaTi2（PO4）3 particles and rGO due to chemical bonding.展开更多
Cell membrane affinity chromatography has been widely applied in membrane protein(MP)-targeted drug screening and interaction analysis.However,in current methods,the MP sources are derived from cell lines or recombina...Cell membrane affinity chromatography has been widely applied in membrane protein(MP)-targeted drug screening and interaction analysis.However,in current methods,the MP sources are derived from cell lines or recombinant protein expression,which are time-consuming for cell culture or purification,and also difficult to ensure the purity and consistent orientation of MPs in the chromatographic stationary phase.In this study,a novel in situ synthesis membrane protein affinity chromatography(iSMAC)method was developed utilizing cell-free protein expression(CFE)and covalent immobilized affinity chromatography,which achieved efficient in situ synthesis and unidirectional insertion of MPs into liposomes in the stationary phase.The advantages of iSMAC are:1)There is no need to culture cells or prepare recombinant proteins;2)Specific and purified MPs with stable and controllable content can be obtained within 2 h;3)MPs maintain the transmembrane structure and a consistent orientation in the chromatographic stationary phase;4)The flexible and personalized construction of cDNAs makes it possible to analyze drug binding sites.iSMAC was successfully applied to screen PDGFRβinhibitors from Salvia miltiorrhiza and Schisandra chinensis.Micro columns prepared by in-situ synthesis maintain satisfactory analysis activity within 72 h.Two new PDGFRβinhibitors,salvianolic acid B and gomisin D,were screened out with KD values of 13.44 and 7.39μmol/L,respectively.In vitro experiments confirmed that the two compounds decreasedα-SMA and collagen Ⅰ mRNA levels raised by TGF-βin HSC-T6 cells through regulating the phosphorylation of p38,AKT and ERK.In vivo,Sal B could also attenuate CCl_(4)-induced liver fibrosis by downregulating PDGFRβdownstream related protein levels.The iSMAC method can be applied to other general MPs,and provides a practical approach for the rapid preparation of MP-immobilized or other biological solid-phase materials.展开更多
In this work,silicon-carbon hybrid materials were adopted as an example to illustrate the novel strategy to in situ construct heterostructure with adjustable microstructure.Based on the temperature-dependent thermodyn...In this work,silicon-carbon hybrid materials were adopted as an example to illustrate the novel strategy to in situ construct heterostructure with adjustable microstructure.Based on the temperature-dependent thermodynamics and kinetics of reaction between Si and C,the processes for Si nanocrystals growth and C decoration were coupled at different zones of plasma flame according to its temperature and velocity fields by theoretical modeling,aiming to intentionally suppress the formation of undesirable carbide,and enable adjusting the microstructure of each counterpart separately in transient process.As a result,well-controlled Si/C nanocomposites,including nanospheres and nanowires with core-shell structures,were achieved,and this continuous and in-flight route is also potential for large-scale production.Further investigation on the electrochemical properties highlights the advantage of as proposed strategy to efficiently construct heterostructures with superior performance for various applications.展开更多
Explorations of new second harmonic generation materials in Ag^+-Hg^2+/Bi^3+-selenites systems afforded three new silver selenium oxides, namely, Ag4 Hg(SeO3)2(SeO4)(1), Ag2Bi2(SeO3)3(SeO4)(2) and Ag5 Bi(SeO3)4(3). Th...Explorations of new second harmonic generation materials in Ag^+-Hg^2+/Bi^3+-selenites systems afforded three new silver selenium oxides, namely, Ag4 Hg(SeO3)2(SeO4)(1), Ag2Bi2(SeO3)3(SeO4)(2) and Ag5 Bi(SeO3)4(3). They exhibit flexible crystal chemistry. Compounds 1 and 2 are mixed valence selenium oxides containing Se(IV) and Se(VI) cations simultaneously. Compounds 1 and 3 exhibit a 3 D open framework with 4-, 6-and 8-member polyhedral ring tunnels along a, b and c axes. Compound 1 crystallized in a polar space group and could display a subtle frequency doubling efficiency about 35% of the commercial KH2PO4(KDP). UV-vis-NIR spectra reveal that compounds 1–3 are wide-band semiconductors with the optical bandgaps of 3.11, 3.65, 3.58 e V respectively. Theoretical calculations disclose that compounds2 and 3 are indirect band gap structures and their bandgaps are determined by Ag, Bi, Se and O atoms together.展开更多
In situ synthesis method was used to prepare V8C7–Cr3C2nanocomposite.Ammonium vanadate, ammonium dichromate and nanometer carbon black were used as raw materials.The products were characterized by X-ray diffractometr...In situ synthesis method was used to prepare V8C7–Cr3C2nanocomposite.Ammonium vanadate, ammonium dichromate and nanometer carbon black were used as raw materials.The products were characterized by X-ray diffractometry(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), thermogravimetric and differential scanning calorimetry(TGDSC) and X-ray photoelectron spectroscopy(XPS) techniques.The results show that V8C7–Cr3C2nanocomposite with an average crystallite size of 25.4 nm can be synthesized at 1200 °C for 1 h.The synthesis temperature required by the method is at least 200 °C lower than that required by the conventional approaches for preparing vanadium and chromium carbides.The powders show good dispersion and are mainly composed of spherical or nearly spherical particles with a mean diameter of about 30 nm.The weight loss ratio of the precursor throughout the reaction process reaches 58 wt%.Three exothermic peaks and four endothermic peaks occur during the reaction.The surface of the specimen is mainly composed of V, Cr, C and O elements.展开更多
ZrB2 in MgO-C composite materials obtained by both microwave sintering synthesis and in-situ reaction at lower temperature was investigated. The test result shows that 66.67 % of reactant changed into Zrb2, and the ot...ZrB2 in MgO-C composite materials obtained by both microwave sintering synthesis and in-situ reaction at lower temperature was investigated. The test result shows that 66.67 % of reactant changed into Zrb2, and the other form Al2O3, which could optimize the properties of carbon containing materials. Therefore, the method of in situ synthesizing ZrB2 acting as antioxidant in carbon containing materials is considered as one of best ways to reduce the cost and ZrB2 as refractories is used on a large-scale.展开更多
The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at ...The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.展开更多
A process for in situ synthesis of terbium complex with salicylic acid by a two-step solgel method in silica matrix has been proposed. The luminescence properties of the silica gelscodoped with terbium and salicylic a...A process for in situ synthesis of terbium complex with salicylic acid by a two-step solgel method in silica matrix has been proposed. The luminescence properties of the silica gelscodoped with terbium and salicylic acid have also been discussed with respect to that of the geldoped with terbium and that of pure terbium complex with salicylic acid.展开更多
This work used the in-situ synthesis of molten-state nitride ceramic phase-reinforced Ni-based alloy coat-ings,aiming to improve the phase-interface bonding through the interdependent co-solidification be-tween molten...This work used the in-situ synthesis of molten-state nitride ceramic phase-reinforced Ni-based alloy coat-ings,aiming to improve the phase-interface bonding through the interdependent co-solidification be-tween molten droplets.The XRD was used to analyze the physical phases of the composite coatings.The microstructure and phase-interface structure were characterized in detail by combining SEM,TEM,HRTEM,FFT,and SAED techniques.Microhardness tester and microforce microhardness tester were em-ployed to measure the surface hardness and elastic modulus of the composite coatings.The fracture be-havior of the composite coatings was characterized by observing the fracture morphology of the coatings using SEM combined with the EDS technique.It was found that the formation mechanisms of inter-facial misfit dislocation assistance,lattice distortion,aggregation of stacking faults,and specific growth orientation between theγ-Ni matrix phase and each ceramic phase in NiCrBSi-TiCrN composite coat-ings improved the lattice matching between the two-phase interface,which resulted in the formation of atomically corresponding coherent lattice relations and stepped interfacial semi-coherent lattice relations,and enhanced the degree of phase-interface bonding.On this basis,the composite coatings with high Cr content further inhibited the expansion of interphase penetration cracks due to the existence of Cr-rich zones at the phase interface,thus exhibiting high fracture toughness.This work provides new opinions on the improvement of phase-interface bonding and composition design of Ni-based composite coatings.展开更多
A novel maskless technique, self-driving micro-fluid porous type printing （SMPTP）, was reported to in situ synthesize oligonucleotide arrays on glass slide, which has the merits of low cost, high quality and simple ...A novel maskless technique, self-driving micro-fluid porous type printing （SMPTP）, was reported to in situ synthesize oligonucleotide arrays on glass slide, which has the merits of low cost, high quality and simple craft. In SMPTP for fabricating gene- chips, porous fiber tubes with a number of nanometric or micron channels functioned as ＂active letters＂ and were assembled in designed patterns, which are identical to the distribution of monomers in each layer of the array, and four patterns were needed for each layer. By means of capillarity, the synthesis solution was automatically taken into porous tubes assembled in a printing plate and reached the surface. An oligonucleotide array of 160 features with four different 15-mer probes was in situ synthesized using this technique. The four specific oligonucleotide probes, including the matched and the mismatched by the fluorescent target sequence, gave obviously different hybridization fluorescent signals.展开更多
基金supported by the Natural Science Foundation of Guangdong Province(No.2023A1515030291)the Dongguan Science and Technology of Social Development Program(No.20211800905282)+8 种基金the National Key Research and Development Program of China(Nos.2022YFC2303600,2020YFA0908000)the Innovation Team and Talents Cultivation Program of National Administration of Traditional Chinese Medicine(No.ZYYCXTDC-202002)the CACMS Innovation Fund(Nos.CI2023E002,CI2021A05101,CI2021A05104)the Scientific and Technological Innovation Project of China Academy of Chinese Medical Sciences(Nos.CI2023D003,CI2021B014)the Science and Technology Foundation of Shenzhen(No.JCYJ20210324115800001)the Science and Technology Foundation of Shenzhen(Shenzhen Clinical Medical Research Center for Geriatric Diseases)the Shenzhen Medical Research Fund(No.B2302051)the Distinguished Expert Project of Sichuan Province Tianfu Scholar(No.CW202002)Shenzhen Science and Technology Program(No.RCBS20210609104424065).
文摘This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate(KMnO_(4))derived manganese dioxide(MnO_(2))micro/nano-adjuvants.Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment,our research establishes KMnO_(4)as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1(αPD-L1)antibodies.The in situ synthesized MnO_(2)adjuvants in the tumor exhibit direct interactions with biological systems,leading to the reduction of MnO_(2)to Mn^(2+)within the tumor,and thereby improving the microenvironment for immune cell activity.Our in vitro and in vivo models demonstrate KMnO_(4)’s capability to induce concentration-dependent cytotoxicity in tumor cells,triggering DNA damage and apoptosis.It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1(HMGB1)on the cell surface.The combination of KMnO_(4)withαPD-L1 antibodies substantially inhibits tumor growth,promotes dendritic cell maturation,and enhances CD8^(+)T cell infiltration,resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile.Our findings advocate for further research into the long-term efficacy of KMnO_(4)and its application in diverse tumor models,emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
基金Supported by the National Natural Science Foundation of China（20736004）
文摘SAPO-34 zeolite is considered to be an effective catalyst for methanol or dimethyl ether conversion to olefins. In this study,we developed the in situ synthesis technology to prepare SAPO-34 zeolite in kaolin micro-spheres as a catalyst for fluidized methanol or dimethyl ether to olefins process. The silicoaluminophosphate zeolite was first time reported to be synthesized in kaolin microspheres. The SAPO-34 content of synthesized catalyst was about 22% as measured by three different quantitative methods(micropore area,X-ray fluorescence and energy dispersive spectroscopy element analysis) . Most of the SAPO-34 zeolites were in nanoscale size and distributed uniformly inside the spheres. The catalytic performance was evaluated in fixed bed and fluidized bed reactors. Compared with the conventional spray-dry catalyst,SAPO/kaolin catalyst showed superior catalytic activities,bet-ter olefin selectivities(up to 94%,exclusive coke) ,and very good hydrothermal stability. The in situ synthesis of SAPO-34 in kaolin microspheres is a facile and economically feasible way to prepare more effective catalyst for fluidized MTO/DTO(methanol to olefins/dimethyl ether to olefins) process.
基金the National Natural Science Foundation of China(Nos.51871046,51902046,51874079,51571054,51771046 and 51674068)the Natural Science Foundation of Liaoning Province(No.201602257)+1 种基金the Natural Science Foundation of Hebei Province(Nos.E2019501097,E2018501091 and E2020501004)the Fundamental Research Funds for the Central Universities(Nos.N182304017,N182304015,N172302001 and N172304044)。
文摘The rational exploitation of non-precious metal catalyst with high activity,strong durability and low cost for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of vital importance for metalair batteries.Herein,a composite of Co_(3)O_(4)nanoparticles confined in three-dimensional(3 D)N-doped porous carbon(Co-NpCs)was prepared by a simple freeze-drying and in situ pyrolysis method.The effect of different dosages of Co(NO_(3))_(2)on the catalytic performance was discussed.The Co-NpC-12%exhibits the best catalytic performance(E_(1/2)=0.78 V,better stability than 20%Pt/C)in ORR and in OER among all the as-synthesized samples.Furthermore,it also exhibits the best bifunctional activity(ΔE=0.849 V).The excellent properties of Co-NpCs are mainly due to the synergy between Co_(3)O_(4)and carbon.Firstly,a high Co_(3)O_(4)loading amount can boost the defect level of the N-doped hierarchical porous carbon and expose more active sites.Secondly,the unique in situ pyrolysis guarantees a largearea contact between Co_(3)O_(4)and carbon as well as a strong C-O-Co bonding,which promotes charge transfer,avoids the peeling of Co_(3)O_(4)nanoparticles and effectively improves the stability of the material.This work is expected to offer a feasible strategy to produce metal oxide/carbon nanocomposite and push forward the development of bifunctional electrocatalyst with high activity and stability.
基金financially supported by the Natural Science Foundation of Jiangsu Province, China (No.BK2011250)the Jiangsu Province Postdoctoral Science Foundation (No. 1101017C)+1 种基金the China Postdoctoral Science Foundation (No. 20100481079)the China Scholarship Council and Outstanding Innovative Talents Support Plan of Hohai University
文摘Fe-based alloy coatings containing TiB2–TiN –（h-BN） were synthesized in situ on Q235 steel substrates by a plasma cladding process using the powders of Fe901 alloy, Ti, and h-BN as raw materials. The effects of Ti/h-BN mass ratio on interfacial bonds between the coating and substrate along with the microstructures and microhardnesses of the coatings were investigated. The results show that the Ti/h-BN mass ratio is a vital factor in the formation of the coatings. Free h-BN can be introduced into the coatings by adding an excess amount of h-BN into the precursor. Decreases in the Ti/h-BN mass ratio improve the microstructural uniformity and compactness and enhance the interfacial bonds of the coatings. At a Ti/h-BN mass ratio of 10/20, the coating is free of cracks and micropores, and mainly consists of Fe-Cr, Fe3B, TiB2, TiN, Ti2N, TiB, FeN, FeB, Fe2B, and h-BN phases. Its average microhardness in the zone between 0.1–2.8 mm from the coating surface is about Hv0.2 551.5.
基金Supported by the National Natural Science Foundation of China(21276050 and21406034)the National Basic Research Program of China(2010CB732206)
文摘In situ surface synthesis of Ca–Mg–Al hydrotalcite(HT) on inorganic ceramic membrane(CM) was investigated with urea as precipitator. The effects of molar ratio of raw materials, crystallization time, and temperature on surface synthesis of HT were examined. The as-prepared HT/CM samples were characterized by XRD and SEM and an in situ growth mechanism of HT on CM was proposed. KF/HT/CM obtained by loading potassium fluoride(KF) on the HT layer by impregnation and calcination method was used as catalyst for transesterification between palm oil and methanol. The comparison of KF/HT/CM and pure KF/HT powder under identical reaction conditions shows that the production of fatty acid methyl ester is equivalent, which means that the use of inorganic catalytic membrane in the transesterification is a viable alternative.
文摘Polypropylene microporous membranes were treated with plasma in a mixture of N2 and H2 (1:2 in volume). Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT1R), X-ray photoelectron spectroscopy (XPS) and ultra-violet (UV) spectra demonstrated the success of grafting amino groups. The density of the polar amino groups on the membrane surface is about 0.59 μmol/cm2. The as-treated membranes were successively applied to the in situ synthesis of oligonucleotides and an average coupling yield was more than 98%. The surface feature of the treated membrane is suggested to be responsible for its advantage over a glass slide.
基金supported by the National Natural Science Foundation of China (No. 22074007)。
文摘Chemodynamic therapy (CDT) has attracted tremendous interest in cancer therapy because it is independent of oxygen and photoirradiation. However, the therapeutic efficacy of CDT is restricted by insufficient H_(2)O_(2) levels in tumor cells. Herein, employing endogenous GSH as a template and cationic polymeric chitosan (CS) as crosslinker and stabilizer exhibiting easy cell uptake, red luminescent gold nanoclusters (denoted CS-GSH@AuNCs) were successfully synthesized in HeLa cells. The in situ synthesized CS-GSH@AuNCs exhibited both superoxidase dismutase (SOD) and peroxidase (POD)-like activity, which could promote the production of H_(2)O_(2) from superoxide anion radicals (O_(2)^(·-)) and then ^(·)OH. The combination of GSH elimination and H_(2)O_(2) elevation boosted the generation of ^(·)OH, which could trigger cancer cell apoptosis and death. The enzyme-like activity of CS-GSH@AuNCs could be effectively activated under acidic conditions, and showed a high killing effect on tumor cells but minimal toxicity to normal cells. The developed GSH consumption and ^(·)OH promotion theranostic platform is an innovative route for enhanced CDT by the amplification of oxidative stress.
基金supported by the National Key Projects of Basic Research and Development Plan(G2000016103)the National Natural Science Foundation of China(39970541)+1 种基金the National Outstanding Youth Science Foundation(3992507)the Doctorate Foundation of the Minister of Education of China(1999004004).
文摘The porcine microsatellite SW943 was regionally localized on 12p11-(2/3p13) by the two methods: the Primed in situ (PRINS) labelling on the pachytene bivalents of pigs using the Dig-11-dUTP as the report molecule and pig X rodent Somatic Cell Hybrid Panel (SCHP) which contains 27 cell lines through PCR amplification. Advantages and disadvantages of the two methods for physical mapping of microsatellites were also discussed.
文摘A novel substrate for in situ synthesis of oligonucleotide was prepared by hydrolyzing microporous polyamide-6 membranes in a 0.01mol/L NaOH/(H2O-CH3OH) mixture medium. The formation of amines (NH2) on the surface was proved by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The treated membrane was applied for in situ synthesis of oligonucleotide and a single step coupling efficiency determined by ultraviolet (UV) spectra was above 98 %.
基金Project(U1261103)jointly supported by the National Natural Science Foundation of China and Shenhua Group Corp
文摘Metal-organic frameworks（MOFs） are important functional materials. MOF-5（IL）（Zn4O（BDC）3（BDC=1,4-benzenedicarboxylate） was in situ synthesized by the electrochemical method using a tunable ionic liquid（IL）, 1-butyl-3-methylimidazolium chloride, as template. The crystallization of distinctly spherical MOF-5（IL） synthsized in ionic liquid by the electrochemical method is attributed to π-π stacking effect, ionic bond, and coordination bond. The analysis results show that the product MOF-5（IL） exhibits better crystallinity and higher thermal stability than MOF-5 generated using the solvothermal method. The cyclic voltammetry reveals that the electrosynthesis reaction is irreversible and controlled by the diffusion. The experiments on methylorange degradation show that the unique structure characteristics of MOF-5（IL） can enhance the photocatalytic ability of Bi OBr. Therefore, MOFs can replace noble metals to improve the photocatalytic properties of bismuth oxyhalide.
文摘A phase-pure NaTi2（PO4）3/reduced graphene oxide （rGO） nanocomposite was prepared using a microwave-assisted one-pot method and subsequent heat treatment. The well-crystallized NaTi2（PO4）3 nanoparticles （30-40 nm） were uniformly precipitated on rGO templates through Ti-O-C bonds. The chemical interactions between the NaTi2（PO4）3 nanoparticles and rGO could immobilize the NaTi2（PO4）3 nanoparticles on the rGO sheets, which might be responsible for the excellent electrochemical performance of the nanocomposite. The NaTi2（PO4）B/rGO nanocomposite exhibited a specific capacity of 128.6 mA-h.g-1 approaching the theoretical value at a 0.1 C-rate with an excellent rate capability （72.9% capacity retention at 50 C-rate） and cycling performance （only 4.5% capacity loss after 1,000 cycles at a high rate of 10 C）. These properties were maintained even when the electrodes were prepared without the use of an additional conducting agent. The excellent sodium storage properties of the NaTi2（PO4）B/rGO nanocomposite could be attributed to the nano-sized NaTi2（PO4）3 particles, which significantly reduced the transport lengths for Na＋ ions, and an intimate contact between the NaTi2（PO4）3 particles and rGO due to chemical bonding.
基金supported by the National Natural Science Foundation of China (Grant Nos. 82073814, 81973275, 82003909, 81973291, 82122066, 81803815)Rising-Star Program of Shanghai Science and Technology Committee (19QA1411500)
文摘Cell membrane affinity chromatography has been widely applied in membrane protein(MP)-targeted drug screening and interaction analysis.However,in current methods,the MP sources are derived from cell lines or recombinant protein expression,which are time-consuming for cell culture or purification,and also difficult to ensure the purity and consistent orientation of MPs in the chromatographic stationary phase.In this study,a novel in situ synthesis membrane protein affinity chromatography(iSMAC)method was developed utilizing cell-free protein expression(CFE)and covalent immobilized affinity chromatography,which achieved efficient in situ synthesis and unidirectional insertion of MPs into liposomes in the stationary phase.The advantages of iSMAC are:1)There is no need to culture cells or prepare recombinant proteins;2)Specific and purified MPs with stable and controllable content can be obtained within 2 h;3)MPs maintain the transmembrane structure and a consistent orientation in the chromatographic stationary phase;4)The flexible and personalized construction of cDNAs makes it possible to analyze drug binding sites.iSMAC was successfully applied to screen PDGFRβinhibitors from Salvia miltiorrhiza and Schisandra chinensis.Micro columns prepared by in-situ synthesis maintain satisfactory analysis activity within 72 h.Two new PDGFRβinhibitors,salvianolic acid B and gomisin D,were screened out with KD values of 13.44 and 7.39μmol/L,respectively.In vitro experiments confirmed that the two compounds decreasedα-SMA and collagen Ⅰ mRNA levels raised by TGF-βin HSC-T6 cells through regulating the phosphorylation of p38,AKT and ERK.In vivo,Sal B could also attenuate CCl_(4)-induced liver fibrosis by downregulating PDGFRβdownstream related protein levels.The iSMAC method can be applied to other general MPs,and provides a practical approach for the rapid preparation of MP-immobilized or other biological solid-phase materials.
基金financially supported by the National Natural Science Foundation of China(No.52174342)Beijing Natural Sci-ence Foundation(No.2232044)Beijing Municipal Education Commission Research Plan General Project(No.KM202410005009).
文摘In this work,silicon-carbon hybrid materials were adopted as an example to illustrate the novel strategy to in situ construct heterostructure with adjustable microstructure.Based on the temperature-dependent thermodynamics and kinetics of reaction between Si and C,the processes for Si nanocrystals growth and C decoration were coupled at different zones of plasma flame according to its temperature and velocity fields by theoretical modeling,aiming to intentionally suppress the formation of undesirable carbide,and enable adjusting the microstructure of each counterpart separately in transient process.As a result,well-controlled Si/C nanocomposites,including nanospheres and nanowires with core-shell structures,were achieved,and this continuous and in-flight route is also potential for large-scale production.Further investigation on the electrochemical properties highlights the advantage of as proposed strategy to efficiently construct heterostructures with superior performance for various applications.
基金supported by the National Natural Science Foundation of China (21773244 and 21875248)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000)the Natural Science Foundation of Fujian Province (2018J01025)
文摘Explorations of new second harmonic generation materials in Ag^+-Hg^2+/Bi^3+-selenites systems afforded three new silver selenium oxides, namely, Ag4 Hg(SeO3)2(SeO4)(1), Ag2Bi2(SeO3)3(SeO4)(2) and Ag5 Bi(SeO3)4(3). They exhibit flexible crystal chemistry. Compounds 1 and 2 are mixed valence selenium oxides containing Se(IV) and Se(VI) cations simultaneously. Compounds 1 and 3 exhibit a 3 D open framework with 4-, 6-and 8-member polyhedral ring tunnels along a, b and c axes. Compound 1 crystallized in a polar space group and could display a subtle frequency doubling efficiency about 35% of the commercial KH2PO4(KDP). UV-vis-NIR spectra reveal that compounds 1–3 are wide-band semiconductors with the optical bandgaps of 3.11, 3.65, 3.58 e V respectively. Theoretical calculations disclose that compounds2 and 3 are indirect band gap structures and their bandgaps are determined by Ag, Bi, Se and O atoms together.
基金financially supported by the National Natural Science Foundation of China (No. 51304063)the Funding Scheme for Young Teachers of Higher School in Henan Province (No. 2013GGJS-076)the Fundamental Research Funds for the Henan Provincial Colleges and Universities (No. 2014YWQQ19)
文摘In situ synthesis method was used to prepare V8C7–Cr3C2nanocomposite.Ammonium vanadate, ammonium dichromate and nanometer carbon black were used as raw materials.The products were characterized by X-ray diffractometry(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), thermogravimetric and differential scanning calorimetry(TGDSC) and X-ray photoelectron spectroscopy(XPS) techniques.The results show that V8C7–Cr3C2nanocomposite with an average crystallite size of 25.4 nm can be synthesized at 1200 °C for 1 h.The synthesis temperature required by the method is at least 200 °C lower than that required by the conventional approaches for preparing vanadium and chromium carbides.The powders show good dispersion and are mainly composed of spherical or nearly spherical particles with a mean diameter of about 30 nm.The weight loss ratio of the precursor throughout the reaction process reaches 58 wt%.Three exothermic peaks and four endothermic peaks occur during the reaction.The surface of the specimen is mainly composed of V, Cr, C and O elements.
基金ItemSponsored by National"863"Plan (2002AA335060) National Natural Science Foundation of China (50332010)
文摘ZrB2 in MgO-C composite materials obtained by both microwave sintering synthesis and in-situ reaction at lower temperature was investigated. The test result shows that 66.67 % of reactant changed into Zrb2, and the other form Al2O3, which could optimize the properties of carbon containing materials. Therefore, the method of in situ synthesizing ZrB2 acting as antioxidant in carbon containing materials is considered as one of best ways to reduce the cost and ZrB2 as refractories is used on a large-scale.
基金Supported by the Education Department of Jiangxi Province (No 2007-125)the Initial Fund for Doctors from Jiangxi Normal University
文摘The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.
文摘A process for in situ synthesis of terbium complex with salicylic acid by a two-step solgel method in silica matrix has been proposed. The luminescence properties of the silica gelscodoped with terbium and salicylic acid have also been discussed with respect to that of the geldoped with terbium and that of pure terbium complex with salicylic acid.
基金supported by the National Natural Science Foundation of China(No.52271055)the Natural Science Foundation of Hebei Province(No.E2021202130).
文摘This work used the in-situ synthesis of molten-state nitride ceramic phase-reinforced Ni-based alloy coat-ings,aiming to improve the phase-interface bonding through the interdependent co-solidification be-tween molten droplets.The XRD was used to analyze the physical phases of the composite coatings.The microstructure and phase-interface structure were characterized in detail by combining SEM,TEM,HRTEM,FFT,and SAED techniques.Microhardness tester and microforce microhardness tester were em-ployed to measure the surface hardness and elastic modulus of the composite coatings.The fracture be-havior of the composite coatings was characterized by observing the fracture morphology of the coatings using SEM combined with the EDS technique.It was found that the formation mechanisms of inter-facial misfit dislocation assistance,lattice distortion,aggregation of stacking faults,and specific growth orientation between theγ-Ni matrix phase and each ceramic phase in NiCrBSi-TiCrN composite coat-ings improved the lattice matching between the two-phase interface,which resulted in the formation of atomically corresponding coherent lattice relations and stepped interfacial semi-coherent lattice relations,and enhanced the degree of phase-interface bonding.On this basis,the composite coatings with high Cr content further inhibited the expansion of interphase penetration cracks due to the existence of Cr-rich zones at the phase interface,thus exhibiting high fracture toughness.This work provides new opinions on the improvement of phase-interface bonding and composition design of Ni-based composite coatings.
文摘A novel maskless technique, self-driving micro-fluid porous type printing （SMPTP）, was reported to in situ synthesize oligonucleotide arrays on glass slide, which has the merits of low cost, high quality and simple craft. In SMPTP for fabricating gene- chips, porous fiber tubes with a number of nanometric or micron channels functioned as ＂active letters＂ and were assembled in designed patterns, which are identical to the distribution of monomers in each layer of the array, and four patterns were needed for each layer. By means of capillarity, the synthesis solution was automatically taken into porous tubes assembled in a printing plate and reached the surface. An oligonucleotide array of 160 features with four different 15-mer probes was in situ synthesized using this technique. The four specific oligonucleotide probes, including the matched and the mismatched by the fluorescent target sequence, gave obviously different hybridization fluorescent signals.
