In situ Synthesis of SAPO-34 Zeolites in Kaolin Microspheres for a Fluidized Methanol or Dimethyl Ether to Olefins Process

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.

In situ synthesis and characterization of Ca–Mg–Al hydrotalcite on ceramic membrane for biodiesel production

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.

In situ Synthesis of Oligonucleotides on Plasma Treated Polypropylene Microporous Membrane

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.

Mapping of Microsatellite SW943 to Porcine Chromosome 12p11-(2/3p13) Using Primed in situ Synthesis and Somatic Cell Hybrid Panel

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.

A Novel Substrate for in situ Synthesis of Oligonucleotides: Hydrolyzed Microporous Polyamide-6 Membrane

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 %.

In situ synthesis of Fe-based alloy clad coatings containing TiB_2–TiN –(h-BN)

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.

In situ Synthesis of Ultrasmall Au Clusters on Thiol-modified CeO_(2) with Enhanced Stability and CO Oxidation Activity

Gold(Au)nanoclusters supported on various supports have been widely used in the fields of energy and catalysis.However,the poor thermal stability of Au nanoclusters on the support interface usually leads to a reduction or even loss of catalytic activity.Herein,we used an in situ reduction method to synthesize Au nanoclusters on ceria(CeO_(2))carriers.In this method,sulfhydryl groups were used to modify CeO_(2) nanospheres first,and then Au clusters with an average diameter of 1.5 nm were grown on the surface of ceria reduced with sodium borohydride.The presence of the Au-S-Ce structure enhances the electron transfer efficiency,making the material exhibit high CO oxidation activity at room temperature.Furthermore,due to the strong binding energy of S and Au,the material exhibits a high stability for long time running process.This strategy provides an idea for designing stable and active supported ultrasmall Au nanoclusters catalytic materials.

In situ electrochemical synthesis of MOF-5 and its application in improving photocatalytic activity of BiOBr

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.

In situ synthesis of Co_(3)O_(4)nanoparticles confined in 3D nitrogendoped porous carbon as an efficient bifunctional oxygen electrocatalyst

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.

In situ synthesis of chemically bonded NaTi2（PO4）3/rGO 2D nanocomposite for high-rate sodium-ion batteries

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.

Ag4Hg（SeO3）2（SeO4）: a novel SHG material created in mixed valent selenium oxides by in situ synthesis

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.

Formation of ZrB2in MgO-C Composite Materials Using In-Situ Synthesis Method

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.

In situ synthesis and unidirectional insertion of membrane proteins in liposome-immobilized silica stationary phase for rapid preparation of microaffinity chromatography

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.

In Situ Hydrothermal Synthesis of a Mononuclear Copper(Ⅱ) Complex: Cu(H_2SIP-O)(bpy)(H_2O) (H_4SIP-O=4-Hydroxyl-5-sulfoisophthalic Acid)

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.

In-Situ Synthesis of Terbium Complex with Salicylic Acid in Silica Matrix by a Two-Step Sol-Gel Process

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.

A novel strategy for in situ maskless synthesis of biochips:Self-driving micro-fluid porous type printing (SMPTP)

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.

In situ Synthesis of Oligonucleotide and Detection of Gold-label-silver-stain on PTFE Slices

Poly（tetrafluoroethylene） （PTFE） was treated with plasma in a mixture of nitrogen and hydrogen （1 ： 2 in volume）. X-ray photoelectron spectroscopy （XPS） demonstrated the success of amino group grafting. The as-treated PTFE slices were successively applied to the in situ synthesis of oligonucleotides. With the detection of gold-label-silver-stain, the hybridization signals were recorded with a gel document and analysis system. A target DNA concentration as low as 10 pmol/L could be detected. The complementary and mismatched sequences were distinguished clearly, and the ratio of background-subtracted gray scale values for perfect match ： 1 base mismatch ： 2 base mismatch ： 3 base mismatch was 72 ： 44.4 ： 22.5 ： 11.4. The sensitivity of in situ synthesis system was 1 order of magnitude higher than that of spotting system, and the signal of the former was about 1.5 times stronger than that of the latter under the same target DNA concentration. These plasma modified PTFE slices might open novel prospects for the in situ synthesis of DNA micro-arrays.

In situ synthesis of red fluorescent gold nanoclusters with enzyme-like activity for oxidative stress amplification in chemodynamic therapy

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.

In situ synthesized Cu-ZSM-5/cordierite for reduction of NO

ZSM-5 zeolites were directly synthesized on the surface of honeycomb cordierite substrates by hydrothermal method and certified by XRD and SEM techniques; the adhesion of ZSM-5 coatings was evaluated by ultrasonic vibration. Cu-ZSM-5/cordierite monolithic catalyst was prepared by ion-exchange and impregnation method and applied for the selective catalytic reduction （SCR） of NO by NH3 using a simulated diesel exhaust. The results show that the cordierite surface is almost completely covered by ZSM-5 crystals and the crystallization time greatly impacts the loadings and adhesion of ZSM-5 coatings on substrate, the NOx removal rate over Cu-ZSM-5/cordierite is above 90% in a temperature range of 240-480℃. Moreover, Cu-ZSM-5/cordierite prepared by different methods shows a wide temperature window （240-540 ℃） with high NO removal activities.

A Novel 3D Zn-La Heterometallic Coordination Polymer Involving in situ Glycinate Ligand Synthesis

One novel 3D 3d-4f coordination polymer, [LaZn（glc）（ox）2（H20）2]n （1, glc = glycinate, ox = oxalate）, was obtained by the in situ synthesis of glycinate from the reaction of tetrazole-l-acetic acid, sodium oxalate, zinc nitrate and lanthanide oxide in the presence of a trace quantity of nitric acid under hydrothermal conditions. Compound 1 is of monoclinic, space group P21/n with a = 0.99601（9）, b = 1.14592（10）, c = 1.19107（10） nm and β = 108.7150（10）°. 1 exhibits an unusual 3D heterometallic coordination framework constructed by heterometallic dinuclear LaZn subunits and mixed ox and glc linkers with a uninodal 6-connected vine {33.43.58.6} net.