In-Situ Immobilization of Ni Complex on Amine-Grafted SiO2 for Ethylene Polymerization.

The results on the In-Situ synthesis of Ni complex on amine-grafted SiO2 and its ethylene polymerization were explained. SiO2/2NS/(DME)NiBr2 and SiO2/3NS/(DME)NiBr2(Ni(II) bromide ethylene glycol dimethyl ether) catalysts were active for ethylene polymerization. The highest activity was shown at the polymerization temperature of 25 °C, and SiO2/2NS/(DME)NiBr2 exhibited higher activity than SiO2/3NS/(DME)NiBr2. The PDI values of SiO2/2NS/(DME)NiBr2 were in the range of 8~18. The aminosilane compounds and Ni were evenly grafted and distributed in the silica. It was proposed that DME ligand was mostly removed during the supporting process, and only NiBr2 was complexed with the amine group of 2NS based on the results of FT-IR and ethylene polymerization.

Construction of late transition metal complex on amine-functionalized SiO2 and SBA-15 for L-lactide polymerization.

We report the in-situ synthesis of a late transition metal catalyst on amine-functionalized SBA-15 and amorphous silica and their ring opening polymerizations of L-lactide. Funtionalizations of SBA-15 and amorphous silica with N-[3-(trimethoxysilyl)propyl]-ethylenediamine (2NS) were carried out to in-situ synthesize late transition metal catalysts on the surface of nanoporous materials. FT-IR spectra indicates that the 1,2-dimethoxyethane ligand did not participate in the reaction when (DME)NiBr2 was immobilized on the amine-functionalized silica. In addition, the XPS spectrum confirmed the presence of Ni compound on the 2NS-functionalized SiO2. SBA-15/2NS/Ni and SBA-15/ 2NS/Pd catalysts showed higher conversion of PLA polymerization in comparison to SiO2/2NS/Ni and SiO2/2NS/Pd, respectively. The molecular weights of PLA produced by SBA-15/2NS/Ni or Pd were larger than those of SiO2/2NS/Ni or Pd, respectively. The effects of polymerization conditions such as the polymerization temperature, time, the catalyst amount in the feed, and the polymerization medium in L-lactide polymerization were also investigated.

Preparation of single-site catalyst inside the functionalized nanopore of silica and its ethylene polymerization.

Amorphous silica have been functionalized with organo-silane, and (n-BuCp)2ZrCI2 and methylaluminoxane (MAO) were subsequently immobilized on the functionalized silica for the further evaluation as a catalyst of ethylene polymerization. Four organo-silanes such as 3-aminopropyltrimethoxysilane (1NS), N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS), N1-[3-(trimethoxysilyl)propyl]diethylenetriamine (3NS), and 4-(triethoxysilyl)butyronitrile (1NCy), were employed for this study. The Zr content and polymerization activity of the supported catalysts were strongly dependent on the kind and structure of organo-silane. 2NS showed the highest Zr content with higher activity, indicating the more Zr could be captured due to a stronger interaction between (n-BuCp)2ZrCl2 and amine group.

A selective functionalized mesoporous silica-supported Rh catalyst for effective 1-octene hydroformylation.

Through different functionalization methods, three kinds of Rh-immobilized mesoporous silicas have successfully been prepared to investigate catalytic behavior, including yield and the linear/branched ratio of aldehyde (L/B) in 1-octene hydroformylation. A conventional post grafting method and two kinds of selective bifunctionalized methods for modification of the mesoporous silica have been applied for this purpose. A relatively high L/B (> 2.0) was effectively achieved using Rh-immobilized inner pores in the MCM-41 support due to the confinement effects of the Rh complex in the nanospace. Moreover, the Rh-immobilized MCM-41 catalyst, passivated with trimethylchlorosilane (TMCS) only on the external surface, showed fairly good yields of the aldehyde (> 40%).

A handheld-type total integrated capillary electrophoresis system for SARS-CoV-2 diagnostics: Power, fluorescence detection, and data analysis by smartphone.

A micro-capillary electrophoresis (µCE) system is one of the widely adopted techniques in the molecular diagnostics and DNA sequencing due to the benefits of high resolution, rapid analysis, and low reagent consumption, but due to the requirements of bulky high-power suppliers and an expensive laser-induced fluorescence detector module, the conventional set-up of µCE system is not adequate for point-of-care (POC) molecular diagnostics. In this study, we constructed a miniaturized and integrated µCE system which can be manipulated by a smartphone. The smartphone not only powers two boost converters and an excited laser, but also controls the relay for the power switch. Moreover, the complementary metal-oxide-semiconductor (CMOS) camera of the smartphone was used for detecting the fluorescence signal of amplicons amplified with reverse transcription-polymerase chain reaction (RT-PCR). We also developed a web-based application so that the raw data of the recorded fluorescence intensity versus the running time can display typical capillary electropherograms on the smartphone. The total size of the hand-held µCE system was 9.6 cm [Width] × 22 cm [Length] × 15.5 cm [Height], and the weight was ∼1 kg, which is suitable for POC DNA testing. In the integrated smartphone-associated µCE system, we could accurately analyze two genes of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), namely N gene and S gene along with two bracket ladders in 6 min to identify SARS-CoV-2. Such an advanced µCE platform can be applied for a variety of on-site molecular diagnostics fields with user-friendliness.

Catalytic pyrolysis of oilsand bitumen over nanoporous catalysts.

The catalytic cracking of oilsand bitumen was performed over nanoporous materials at atmospheric conditions. The yield of gas increased with application of nanoporous catalysts, with the catalytic conversion to gas highest for Meso-MFI. The cracking activity seemed to correlate with pore size rather than weak acidity or surface area.

Influence of nanopores of MCM-41 and SBA-15 confining (n-BuCp)2ZrCl2 on copolymerization of ethylene-alpha-olefin.

The effect of nanopore in mesoporous materials confining (n-BuCp),ZrCl2 and methylaluminoxane (MAO) on ethylene-1-hexene and ethylene-1-octene copolymerization was investigated on the basis of the copolymerization results, and the analysis of the supported catalyst and the copolymers. SBA-15 and MCM-41 together with amorphous silica were employed as supports, which are capable of confining (n-BuCp)2ZrCl2 and MAO in the nanopore. The copolymerization activities of MCM-41-supported (n-BuCp)2ZrCl2 were higher than those of SBA-15 and SiO2 although that its Zr content was quite lower than those of SBA-15 and SiO2. SBA-15 and MCM-41 showed a remarkable decrease in BET surface area after confining MAO and (n-BuCp)2ZrCl2 compared to SiO2, explaining an even adsorption of MAO and (n-BuCp)2ZrCl2 complexes on the nanopore surface. Temperature rising elution fractionation (TREF) results showed bimodal curves of MCM-41-supported (n-BuCp)2ZrCl2 at the C6/C2 and C8/C2 molar ratios of 0.6 and 0.5, respectively, which was attributed to the differences in ethylene and alpha-olefin concentrations along with the cylindrical nanopore of MCM-41 due to the narrow nanospace.

Synthesis of functionalized mesoporous material with various organo-silanes.

Two kinds of ordered mesoporous silicas, SBA-15 and MSU-H, have been synthesized and functionalized by direct and post synthesis method to widen their various application possibilities. In this study, phenyltrimethoxysilane (PTMS), methacryloxy-methyltrimethoxysilane (MAMTMS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETMS), and N(beta-aminoethyl)-gamma-aminopropylmethyldimethoxysilane (AEAPMDMS) were used as a silane precursor for the functionalization. The post synthesis was more effective method to sustain ordered pore structure than the direct synthesis method under our experimental conditions. The surface area and pore size of mesoporous silica SBA-15 and MSU-H decreased through the functionalization process. FT-IR and XPS results confirmed the functionalized silane existence in the SBA-15/MAMTMS. These functional groups (vinyl, epoxide, and amine group) could be useful for various applications such as a linker of functional organic materials or active metal for heterogeneous catalysts. As a practical instance, rhodium immobilized on the aminated SBA-15 was investigated as a 1-octene hydroformylation.

The preparation and low-k application of asymmetric functionalized cyclodextrin templated nanoporous silsesquioxane films.

Several kinds of Asymmetric Functionalized Cyclodextrin (AFCD), as a porogen, have been introduced for the first time to investigate their potential in the field of low-k applications. The novel AFCD templated films were compared in terms of their pore forming efficiency and the pore structure, such as pore size and pore size distribution. Of the AFCDs, btCD and tbsCD showed fairly good pore forming efficiencies. The pore diameter generating form of AFCD was larger than that of conventional CD (tCD) at a high porogen loading (> 30 wt%), which might have been due to the micelle-like assembled behavior of the AFCD porogen as a supramolecular surfactant. Ultra low-k films (k < 1.5) can be effectively made using the AFCD porogen. Mechanical properties, such as hardness and elastic modulus, decrease with increasing AFCD porogen loading.

Catalytic decomposition of 1,2-dichlorobenzene using Pt-loaded nanoporous zeolite MFI catalyst.

Nanoporous zeolite MFI was prepared by using HClO4 as a promoter. A significant proportion of the synthesized zeolite MFI nanoparticles exhibited nanoporous characteristics. Although the synthesis of the zeolite MFI was completed within 6 h, the crystallinity of all the zeolite MFI was shown to be high. The synthesis time of approximately 6 h used in this study was much shorter than the conventional hydrothermal method. The feasibility of the new nanoporous zeolite MFI towards the gas phase catalytic oxidation of a model for dioxin, 1,2-dichlorobenzene, was tested by comparing the catalytic activity of Pt/nanoporous zeolite MFI with that of a Pt/gamma-Al2O3 catalyst. The catalytic activity of the Pt/nanoporous zeolite MFI was higher than that of the Pt/gamma-Al2O3 catalyst. The internal surface area and acidity appears to be a major factor for the decomposition of 1,2-dichlorobenzene.

L-Lactide Ring-Opening Polymerization with Tris(acetylacetonate)Titanium(IV) for Renewable Material.

A new Ti-type of catalyst for L-lactide polymerization was synthesized by reaction of titanium(IV) isopropoxide (TTIP) with acetylacetone (AA). Moreover, PLA was prepared by the bulk ring-opening polymerization using synthesized Ti catalyst. Polymerization behaviors were examined depending on monomer/catalyst molar ratio, polymerization temperature and time. The structure of synthesized catalysts was verified with FT-IR and 1H NMR and the properties of poly(L-lactide) (PLLA) were examined by GPC, DSC and FT-IR. There existed about 30 minutes of induction time at the monomer/catalyst molar ratio of 300. The molecular weight (MW) increased as monomer/catalyst molar ratio increased. The MW increased almost linearly as polymerization progressed. Increasing polymerization temperature increased the molecular weight of PLLA as well as monomer/catalyst molar ratio. The melting point (T(m)) of polymers was in the range of 142 to 167 degrees C. Lower T(m) was expected to be resulted from relatively lower molecular weight.

Epoxide-functionalization of polyethyleneimine for synthesis of stable carbon dioxide adsorbent in temperature swing adsorption.

Amine-containing adsorbents have been extensively investigated for post-combustion carbon dioxide capture due to their ability to chemisorb low-concentration carbon dioxide from a wet flue gas. However, earlier studies have focused primarily on the carbon dioxide uptake of adsorbents, and have not demonstrated effective adsorbent regeneration and long-term stability under such conditions. Here, we report the versatile and scalable synthesis of a functionalized-polyethyleneimine (PEI)/silica adsorbent which simultaneously exhibits a large working capacity (2.2 mmol g(-1)) and long-term stability in a practical temperature swing adsorption process (regeneration under 100% carbon dioxide at 120 °C), enabling the separation of concentrated carbon dioxide. We demonstrate that the functionalization of PEI with 1,2-epoxybutane reduces the heat of adsorption and facilitates carbon dioxide desorption (>99%) during regeneration compared with unmodified PEI (76%). Moreover, the functionalization significantly improves long-term adsorbent stability over repeated temperature swing adsorption cycles due to the suppression of urea formation and oxidative amine degradation.

Synthesis, X-ray structures, and controlled ring opening polymerization behavior of L-lactide using titanium complexes chelated by tetradentate diamine-diethanolate ligand.

The synthesis and characterization of LTi(O-i-Pr)(2) (1) and LTiCl(2) (2) complexes containing a new [ONNO]-type tetradentate diamine-diethanolate ligand such as (HOCMe(2)CH(2)NMeCH(2)CH(2)NMeCH(2)CMe(2)OH) (LH(2)) was achieved. Single-crystal X-ray analyses revealed that monomeric complexes 1 and 2 had pseudo-C(2) and pseudo-C(1) symmetric distorted octahedral geometry, respectively. Interestingly, complex 1 has fac-fac geometry for tetradentate L around a Ti centre in both solid and solution, whereas complex 2 has different geometry in solid (mer-fac, C(1)) and solution (fac-fac, C(2)). They are effective catalysts for the controlled ring opening polymerization of L-lactide, as shown by the linearity of the number average of the molecular weight of polylactides versus conversion, as well as narrow PDI values.