Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences
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A new approach to thiazoloisoindigo and derivatives using a lithium tetramethylpiperidine promoted cyclization to thiazoloisatin
No full textBrominated thiazoloisoindigo was synthesized for the first time from thiazoloisatin, which was obtained via an unprecedented nucleophilic cyclization strategy. Thiazoloisoindigo was shown to exhibit a deeper LUMO energy level than isoindigo and thienoisoindigo, which makes it a potential building block for n-type semiconductors. Moreover, brominated thiazoloisoindigo is sensitive toward nucleophilic attack, and its reaction with aniline resulted in an unexpectedly much more stable acceptor with a LUMO energy level as low as −3.82 e
Methylamine Gas Based Synthesis and Healing Process Toward Upscaling of Perovskite Solar Cells: Progress and Perspective
No full text化学工程
No full textWith the development of economy and society, petroleum resource drying up, while more and more high quality liquid fules are needed from industrial production, transportation, military and aviation, etc. So, development of non-petroleum routes to produce clean fuels has important strategic significance for producing environmental friendly liquid fuels as well as adjusting energy structure in our country. The oligomerization reaction of light olefins is not only an effective way to produce motor fuel, plasticizer, lubricating oil, antifreeze and other chemicals, but also an important way to prepare high quality clean liquid fuels. Research and optimization of catalyst is the key to the progress of oligomerization technology. Owning the unique MFI three - dimensional channel structure, good acidic and suitable channel confined effect, HZSM-5 showed good resisrant to carbon deposition capability, and the products are not easy to be branched chain, so it is considered to be the most promising catalysts for C3= and C4= olefins oligomerization.
In this work, HZSM-5 zeolite was studied as catalyst for olefin oligomerization. Biomass hemicellulose was used as additive to modify it, ammonium persulphate and tetramethylethylenediamine were added as initiator to explore the crystallization process and properties of HZSM-5 further. Butene oligomerization was tested to inspect the catalytic ability on light olifins oligomerization reaction of modified HZSM-5. The main bodies of the work included the following aspects:
With hemicellulose as additive, ZSM-5 was prepared using hydrothermal method. The macromolecular carbon skeleton structure and the rich hydroxyl of hemicelluloses were used to improve the morphology, texture characteristics as well as acidity of HZSM-5. Preparation of the modified HZSM-5 with different content of hemicellulose, the results indicated that the HZSM-5 with 1.6 wt. % hemicellulose has the biggest BET surface and mesoporous volume, and the strongest acidity, and exhibited the best activity and stability on the butene oligomerization reaction, the conversion maintained about 80% after 140 h on stream. What’s more, it includes the highest selectivities of the trimer, tetramer and diesel component in the products.
For activation the surface hydroxyl groups on the hemicellulose, ammonium persulphate and tetramethylethylenediamine were added as initiator on the basis of the hemicellulose to accelerate the crystallization ZSM-5. The results show, crystallinity and morphology of ZSM-5 can influnced by the initiator in a short time. The acidity of the modified HZSM-5 with 0.5 wt. % initiator enhanced obviously, catalytic ability on butene oligomerizaiton further improved, the conversion maintained above 90% for 60 h on stream, and the bset selectivity of diesel remained above 90%.中
Solid-Phase Synthesis of a Special Phosphorylated Peptide as a Biomarker for LC–MS/MS Detection for OPNA Exposure
No full textFour Simple Structure Carbazole-Based Conjugated Microporous Polymers with Different Soft Connected Chains
No full textFour carbazole-spacer-carbazole polymers PCz-Cn-Cz (n = 3-6) with the similar topological model structures are designed and prepared by FeCl3 oxidative coupling polymerization. The Brunauer-Emmett-Teller (BET) specific surface areas of polymers are 862, 870, 768 and 785 m(2) g(-1), respectively. Interestingly, there are no obvious differences in the domain pore width (centered at 0.5 nm) and the pore size distribution among four polymers, although they have different length soft alkylene chains to interlink same rigid backbone carbazole. Gas adsorption isotherms show that H-2 storage of polymers can be up to 1.33 wt% at 1.0 bar and 77 K, the uptake capacity for CO2 can reach 16.8 wt% at 1.0 bar and 273 K, CH4 uptake can reach 2.11 wt% at 1.0 bar and 273 K, and the CO uptake performance can be up to 1.37 wt% at 298 K and 1.0 bar. Selective adsorption of CO2/N-2 and CO2/CH4 calculated using the initial gas uptake slopes shows that these networks display good selectivity with a maximum value of 47.7 (33.8) and 14 (7.3) at 273 K (298 K). The high selective adsorption performances make these materials potential candidates for gas separation and other environmental applications
Improved Methane Hydrate Formation and Dissociation with Nanosphere-Based Fixed Surfactants As Promoters
No full text<p>
The fixation of surfactants is very important in surfactant-promoted gas hydrate formation. In this work, three surfactants were fixed on the surface of polystyrene nanospheres through emulsion polymerization (named as Surfactant@PSNS) and then used in methane hydrate formation and dissociation, which were sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), and dodecyl alcohol ethoxylates (AEO). The fixation of the surfactants could reduce the induction periods and improve the apparent densities and storage capacities of the formed hydrates, especially at low surfactant concentrations. During hydrate dissociation, the fixation of surfactants resulted in the hydrates dissociating more slowly. The methane recoveries were improved from 76.37%, 27.87%, and 32.35% to 87.55%, 43.43%, and 60.20% for the fixation of SDS, CTAB, and AEO, respectively. Moreover, with surfactants fixed, the foam generation during hydrate dissociation was obviously controlled.</p
Bcl-2/MDM2 Dual Inhibitors Based on Universal Pyramid-Like alpha-Helical Mimetics
No full text<p>
No alpha-helical mimetic that exhibits Bd-2/MDM2 dual inhibition has been rationally designed due to the different helicities of the alpha-helixes at their binding interfaces. Herein, we extracted a one-turn alpha-helix-mimicking ortho-triarene unit from o-phenylene foldamers. Linking benzamide substrates with a rotatable C-N bond, we constructed a novel semirigid pyramid-like scaffold that could support its two-turn alpha-helix mimicry without aromatic stacking interactions and could adopt the different dihedral angles of the key residues of p53 and BH3-only peptides. On the basis of this universal scaffold, a series of substituent groups were installed to capture the key residues of both p53TAD and BimBH3 and balance the differences of the bulks between them. Identified by FP, ITC, and NMR spectroscopy, a compound 6e (zq-1) that directly binds to Mcl-1, Bcl-2, and MDM2 with balanced submicromolar affinities was obtained. Cell-based experiments demonstrated its antitumor ability through Bcl-2/MDM2 dual inhibition simultaneously.</p
The Miscanthus NAC transcription factor MlNAC9 enhances abiotic stress tolerance in transgenic Arabidopsis
No full textNAC (NAM, ATAF1/2, and CUC2) transcription factors are known to play important roles in responses to abiotic stresses in plants. Currently, little information regarding the functional roles of NAC genes in stress tolerance is available in Miscanthus lutarioriparius, a promising bioenergy plant for cellulosic ethanol production. In this study, we carried out the functional characterization of MlNAC9 in abiotic stresses. MlNAC9 was shown to act as a nuclear localized transcription activator with the activation domain in its C-terminus. The overexpression of MlNAC9 in Arabidopsis conferred hypersensitivity to abscisic acid (ABA) at seed germination and root elongation stages. In addition, the overexpression of MlNAC9 led to increased seed germination rate and root growth under salt (NaCl) treatment. Meanwhile, the transgenic Arabidopsis overexpressing MlNAC9 showed enhanced tolerance to drought and cold stresses. The expression of stress-responsive marker genes was significantly increased in MlNAC9 overexpression lines compared to that of WT under ABA, drought, salt, and cold stresses. Correspondingly, the activities of antioxidant enzymes superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT) were significantly increased and the malondialdehyde (MDA) content was lower accumulated in MlNAC9 overexpression lines under drought and salt treatments. These results indicated that the overexpression of MlNAC9 improved the tolerance to abiotic stresses via an ABA-dependent pathway, and the enhanced tolerance of transgenic plants was mainly attributed to the increased expression of stress-responsive genes and the enhanced scavenging capability of reactive oxygen species (ROS). (C) 2016 Elsevier B.V. All rights reserved
Corrosion Resistance of the Superhydrophobic Mg(OH)(2)/Mg-Al Layered Double Hydroxide Coatings on Magnesium Alloys
No full textCoatings of the Mg(OH)(2)/Mg-Al layered double hydroxide (LDH) composite were formed by a combined co-precipitation method and hydrothermal process on the AZ31 alloy substrate in alkaline condition. Subsequently, a superhydrophobic surface was successfully constructed to modify the composite coatings on the AZ31 alloy substrate using stearic acid. The characteristics of the composite coatings were investigated by means of X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electronic microscope (SEM) and contact angle (CA). The corrosion resistance of the coatings was assessed by potentiodynamic polarization, the electrochemical impedance spectrum (EIS), the test of hydrogen evolution and the immersion test. The results showed that the superhydrophobic coatings considerably improved the corrosion resistant performance of the LDH coatings on the AZ31 alloy substrate
A novel method for fabricating hybrid biobased nanocomposites film with stable fluorescence containing CdTe quantum dots and montmorillonite-chitosan nanosheets
No full text<p>
A method was presented for fabricating the fluorescent nanocomposites containing CdTe quantum dots (QDs) and montmorillonite (MMT)-chitosan (CS). MMT-CS/CdTe QDs nanocomposites were prepared via a simple, versatile and robust approach combination of covalent and electrostatic assembly methods (Scheme 1). The negatively charged MMT was initially modified with positively charged CS through electrostatic assembly, followed by incorporation of CdTe-QDs into the MMT-CS nanosheets by covalent connections between the amino groups of CS and the carboxylic acid groups of thioglycollic acid (TGA). The X-ray diffraction (XRD), High resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM) and the FTIR were used to prove the QDs have intercalated into the MMT-CS matrix. The fluorescence emission spectra showed that the MMT-CS/CdTe QDs nanocomposites had the best fluorescence intensity compared with the bare CdTe QDs and CS-QDs. (C) 2016 Elsevier Ltd. All rights reserved.</p