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1.
J Org Chem ; 87(14): 8841-8848, 2022 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-35290059

RESUMO

Three acene-extended triptycenes, TIPS-Antrip, TIPS-Tetrip, and TIPS-Pentrip, which contain TIPS-ethynyl functionalized anthracene, tetracene, and pentacene as subunits, respectively, are synthesized and characterized. It is found that the optoelectronic properties and crystal packing motifs could be modulated by changing the subunits. A preliminary exploration of the excited-state behavior of these molecules indicates that TIPS-Tetrip and TIPS-Pentrip exhibit intramolecular singlet fission (iSF).

2.
Chem Commun (Camb) ; 58(29): 4671-4674, 2022 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-35319555

RESUMO

Two novel π-expanded triple [5]helicenes containing three dibenzocoronene monoimide subunits have been synthesized and characterized. The helicenes exhibit low-energy conformational interconversions, as supported by NMR spectra. The single-crystal X-ray analysis reveals a C1 conformation in the solid state. Furthermore, the helicenes exhibit ambipolar transport characteristics in thin film transistors.

3.
AMB Express ; 11(1): 179, 2021 Dec 27.
Artigo em Inglês | MEDLINE | ID: mdl-34958433

RESUMO

5-aminolevulinic acid (ALA) has broad potential applications in the medical, agricultural and food industries. Several strategies have been implemented successfully to try to improve ALA synthesis. Nonetheless, the low yield has got in the way of large-scale bio-manufacture of 5-ALA. In this study, we explored strain engineering strategies for high-level 5-ALA production in Corynebacterium glutamicum F343 using the C4 pathway. Initially, the glutamate dehydrogenase-encoding gene gdhA was deleted to reduce glutamate yield. Then the C4 pathway was introduced in the gdhA mutant strain F2-A (∆gdhA + hemA), resulting in a 5-ALA yield of up to 3.2 g/L. Furthermore, the accumulations of downstream metabolites such as heme, porphobilinogen, and protoporphyrin IX, were decreased. After evaluating the mechanisms of this synthetic pathway by RNA-Seq, the results showed that genes involved in both the C5 pathway and heme pathways were down-regulated in strain F2-A (∆gdhA + hemA). Interestingly, upstream genes of succinyl-CoA in the tricarboxylic acid (TCA) cycle, such as icd, lpdA, were up-regulated, while its downstream genes, including sucC, sucD, sdhB, sdhA, sdhCD, were down-regulated. These changes amplify the sources of succinyl-CoA and reduce its expenditure, before pulling the carbon flux to produce 5-ALA. Furthermore, the down-regulation of most genes of the heme pathway could reduce the drainage of 5-ALA, which further enhance its accumulation. To alleviate competition between glyoxylate and the TCA cycle, the isocitrate dehydrogenase-encoding gene aceA was also knocked out, resulting in 3.86 g/L of 5-ALA. Finally, the fermentation conditions were optimized, resulting in a maximum 5-ALA yield of 5.6 g/L. Overall, the blocking of the glutamate synthesis pathway could be a powerful strategy to re-allocate the carbon flux to produce 5-ALA. It could also enable the efficient synthesis of other TCA derivatives in C. glutamicum.

4.
Se Pu ; 28(7): 697-701, 2010 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-21043347

RESUMO

Inverse gas chromatography (IGC) was used to measure the surface tension and solubility parameter of E51 epoxy resin in this work. By using the Schultz method, decane, nonane, octane and heptane were chosen as the neutral probes to calculate the dispersive surface tensions (gamma(D)). Based on the Good-van Oss equation, the specific surface tension (gamma(SP)) of E51 epoxy resin was calculated with the acidic probe of dichloromethane and the basic probe of toluene. The results showed that the gamma(D) and gamma(SP) of the E51 resin decreased linearly with the increase of temperature. According to the Flory-Huggins parameters (chi) between the resin and a series of probes, the solubility parameters (delta) of E51 resin at different temperatures were estimated using the method developed by DiPaola-Baranyi and Guillet. It was found that the values of delta of the E51 resin were 11.78, 11.57, 11.48 and 11.14 MPa1/2 at 30, 40, 50 and 60 degrees C, respectively. The dispersive component (delta(D)) and the specific component (delta(SP)) of solubility parameter at different temperatures of the E51 resin were investigated according to the relationships between surface tension, cohesion energy and solubility parameter. The results showed that the values of delta(D) were higher than those of delta(SP) for the epoxy resin, and both of them decreased with the increase of temperature.

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