Improvement in thermodynamic characteristics of sodium acetate trihydrate composite phase change material with expanded graphite

In this study, three different volume expansion ratios of expanded graphite (EG) are prepared and investigated to enhance the heat transfer efficiency of the sodium acetate trihydrate (SAT) composites. A series of SAT composite phase change materials (CPCMs) with EG were prepared. The influence of volume expansion ratio and mass fraction of EG on thermodynamic characteristics of SAT CPCMs was examined, including thermal conductivity, phase change temperature, enthalpy, latent heat storage and release time, and the degree of supercooling. Results showed that SAT CPCMs can be absorbed adequately by EG, and EG could enhance the heat transfer efficiency effectively. But it also brought some problems with the addition of all the three volume expansion ratios of EG, such as the poor enthalpy and serious supercooling. Particularly, the situation gets worse with the increase in mass and expansion ratio of EG. Therefore, it is better to choose the EG with proper expansion ratio or reduce the proportion of the EG which possesses higher expansion ratio. Besides, thermal cycling test and thermogravimetric analysis revealed that the SAT CPCMs with 3 mass% EG showed a good thermal stability.

     

Chiral DMAP‐N‐oxides as Acyl Transfer Catalysts: Design,Synthesis, and Application in Asymmetric Steglich Rearrangement

A DMAP‐N‐oxide, featuring an α‐amino acid as the chiral source, was developed, synthesized and applied in asymmetric Steglich rearrangement. A series of O‐acylated azlactones afforded C‐acylated azlactones possessing a quaternary stereocenter in high yields (up to 97 % yield) and excellent enantioselectivities (up to 97 % ee). Compared to the widespread use of pyridine nitrogen, which serves as the nucleophilic site in the asymmetric acyl transfer reaction, we discovered that chiral DMAP‐N‐oxides, in which the oxygen now acts as the nucleophilic site, are efficient acyl transfer catalysts. Our finding might open a new door for the development of chiral DMAP‐N‐oxides for asymmetric acyl transfer reactions.     

Dehydrogenative Silylation of Alkenes for the Synthesis of Substituted Allylsilanes by Photoredox,Hydrogen‐Atom Transfer,and Cobalt Catalysis

A synergistic catalytic method combining photoredox catalysis, hydrogen‐atom transfer, and proton‐reduction catalysis for the dehydrogenative silylation of alkenes was developed. With this approach, a highly concise route to substituted allylsilanes has been achieved under very mild reaction conditions without using oxidants. This transformation features good to excellent yields, operational simplicity, and high atom economy. Based on control experiments, a possible reaction mechanism is proposed.     

Efficient Non-Fullerene Organic Solar Cells Based on a Wide-Bandgap Polymer Donor Containing an Alkylthiophenyl-Substituted Benzodithiophene Moiety

Two wide-bandgap polymer donors containing an alkylthiophenyl substituted benzo[1,2-b : 4,5-b′]dithiophene moiety, namely PTZPO and PTZPS, were designed and synthesized. Both polymers exhibit relatively wide optical bandgap of 1.95 V with similar absorption profiles. The polymer PTZPS with alkylthiophenyl substituted benzo[1,2-b : 4,5-b′]dithiophene units showed enhanced light-harvesting capabilities, leading to improved short-circuit current densities. The PTZPS : ITIC film shows more appreciable film morphology and phase separation than the film composed of a blend of ITIC with alkoxyl substitutions containing copolymer PTZPO, which facilitates exciton dissociation and charge transport. The PTZPS : ITIC-based non-fullerene organic solar cells show clearly improved short-circuit current density and an impressively high power conversion efficiency of more than 11 %. These observations demonstrate the great promise of using PTZPS as electron-donating materials for high-performance non-fullerene organic solar cells.     

Continuous separation of maslinic and oleanolic acids from olive pulp by high‐speed countercurrent chromatography with elution‐extrusion mode

In this work, a continuous high‐speed countercurrent chromatography method has been developed on the basis of elution‐extrusion mode and this method was successfully applied to the separation of maslinic and oleanolic acid from the extract of olive pulp. In the process of ‘elution’, the sample solution was continuously loaded into the column and the maslinic acid was steadily eluted out in this step while highly retained oleanlic acid always stayed in the column. In the process of ‘extrusion’, the oleanlic acid was pushed out of the column with the stationary phase. In this way, we achieved a large sample loading. A total of 120 mL sample solution (about 89.55% of the column volume) which contains 600 mg olive pulp extract was pumped in the apparatus by a constant‐flow pump and the maslinic and oleanolic acids were largely separated within 120 min. Both of these two compounds presented high yields and high purities (271.6 mg for maslinic acid with 86.7% and 83.9 mg oleanolic acids with 83.4%).     

Reaction Kinetics between Thiobases and Singlet Oxygen Studied by Direct Detection of the 1O2 Luminescence Decay

Thiobase derivatives have received important investigations due to their wide usage as phototherapeutic agents and their potential carcinogenic side effects as immunosuppressants. The substitution of oxygen atom by the sulfur atom makes the ultraviolet absorption of thiobases redshifted and absorbs UVA light (>300 nm), resulting in unusual high quantum yield of triplet state to generate the singlet oxygen (¹O₂) through photosensitization. As a type of reactive oxygen species, ¹O₂ is highly reactive toward thiobases. Herein, we report the measurements of reaction rate constants between di erent thiobases and ¹O₂ in different solvents through the direct detection of ¹O₂ luminescence decay kinetics at 1270 nm. The rate constants of thiouracils with ¹O₂ are five times smaller than that of thioguanine with ¹O₂, which suggests that thiopurines are more reactive than thiopyrimidines and thus less suitable to be a photosensitive drug on the application of photodynamic therapy. Additionally, the rate constants of thiobases and ¹O₂ were found to be obviously influenced by the solvent polarity. With the increase of solvent polarity, the rate constants of thiobases and ¹O₂ decrease.     

Efficient organic-inorganic hybrid cathode interfacial layer enabled by polymeric dopant and its application in large-area polymer solar cells

An organic-inorganic hybrid cathode interfacial layer(CIL) was developed by doping ZnO with the naphthalene-diimide based derivative NDI-PFNBr. It was found the resulting organic-inorganic hybrid CIL showed apparently improved conductivity and could act as an effective cathode interlayer to modify indium tin oxide(ITO) transparent electrodes. As a result, by employing the blend of PTB7-Th:PC71BM as the photoactive layer, the inverted polymer solar cells(PSCs) exhibited a remarkable enhancement of power conversion efficiency(PCE) from 8.52% for the control device to 10.04% for the device fabricated with the hybrid CIL. Moreover, all device parameters were simultaneously improved by using this hybrid CIL. The improved open-circuit voltage(VOC) was attributed to the reduced work function of the ITO cathode, whereas the enhancements in fill factor(FF) and short-circuit current density(JSC) were assigned to the increased conductivity and more effective charge extraction and collection at interface. Encouragingly, when the thickness of the hybrid CIL was increased to 80 nm, the resulting device could still keep a PCE of 8.81%, exhibiting less thickness dependence. Considering these advantages, 16 and 93 cm2large-area PSCs modules were successfully fabricated from the hybrid CIL by using doctor-blade coating techniques and yielded a remarkable PCE of8.05% and 4.49%, respectively. These results indicated that the hybrid CIL could be a promising candidate to serve as the cathode interlayer for high-performance large-area inverted PSCs.     

A special attack on the multiparty quantum secret sharing of secure direct communication using single photons

The security of a multiparty quantum secret sharing protocol [L.F. Han, Y.M. Liu, J. Liu, Z.J. Zhang, Opt. Commun. 281 (2008) 2690] is reexamined. It is shown that any one dishonest participant can obtain all the transmitted secret bits by a special attack, where the controlled-(-iσ_y) gate is employed to invalidate the role of the random phase shift operation. Furthermore, a possible way to resist this attack is discussed.