Photodynamic therapy (PDT) stands as an efficacious modality for the treatment of cancer and various diseases, in which optimization of the electron transfer and augmentation of the production of lethal reactive oxygen species (ROS) represent pivotal challenges to enhance its therapeutic efficacy. Empirical investigations have established that the spontaneous initiation of redox reactions associated with electron transfer is feasible and is located in the gas-liquid interfaces. Meanwhile, nanobubbles (NBs) are emerging as entities capable of furnishing a plethora of such interfaces, attributed to their stability and large surface/volume ratio in bulk water. Thus, NBs provide a chance to expedite the electron-transfer kinetics within the context of PDT in an ambient environment. In this paper, we present a pioneering exploration into the impact of nitrogen nanobubbles (N2-NBs) on the electron transfer of the photosensitizer levofloxacin (LEV). Transient absorption spectra and time-resolved decay spectra, as determined through laser flash photolysis, unequivocally reveal that N2-NBs exhibit a mitigating effect on the decay of the LEV excitation triplet state, thereby facilitating subsequent processes. Of paramount significance is the observation that the presence of N2-NBs markedly accelerates the electron transfer of LEV, albeit with a marginal inhibitory influence on its energy-transfer reaction. This observation is corroborated through absorbance measurements and offers compelling evidence substantiating the role of NBs in expediting electron transfer within the ambit of PDT. The mechanism elucidated herein sheds light on how N2-NBs intricately influence both electron-transfer and energy-transfer reactions in the photosensitizer LEV. These findings not only contribute to a nuanced understanding of the underlying processes but also furnish novel insights that may inform the application of NBs in the realm of photodynamic therapy.

Efficient recovery of lithium from mother liquor of Li2CO3 is considered as an effective way to mitigate the rapidly growing demand of lithium but poses a daunting challenge. Herein, a series of synergistic hydrophobic deep eutectic solvents (HDESs) coupling beta-diketones and neutral extractants were developed as novel extraction media for recovery of Li+ from aqueous solution. The newly developed HDES exhibited very low viscosity and high hydrophobicity, enabling their direct use in liquid-liquid extraction. The extraction performance of the systems could be easily manipulated by simply altering the composition of HDESs, with the thenoyltrifluoroacetone-tributyl phosphate (HTTA-TBP) and thenoyltrifluoroacetone-trioctylphosphine (HTTA-TOPO) HDES displaying excellent extraction capacity and selectivity towards Li+. The selective extraction mechanism was exemplified by HTTA-TBP HDES and revealed by molecular dynamics simulation for the first time, whereby Li+ was driven into HDES phase mainly through its strong electrostatic interaction with deprotonated HTTA, while TBP interacted with Li+ via the coordination effect. The stoichiometry of extracted complex was 1:1:1, with the form of Li+center dot TTA(-)center dot TBP. The cooperation of HTTA and TBP in HDES prohibited the participation of water molecule in the formation of extracted complex, thus preventing the emulsification during extraction. Interaction energy analysis demonstrated that Li+ interacted with both TTA(-) and TBP much more strongly than Na+ and K+, explicitly elucidating the high selectivity of HDES towards Li+ over Na+ and K+. Finally, both of the HTTA-TBP and HTTA-TOPO HDES were utilized to recover Li+ from the mother liquor of Li2CO3, with recovery rates of Li+ over 80 % through single-stage extraction, scrubbing and stripping. Moreover, the stripped HDESs could be directly used in subsequent extraction cycles without regeneration, and their extraction performances remained virtually unchanged, suggesting that the developed HEDSs are highly promising and feasible.

Amphiphilic block copolymers/ionic liquids mixtures have been emerging as a new class of "chemical entity' with numerous advanced applications. However, interaction mechanism governing the aggregation and the microstructure of aggregates are still far from full understanding. Herein, the role of noncovalent interactions in regulation of aggregation behaviors of mixtures of Pluronic F127 and surface-active ionic liquids, i.e. C(n)mimBr, CnPyBr and CnMPB is investigated by DLS, cryo-TEM, NMR and molecular dynamics simulation. The interaction modes between F127 and SAILs are remarkably dependent on the concentration and cationic headgroup of SAIL. At low SAIL concentration (< CMC), mixed micelles mainly composed of F127 with some SAIL cations embedded into micelles are formed, which was primarily driven by hydrophobic interaction. However, the residence of C(n)mimBr cations in micelles is quite different from that of CnPyBr and CnMPB cations due to its distinctive hydrogen bonding with PEO segment of F127. Upon further addition of SAILs (C-SAILs > CMC), gradual disintegration of F127-rich micelles was observed due to the enhanced repulsive electrostatic force at micellar core-corona interface, accompanying with the re-formation of two types of micelles: one consisting of pure SAILs and one that SAIL micelles bound with F127 monomers via hydrogen bonding and/or hydrophobic interactions. This work provides new insight into the aggregation mechanism of these complex systems and will be helpful to rational tailoring innovative copolymers /IL-based system for specific applications. (C) 2022 Elsevier B.V. All rights reserved.

以不同链长的有机胺为模板,选用不同的铝源,采用水热法合成AHT型分子筛。考察铝源、原料摩尔比和有机模板剂对AHT型磷酸铝分子筛（AlPO 4 -H2）合成的影响,并利用XRD、SEM、BET、TG/DTG等技术对合成的AHT构型磷酸铝分子筛进行表征。结果表明,在所测试的4种铝源中,只有以拟薄水铝石为铝源时才能获得AHT型分子筛;反应混合物中水的含量对AHT型磷酸铝分子筛的合成具有显著的影响,当n（H 2 O）/n（Al 2 O 3 ）大于或小于20时,均有杂相生成;在优化的条件下,以烷基链长度大于4的有机胺为模板剂,均能获得纯相的AHT型磷酸铝分子筛。当有机胺烷基链长度小于或等于4时,有机胺的最大伸展长度达不到AHT型磷酸铝分子筛的晶胞参数c值,无法合成纯相AHT型磷酸铝分子筛。合成的AHT型磷酸铝分子筛形貌为针状或棒状,结构骨架中磷铝摩尔比为1,是一种典型的磷酸铝分子筛。该分子筛具有良好的酸碱稳定性,但高温容易导致其结构转变。

Hydrogen bonding interaction has been increasingly recognized as a viable tool for manipulating the morphology of amphiphilic block copolymers aggregates in selective media. In this regard, mechanistic understanding on the impact of the strength of such an interaction on the morphological transition of the aggregates is of crucial importance for rational design targeting functional assemblies, yet still remains poorly understood. By performing multiple experimental techniques and molecular dynamics simulations (MDS), we here demonstrate how the morphology of Pluronic P123 micelles evolves by introduction of three octane derivatives (i.e., n-octanol, n-octylamine and n-octanoic acid) capable of forming distinct hydrogen bonding strength with P123 in aqueous solution. It is found that the P123-n-octanol mixture exhibits spherical aggregates as P123 alone. However, upon adding n-octylamine, the P123 micelles undergo sphere-short rod-long worm transition in both concentration and temperature-dependent manners. Interestingly, n-octanoic acid brings about a series of morphological transition from sphere, long worm to unilamellar vesicles as the concentration increases and the formed vesicles are fairly stable in the tested temperature range (20-60 degrees C). The nature of the additives acting on the copolymer aggregates was probed by 2D-NMR and MDS. Although both of the hydrophobic and hydrogen bonding interactions between the additives and block copolymers affect the architecture of the copolymer aggregates, the diverse strength of the latter generating from the functional groups (viz. -OH, -NH2 and -COOH) of the additives with the ether oxygen atoms on P123 backbone results in distinct location of the three additives in the micelles, consequently leading to varying micellar morphologies. This work enriches our knowledge of hydrogen bonding driven morphological transition of amphiphilic block copolymers aggregates, and as a result the fabrication of a desired nano-material through fine-tuning the hydrogen bonding strength can be straightforwardly envisaged. (C) 2021 Elsevier B.V. All rights reserved.