Orthogonal Design of Supramolecular Prodrug Vesicles via Water-Soluble Pillar[5]arene and Betulinic Acid Derivative for Dual Chemotherapy.

Supramolecular prodrug vesicles with efficient property for dual chemotherapy have been successfully constructed based on the orthogonal self-assembly between a water-soluble pillar[5]arene host (WP5) and a betulinic acid guest (BA-D) as well as doxorubicin (DOX). Under the acidic microenvironment of cancer cells, both the encapsulated anticancer drug DOX and prodrug BA-D can be effectively released from DOX-loaded WP5⊃BA-D prodrug vesicles for combinational chemotherapy. Furthermore, bioexperiments indicate that DOX-loaded prodrug vesicles can obviously enhance the anticancer efficiency based on the cooperative effect of DOX and BA-D, while remarkably reducing the systematic toxicity in tumor-mice, displaying great potential applications in combinational chemotherapy for cancer treatments.

Liquid-Phase Ion Trap for Ion Trapping, Transfer, and Sequential Ejection in Solutions.

In this study, a new method/mechanism to manipulate ions in solution was developed, based on which liquid-phase ion trap was built. In this liquid-phase ion trap, ion manipulations conventionally performed in a quadrupole ion trap or in a trapped ion mobility spectrometer placed in a vacuum were achieved in solutions. Through theoretical derivation and numerical simulation, it is found that ions have different motional characteristics than those in vacuum. Instead of a radio frequency quadrupole electric field, tunable DC electric fields together with a constant liquid flow were applied to control ion motions in solution. Different ions could be trapped and focused in a potential well, and ion densities could be increased by over 100-fold. By adjusting the DC electric field of the potential well, trapped ions could be transferred into another trapping region or sequentially released for detection. Ions released from the liquid-phase ion trap were then detected by a mass spectrometer interfaced with an electrospray ionization source. Since the ion manipulation mechanism in solution is different and complementary to that in vacuum, the use of a liquid-phase ion trap could also boost detection sensitivity and the mixture analysis capability of a mass spectrometer.

A Supramolecular Artificial Light-Harvesting System with Two-Step Sequential Energy Transfer for Photochemical Catalysis.

An artificial light-harvesting system with sequential energy-transfer process was fabricated based on a supramolecular strategy. Self-assembled from the host-guest complex formed by water-soluble pillar[5]arene (WP5), a bola-type tetraphenylethylene-functionalized dialkyl ammonium derivative (TPEDA), and two fluorescent dyes, Eosin Y (ESY) and Nile Red (NiR), the supramolecular vesicles achieve efficient energy transfer from the AIE guest TPEDA to ESY. ESY can function as a relay to further transfer the energy to the second acceptor NiR and realize a two-step sequential energy-transfer process with good efficiency. By tuning the donor/acceptor ratio, bright white light emission can be successfully achieved with a CIE coordinate of (0.33, 0.33). To better mimic natural photosynthesis and make full use of the harvested energy, the WP5⊃TPEDA-ESY-NiR system can be utilized as a nanoreactor: photocatalyzed dehalogenation of α-bromoacetophenone was realized with 96 % yield in aqueous medium.

Pseudo-Multiple Reaction Monitoring (Pseudo-MRM) Mode on the "Brick" Mass Spectrometer, Using the Grid-SWIFT Waveform.

Besides portability and increasingly improved performances, the ability of screening target analyte from complex compounds is a crucial function of miniature mass spectrometers, especially for in situ analysis. Selected reaction monitoring (SRM) and multiple reaction monitoring (MRM) operation modes are the most widely used mass spectrometry operation methods for target analyte quantitation. As a continuous effort to improve the analytical performances of the "brick" mass spectrometer, built in-house, pseudo-SRM and pseudo-MRM modes were realized on the linear ion trap mass analyzer in the device. A broadband excitation waveform in both time and frequency domains, namely, the Grid-SWIFT waveform, was constructed and compared with the conventional SWIFT waveform. By isolating target ions during the ion introduction period using the Grid-SWIFT waveform, target ions could be efficiently accumulated inside the ion trap without experiencing space charge effects and interferences from nontarget ions in the samples. As a result, not only the detection sensitivity of the target analyte could be increased, but also the quantitation accuracy over a relatively wide concentration range could be improved.

Bifunctional supramolecular prodrug vesicles constructed from a camptothecin derivative with a water-soluble pillar[5]arene for cancer diagnosis and therapy.

Bifunctional supramolecular prodrug vesicles have been successfully constructed based on the complexation between a glutathione (GSH)-responsive prodrug guest molecule (DNS-CPT) and a water-soluble pillar[5]arene (WP5) for cancer diagnosis and therapy. Under the microenvironment of cancer cells with high GSH concentration, 7-ethyl-10-hydroxycamptothecin (SN-38) with strong yellow fluorescence can be efficiently released from the prodrug DNS-CPT for drug location and cancer therapy.

Electric modeling and characterization of pulsed high-voltage nanoelectrospray ionization sources by a miniature ion trap mass spectrometer.

A better understanding of nanoelectrospray ionization (nano-ESI) would be beneficial in further improving the performances of nano-ESI. In this work, the pulsed high-voltage (HV) nano-ESI has been electrically modeled and then systematically characterized by both voltage-current and mass spectrometry measurements. First, the equivalent resistance of a nano-ESI source changes with respect to both emitter tip diameter and the HV applied. Increased voltage could improve both spray current and ionization efficiency of the pulsed HV nano-ESI. Compared with conventional DC HV method, a pulsed HV has less heating effect on the capillary tip and thus allowing the application of a much higher voltage onto a nano-ESI source. As a result, a pulsed HV nano-ESI could further boost the ionization efficiency of nano-ESI by employing even higher voltages than conventional DC nano-ESI sources.

Multiresponsive Supramolecular Theranostic Nanoplatform Based on Pillar[5]arene and Diphenylboronic Acid Derivatives for Integrated Glucose Sensing and Insulin Delivery.

A closed-loop "smart" insulin delivery system with the capability to mimic pancreatic cells will be highly desirable for diabetes treatment. This study reports a multiple stimuli-responsive insulin delivery platform based on an explicit supramolecular strategy. Self-assembled from a well-designed amphiphilic host-guest complex formed by pillar[5]arene and a diphenylboronic acid derivative and loaded with insulin and glucose oxidase, the obtained insulin-GOx-loaded supramolecular vesicles can selectively recognize glucose, accompanied by the structure disruption and efficient release of the entrapped insulin triggered by the high glucose concentration as well as the in situ generated H2 O2 and acid microenvironment during the GOx-promoted specific oxidation of glucose into gluconic acid. Moreover, such a "smart" supramolecular theranostic nanoplatform is able to function as both a glucose sensor and a controlled insulin delivery actuator. In vivo experiments further demonstrate that this smart supramolecular nanocarrier shows fast response to hyperglycemic circumstances and can effectively regulate the glucose levels in a mouse model of type I diabetes.

Warm/cool-tone switchable thermochromic material for smart windows by orthogonally integrating properties of pillar[6]arene and ferrocene.

Functional materials play a vital role in the fabrication of smart windows, which can provide a more comfortable indoor environment for humans to enjoy a better lifestyle. Traditional materials for smart windows tend to possess only a single functionality with the purpose of regulating the input of solar energy. However, different color tones also have great influences on human emotions. Herein, a strategy for orthogonal integration of different properties is proposed, namely the thermo-responsiveness of ethylene glycol-modified pillar[6]arene (EGP6) and the redox-induced reversible color switching of ferrocene/ferrocenium groups are orthogonally integrated into one system. This gives rise to a material with cooperative and non-interfering dual functions, featuring both thermochromism and warm/cool tone-switchability. Consequently, the obtained bifunctional material for fabricating smart windows can not only regulate the input of solar energy but also can provide a more comfortable color tone to improve the feelings and emotions of people in indoor environments.