Freestanding paper-like electrode materials have trigged significant research interest for their practical application in flexible and lightweight energy storage devices. In this work, we reported a new type of flexible nanohybrid paper electrode based on full inkjet printing synthesis of a freestanding graphene paper (GP) supported three-dimensional (3D) porous graphene hydrogel (GH)-polyaniline (PANI) nanocomposite, and explored its practical application in flexible all-solid-state supercapacitor (SC). The utilization of 3D porous GH scaffold to load nanostructured PANI dramatically enhances the electrical conductivity, the specific capacitance and the cycle stability of the GH-PANI nanocomposite. Additionally, GP can intimately interact with GH-PANI through π-π stacking to form a unique freestanding GP supported GH-PANI nanocomposite (GH-PANI/GP) with distinguishing mechanical, electrochemical and capacitive properties. These exceptional attributes, coupled with the merits of full inkjet printing strategy, lead to the formation of a high-performance binder-free paper electrode for flexible and lightweight SC application. The flexible all-solid-state symmetric SC based on GH-PANI/GP electrode and gel electrolyte exhibits remarkable mechanical flexibility, high cycling performance and acceptable energy density of 24.02 Wh kg(-1) at a power density of 400.33 W kg(-1). More importantly, the proposed simple and scale-up full inkjet printing procedure for the preparation of freestanding GP supported 3D porous GH-PANI nanocomposite is a modular approach to fabricate other graphene-based nanohybrid papers with tailorable properties and optimal components.

Ethylene (C2H4) purification from multicomponent mixtures by physical adsorption presents a great challenge in the chemical industry. This work successfully uses the postsynthetic method of crystal transformation in boiling alkaline solution to synthesize a trap‐and‐flow channel crystal (namely NTU‐67), the flow channel of which provides an effective shape‐ and size‐dependent sieving path for linear molecules such as acetylene (C2H2) and carbon dioxide (CO2), while the adjacent channel possesses customized space for efficient molecular trapping. The three‐bladed array of the nanospace enables the crystal to afford a record productivity of C2H4 (121.5 mL g−1, >99.95%) from C2H2/CO2/C2H4 (1/9/90, v/v/v) mixtures in a single adsorption–desorption cycle under humid and dynamic conditions, even at a high temperature of 343 K and wide gas ratio. The molecular‐level insight and mechanism of the cooperative role of the trap‐and‐flow channel, found computationally and observed experimentally, demonstrates a new design philosophy toward extending the application boundaries of porous coordination polymers to further challenging tasks.

Polymer nanoparticles (PNPs) that exhibit selective stimuli-responsive degradation and drug release at tumor sites are promising candidates in the development of smart nanomedicines. In this thesis, we demonstrate a microfluidic approach to manufacturing biological stimuli-responsive PNPs with flow-tunable physicochemical and pharmacological properties. The investigated PNPs contain cleavable disulfide linkages in two different locations (core and interface, DualM PNPs) exhibiting responsivity to elevated levels of glutathione (GSH), such as those found within cancerous cells.First, we conduct a mechanistic study on the microfluidic formation of DualM PNPs without encapsulated drug. We show that physicochemical properties, including size, morphology, and internal structure, of DualM PNPs are tunable with manufacturing flow rate. Microfluidic formation of DualM PNPs is explained by the interplay of shear-induced coalescence, shear-induced breakup, and intraparticle chain rearrangements. In addition, we demonstrate that rates of GSH-triggered changes in size and internal structure are linearly correlated with initial PNP sizes and internal structures, respectively.Next, we expand our study to focus on microfluidic control of pharmacological properties of DualM PNPs containing either an anticancer drug (paclitaxel, PAX-PNPs) or a fluorescent drug surrogate (DiI-PNPs). Microfluidic PAX-PNPs and DiI-PNPs show similar sizes and morphologies with their non-drug-loaded counterparts under the same flow conditions. We then show that pharmacological properties of DualM PNPs, including encapsulation efficiency, GSH-triggered release rate, cell uptake, cytotoxicity against MCF-7 (cancerous) and HaCaT (healthy), and relative difference in MCF-7 and HaCaT cytotoxicity, all increase linearly as flow-directed PNP size decreases, providing remarkably simple process-structure-property relationships. In addition, we show that microfluidic manufacturing improves encapsulation homogeneities within PNPs relative to bulk nanoprecipitation. These results highlight the potential of flow-directed shear iv processing in microfluidics for providing controlled manufacturing routes to biological stimuli-responsive nanomedicines optimized for specific therapeutic applications.Finally, we summarize various design strategies of biological stimuli-responsive PNPs. We show that the location and density of disulfide linkages within PNPs determines stimulus-triggered degradation mechanism and kinetics. In addition, we show various bottom-up approaches to tune PNP responsivities that involves chemical processing, including formulation chemistry and intramolecular forces. Along with the top-down microfluidic approach that we demonstrate experimentally, this chapter provides a more comprehensive understanding of process-structure-property relations opening up vast possibilities for manufacturing smarter nanomedicines.

Energy-efficient separation of propylene (C 3 H 6 )/ propane (C 3 H 8 ) is in high demand for the chemical industry. However, this process is challenging due to the imperceptible difference in molecular sizes of these gases. Here, we report a continuous water nanotube dedicatedly confined in a Cu 10 O 13based metal−organic framework (MOF) that can exclusively adsorb C 3 H 6 over C 3 H 8 with a record-high selectivity of 1570 (at 1 bar and 298 K) among all the porous materials. Such a high selectivity originates from a new mechanism of initial expansion and subsequent contraction of confined water nanotubes (∼4.5 Å) caused by C 3 H 6 adsorption rather than C 3 H 8 . Such unique response was further confirmed by breakthrough measurements, in which one adsorption/desorption cycle yields each component of the binary mixture high purity (C 3 H 6 : 98.8%; C 3 H 8 : >99.5%) and good C 3 H 6 productivity (1.6 mL mL −1 ). Additionally, benefiting from the high robustness of the framework, the water nanotubes can be facilely recovered by soaking the MOF in water, ensuring long-term use. The molecular insight here demonstrates that the confining strategy opens a new route for expanding the function of MOFs, particularly for the sole recognition from challenging mixtures.

The internal availability of silent speech serves as a translator for people with aphasia and keeps human–machine/human interactions working under various disturbances. This paper develops a silent speech strategy to achieve all-weather, natural interactions. The strategy requires few usage specialized skills like sign language but accurately transfers high-capacity information in complicated and changeable daily environments. In the strategy, the tattoo-like electronics imperceptibly attached on facial skin record high-quality bio-data of various silent speech, and the machine-learning algorithm deployed on the cloud recognizes accurately the silent speech and reduces the weight of the wireless acquisition module. A series of experiments show that the silent speech recognition system (SSRS) can enduringly comply with large deformation (~45%) of faces by virtue of the electricity-preferred tattoo-like electrodes and recognize up to 110 words covering daily vocabularies with a high average accuracy of 92.64% simply by use of small-sample machine learning. We successfully apply the SSRS to 1-day routine life, including daily greeting, running, dining, manipulating industrial robots in deafening noise, and expressing in darkness, which shows great promotion in real-world applications.