Fabrication of Coffee-Ring Nanostructured Membranes for Organic Solvent Nanofiltration.

Organic solvent nanofiltration (OSN) plays important roles in pharmaceutical ingredients purification and solvent recovery. However, the low organic solvent permeance under cross-flow operation of OSN membrane hampers their industrial applications. Herein, we report the construction of coffee-ring structured membrane featuring high OSN permeance. A water-insoluble crystal monomer that dissolved in EtOH/H2O mixed solvent was designed to react with trimesoyl chloride via interfacial polymerization. Owing to the diffusion of EtOH to n-hexane, coffee-ring nanostructure on the support membrane appeared, which served as the template for construction of coffee-ring structured membrane. The optimal nanostructured membrane demonstrated 2.6-fold enhancement in the effective surface area with reduced membrane thickness. Resultantly, the membrane afforded a 2.7-fold enhancement in organic solvent permeance, e.g., ~13 LMH/bar for MeOH, without sacrificing the rejection ability. Moreover, due to the rigid monomer structure, the fabricated membrane shows distinctive running stability in active pharmaceutical ingredients purification and the ability for concentration of medicines.

Tailored Polypyrrole Nanofibers as Ion-to-Electron Transduction Membranes for Wearable K+ Sensors.

Conductive polymers are recognized as ideal candidates for the development of noninvasive and wearable sensors for real-time monitoring of potassium ions (K+) in sweat to ensure the health of life. However, the low ion-to-electron transduction efficiency and limited active surface area hamper the development of high-performance sensors for low-concentration K+ detection in the sweat. Herein, a wearable K+ sensor is developed by tailoring the nanostructure of polypyrrole (PPy), serving as an ion-to-electron transduction layer, for accurately and stably tracing the K+ fluctuation in human sweat. The PPy nanostructures can be tailored from nanospheres to nanofibers by controlling the supramolecular assembly process during PPy polymerization. Resultantly, the ion-to-electron transduction efficiency (17-fold increase in conductivity) and active surface area (1.3-fold enhancement) are significantly enhanced, accompanied by minimized water layer formation. The optimal PPy nanofibers-based K+ sensor achieved a high sensitivity of 62 mV decade-1, good selectivity, and solid stability. After being integrated with a temperature sensor, the manufactured wearable sensor realized accurate monitoring of K+ fluctuation in the human sweat.

Dormancy and double-activation strategy for construction of high-performance mixed-matrix membranes.

Mixed-matrix membranes (MMMs) have the potential for energy-efficient gas separation by matching the superior mass transfer and anti-plasticization properties of the fillers with processability and scaling up features of the polymers. However, construction of high-performance MMMs has been prohibited due to low filler-loading and the existence of interfacial defects. Here, high MOF-loaded, i.e., 55 wt %, MMMs are developed by a 'dormancy and double-activation' (DDA) strategy. High MOF precursor concentration suppresses crystallization in the membrane casting solution, realizing molecular level mixing of all components. Then, the polymeric matrix was formed with uniform encapsulation of MOF nutrients. Subsequently, double-activation was employed to induce MOF crystallization: the alkali promotes MOFs nucleation to harvest small porous nanocrystals while excessive ligands activate the metal ions to enhance the MOFs conversion. As such, quasi-semi-continuous mass transfer channels can be formed in the MMMs by the connected MOFs nanocrystals to boost the gas permeability. The optimized MMM shows significantly ameliorated CO2 permeability, i.e., 2841 Barrer, five-fold enhancement compared with pristine polymer membrane, with a good CO2 /N2 selectivity of 36. Besides, the nanosized MOFs intensify their interaction with polymer chains, endowing the MMMs with good anti-plasticization behaviour and stability, which advances practical application of MMMs in carbon capture.

The combined effects of arteriosclerosis and diabetes on cardiovascular disease risk.

The morbidity and mortality of cardiovascular disease (CVD) rank first among common diseases. Arteriosclerosis and diabetes are risk factors for CVDs, which influence each other. However, their combined effects on CVDs are still unclear. In this study, people who participated in brachial-ankle pulse wave velocity (baPWV) testing and the annual physical examination of the Kailuan Group Finance Co., Ltd., from January 1, 2010, to December 31, 2020, were selected, and their anthropometric, biochemical and epidemiological data were collected. The participants were divided into four groups according to diabetes and arteriosclerosis diagnosis and follow-up. Cox proportional hazards regression and subdistribution hazard models were used to analyse the combined effects of arteriosclerosis and diabetes on CVDs. Multiple sensitivity analyses were also performed. A total of 59,268 Asian populations were selected, including 14,425 females (28.11%) with an average age of 48.10 (± 12.72) years. During follow-up, 1830 subjects developed CVDs (mean follow-up period, 4.72 years). The cumulative incidence rates of the healthy control, diabetes, arteriosclerosis, and comorbidity groups were 5.04% (807/38781), 15.17% (253/3860), 17.04% (465/5987), and 25.59% (305/2684), respectively. The results of multivariate Cox regression analysis showed that compared with the healthy control group, the risk of CVD in the diabetes, arteriosclerosis, and comorbidity groups was significantly increased. Their HR values were 1.88 (95% CI 1.62-2.18), 1.40 (95% CI 1.23-1.60), and 2.10 (95% CI 1.80-2.45), respectively. The results of the sensitivity analysis were robust. For each one standard increase in fasting blood glucose or baPWV, the HR values for CVDs were 1.16 (95% CI 1.12-1.20) and 1.22 (95% CI 1.16-1.28), respectively. The results indicated that both arteriosclerosis and diabetes lead to an increased risk of CVDs. The risk of CVDs, coronary atherosclerotic heart disease, heart failure, stroke, coronary artery bypass grafting and ischemic stroke in patients with arteriosclerosis and diabetes was significantly higher than that in patients with arteriosclerosis or diabetes alone. Therefore, the primary prevention of CVDs in patients with arteriosclerosis complicated with diabetes needs more attention.

Micro/Nano-Fabrication of Flexible Poly(3,4-Ethylenedioxythiophene)-Based Conductive Films for High-Performance Microdevices.

With the increasing demands for novel flexible organic electronic devices, conductive polymers are now becoming the rising star for reaching such targets, which has witnessed significant breakthroughs in the fields of thermoelectric devices, solar cells, sensors, and hydrogels during the past decade due to their outstanding conductivity, solution-processing ability, as well as tailorability. However, the commercialization of those devices still lags markedly behind the corresponding research advances, arising from the not high enough performance and limited manufacturing techniques. The conductivity and micro/nano-structure of conductive polymer films are two critical factors for achieving high-performance microdevices. In this review, the state-of-the-art technologies for developing organic devices by using conductive polymers are comprehensively summarized, which will begin with a description of the commonly used synthesis methods and mechanisms for conductive polymers. Next, the current techniques for the fabrication of conductive polymer films will be proffered and discussed. Subsequently, approaches for tailoring the nanostructures and microstructures of conductive polymer films are summarized and discussed. Then, the applications of micro/nano-fabricated conductive films-based devices in various fields are given and the role of the micro/nano-structures on the device performances is highlighted. Finally, the perspectives on future directions in this exciting field are presented.

Rapid Fabrication of High-Permeability Mixed Matrix Membranes at Mild Condition for CO2 Capture.

Mixed matrix membranes (MMMs), conjugating the advantages of flexible processing-ability of polymers and high-speed mass transfer of porous fillers, are recognized as the next-generation high-performance CO2 capture membranes for solving the current global climate challenge. However, controlling the crystallization of porous metal-organic frameworks (MOFs) and thus the close stacking of MOF nanocrystals in the confined polymer matrix is still undoable, which thus cannot fully utilize the superior transport attribute of MOF channels. In this study, the "confined swelling coupled solvent-controlled crystallization" strategy is employed for well-tailoring the in-situ crystallization of MOF nanocrystals, realizing rapid (<5 min) construction of defect-free freeway channels for CO2 transportation in MMMs due to the close stacking of MOF nanocrystals. Consequently, the fabricated MMMs exhibit approximately fourfold enhancement in CO2 permeability, i.e., 2490 Barrer with a CO2 /N2 selectivity of 37, distinctive antiplasticization merit, as well as long-term running stability, which is at top-tier level, enabling the large-scale manufacture of high-performance MMMs for gas separation.

Recent developments in polymeric nano-based separation membranes.

Polymeric nanomaterials, which have tuneable chemical structures, versatile functionalities, and good compatibility with polymeric matrices, have attracted increasing interest from researchers for the construction of polymeric nano-based separation membranes. With their distinctive nanofeatures, polymeric nano-based membranes show great promise in overcoming bottlenecks in polymer membranes, namely, the trade-off between permeability and selectivity, low stability, and fouling issues. Accordingly, recent studies have focused on tuning the structures and tailoring the surface properties of polymeric nano-based membranes via exploitation of membrane fabrication techniques and surface modification strategies, with the objective of pushing the performance of polymeric nano-based membranes to a new level. In this review, first, the approaches for fabricating polymeric nano-based mixed matrix membranes and homogeneous membranes are summarized, such as surface coating, phase inversion, interfacial polymerization, and self-assembly methods. Next, the manipulation strategies of membrane surface properties, namely, the hydrophilicity/hydrophobicity, charge characteristics, and surface roughness, and interior microstructural properties, namely, the pore size and content, channel construction and regulation, are comprehensively discussed. Subsequently, the separation performances of liquid ions/molecules and gas molecules through polymeric nano-based membranes are systematically reported. Finally, we conclude this review with an overview of various unsolved scientific and technical challenges that are associated with new opportunities in the development of advanced polymeric nano-based membranes.

Acid-Resistance and Self-Repairing Supramolecular Nanoparticle Membranes via Hydrogen-Bonding for Sustainable Molecules Separation.

Functional membranes generally wear out when applying in harsh conditions such as a strong acidic environment. In this work, high acid-resistance, long-lasting, and low-cost functional membranes are prepared from engineered hydrogen-bonding and pH-responsive supramolecular nanoparticle materials. As a proof of concept, the prepared membranes for dehydration of alcohols are utilized. The synthesized membranes have achieved a separation factor of 3000 when changing the feed solution pH from 7 to 1. No previous reports have demonstrated such unprecedentedly high-record separation performance (pervaporation separation index is around 1.1 × 107  g m-2  h-1 ). More importantly, the engineered smart membrane possesses fast self-repairing ability (48 h) that is inherited from the dynamic hydrogen bonds between the hydroxyl groups of polyacrylic acid and carbonyl groups of polyvinylpyrrolidone. To this end, the designed supramolecular materials offer the membrane community a new material type for preparing high acid resistance and long-lasting membranes for harsh environmental cleaning applications.

Superfast Water Transport Zwitterionic Polymeric Nanofluidic Membrane Reinforced by Metal-Organic Frameworks.

Nanofluidics derived from low-dimensional nanosheets and protein nanochannels are crucial for advanced catalysis, sensing, and separation. However, polymer nanofluidics is halted by complicated preparation and miniaturized sizes. This work reports the bottom-up synthesis of modular nanofluidics by confined growth of ultrathin metal-organic frameworks (MOFs) in a polymer membrane consisting of zwitterionic dopamine nanoparticles (ZNPs). The confined growth of the MOFs on the ZNPs reduces the chain entanglement between the ZNPs, leading to stiff interfacial channels enhancing the nanofluidic transport of water molecules through the membrane. As such, the water permeability and solute selectivity of MOF@ZNPM are one magnitude improved, leading to a record-high performance among all polymer nanofiltration membranes. Both the experimental work and the molecular dynamics simulations confirm that the water transport is shifted from high-friction-resistance conventional viscous flow to ultrafast nanofluidic flow as a result of rigid and continuous nanochannels in MOF@ZNPM.

Fundamentals of Optical Imaging.

Optical imaging, which possesses noninvasive and high-resolution features for biomedical imaging, has been used to study various biological samples, from in vitro cells, ex vivo tissue, to in vivo imaging of living organism. Furthermore, optical imaging also covers a very wide scope of spatial scale, from submicron sized organelles to macro-scale live biological samples, enabling it a powerful tool for biomedical studies. Before introducing these superior optical imaging methods to researchers, first of all, it is necessary to present the basic concept of light-matter interactions such as absorption, scattering, and fluorescence, which can be used as the imaging contrast and also affect the imaging quality. And then the working mechanism of various imaging modalities including fluorescence microscopy, confocal microscopy, multiphoton microscopy, super-resolution microscopy, optical coherence tomography (OCT), diffuse optical tomography (DOT), etc. will be presented. Meanwhile, the main features and typical bioimaging applications of these optical imaging technologies are discussed. Finally, the perspective of future optical imaging methods is presented. The aim of this chapter is to introduce the background and principle of optical imaging for grasping the mechanism of advanced optical imaging modalities introduced in the following chapters.

Graphene oxide membranes with stable porous structure for ultrafast water transport.

The robustness of carbon nanomaterials and their potential for ultrahigh permeability has drawn substantial interest for separation processes. However, graphene oxide membranes (GOms) have demonstrated limited viability due to instabilities in their microstructure that lead to failure under cross-flow conditions and applied hydraulic pressure. Here we present a highly stable and ultrapermeable zeolitic imidazolate framework-8 (ZIF-8)-nanocrystal-hybridized GOm that is prepared by ice templating and subsequent in situ crystallization of ZIF-8 at the nanosheet edges. The selective growth of ZIF-8 in the microporous defects enlarges the interlayer spacings while also imparting mechanical integrity to the laminate framework, thus producing a stable microstructure capable of maintaining a water permeability of 60 l m-2 h-1 bar-1 (30-fold higher than GOm) for 180 h. Furthermore, the mitigation of microporous defects via ZIF-8 growth increased the permselectivity of methyl blue molecules sixfold. Low-field nuclear magnetic resonance was employed to characterize the porous structure of our membranes and confirm the tailored growth of ZIF-8. Our technique for tuning the membrane microstructure opens opportunities for developing next-generation nanofiltration membranes.

Flexible porphyrin doped polymer optical fibers for rapid and remote detection of trace DNT vapor.

With the rapid growth of anti-terrorist activities worldwide, it becomes an emerging requirement to rapidly and accurately detect hidden explosive threats. However, the safety issue during the explosive material detection, e.g. unexpected explosion, is still an insurmountable challenge. In this study, we design and mass-produce a novel kind of flexible 5,10,15,20-tetrakis(4-aminophenyl)porphyrin doped polymer optical fiber (PPOF) for rapid and accurate detection of trace 2,4-dinitrotoluene (DNT) vapor based on the DNT induced florescence quenching mechanism. The influence of doping concentration, bending, and temperature on the sensing performance is investigated. PPOF shows immunity to bending, enabling it to work in a harsh environment. It is experimentally demonstrated that the limit of detection and response time of the proposed PPOF could reach around 120 ppb and 3 minutes, respectively, which make it much better than other techniques. Owning to its inherent advantages including low-cost, remote-control capability, and compatibility with optical communication networking, PPOF can be constructed the quasi-distributed sensing networking of explosive matters in the future, providing a new strategy for anti-terrorism.

Precise Micropatterning of a Porous Poly(ionic liquid) via Maskless Photolithography for High-Performance Nonenzymatic H2O2 Sensing.

Porous poly(ionic liquid)s (PILs) recently have been serving as a multifunctional, interdisciplinary materials platform in quite a few research areas, including separation, catalysis, actuator, sensor, and energy storage, just to name a few. In this context, the capability of photopatterning PIL microstructures in a porous state on a substrate is still missing but is a crucial step for their real industrial usage. Here, we developed a method for in situ rapid patterning of porous PIL microstructures via a maskless photolithography approach coupled with a simple electrostatic complexation treatment. This breakthrough enables design of miniaturized sensors. As exemplified in this work, upon loading Pt nanoparticles into porous PIL microstructures, the hybrid sensor showed outstanding performance, bearing both a high sensitivity and a wide detection range.

Solution-Processed Bilayer Dielectrics for Flexible Low-Voltage Organic Field-Effect Transistors in Pressure-Sensing Applications.

Flexible pressure sensors based on organic field-effect transistors (OFETs) have emerged as promising candidates for electronic-skin applications. However, it remains a challenge to achieve low operating voltages of hysteresis-free flexible pressure sensors. Interface engineering of polymer dielectrics is a feasible strategy toward sensitive pressure sensors based on low-voltage OFETs. Here, a novel type of solution-processed bilayer dielectrics is developed by combining a thick polyelectrolyte layer of polyacrylic acid (PAA) with a thin poly(methyl methacrylate) (PMMA) layer. This bilayer dielectric can provide a vertical phase separation structure from hydrophilic interface to hydrophobic interface which adjoins well to organic semiconductors, leading to improved stability and remarkably reduced leakage currents. Consequently, OFETs using the PMMA/PAA dielectrics reveal greatly suppressed hysteresis and improved mobility compared to those with a pure PAA dielectric. Using the optimized PMMA/PAA dielectric, flexible OFET-based pressure sensors that show a record high sensitivity of 56.15 kPa-1 at a low operating voltage of -5 V, a fast response time of less than 20 ms, and good flexibility are further demonstrated. The salient features of high capacitance, good dielectric performance, and excellent reliability of the bilayer dielectrics promise a bright future of flexible sensors based on low-voltage OFETs for wearable electronic applications.

Optical fiber LPG biosensor integrated microfluidic chip for ultrasensitive glucose detection.

An optical fiber sensor integrated microfluidic chip is presented for ultrasensitive detection of glucose. A long-period grating (LPG) inscribed in a small-diameter single-mode fiber (SDSMF) is employed as an optical refractive-index (RI) sensor. With the layer-by-layer (LbL) self-assembly technique, poly (ethylenimine) (PEI) and poly (acrylic acid) (PAA) multilayer film is deposited on the SDSMF-LPG sensor for both supporting and signal enhancement, and then a glucose oxidase (GOD) layer is immobilized on the outer layer for glucose sensing. A microfluidic chip for glucose detection is fabricated after embedding the SDSMF-LPG biosensor into the microchannel of the chip. Experimental results reveal that the SDSMF-LPG biosensor based on such a hybrid sensing film can ultrasensitively detect glucose concentration as low as 1 nM. After integration into the microfluidic chip, the detection range of the sensor is extended from 2 µM to 10 µM, and the response time is remarkablely shortened from 6 minutes to 70 seconds.

Rapid 3D Patterning of Poly(acrylic acid) Ionic Hydrogel for Miniature pH Sensors.

Poly(acrylic acid) (PAA), as a highly ionic conductive hydrogel, can reversibly swell/deswell according to the surrounding pH conditions. An optical maskless -stereolithography technology is presented to rapidly 3D pattern PAA for device fabrication. A highly sensitive miniature pH sensor is demonstrated by in situ printing of periodic PAA micropads on a tapered optical microfiber.

Label-free, disposable fiber-optic biosensors for DNA hybridization detection.

A novel and highly sensitive fiber-optic DNA sensor based on a thin-core fiber modal interferometer (TCFMI) is demonstrated by using a layer-by-layer (LbL) self-assembly technology. Poly(ethylenimine) (PEI), poly(acrylic acid) (PAA) and single-stranded DNA (ssDNA) were used for the preparation of a polyelectrolyte multilayer film for DNA detection. The film thickness was measured through a surface profilometer. The surface morphologies of (PEI/PAA)4, (PEI/PAA)4.5 and (PEI/PAA)4(PEI/DNA)1 multilayer films were characterized by atomic force microscopy. The fabricated DNA sensors were tested with different types of target ssDNA solutions with a concentration of 1 µM. The results show that the sensitivity of the TCFMI-based ssDNA sensor is 0.27 nm/matched-base at the concentration of 1 µM and can even distinguish the number of matched bases of ssDNA chains.

Fiber optic pH sensor with self-assembled polymer multilayer nanocoatings.

A fiber-optic pH sensor based on a tilted fiber Bragg grating (TFBG) with electrostatic self-assembly multilayer sensing film is presented. The pH sensitive polymeric film, poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) was deposited on the circumference of the TFBG with the layer-by-layer (LbL) electrostatic self-assembly technique. The PDDA/PAA film exhibits a reduction in refractive index by swelling in different pH solutions. This effect results in wavelength shifts and transmission changes in the spectrum of the TFBG. The peak amplitude of the dominant spectral fringes over a certain window of the transmission spectrum, obtained by FFT analysis, has a near-linear pH sensitivity of 117 arbitrary unit (a.u.)/pH unit and an accuracy of ±1 a.u. (in the range of pH 4.66 to pH 6.02). The thickness and surface morphology of the sensing multilayer film were characterized to investigate their effects on the sensor's performance. The dynamic response of the sensor also has been studied (10 s rise time and 18 s fall time for a sensor with six bilayers of PDDA/PAA).

Low-cost high-performance fiber-optic pH sensor based on thin-core fiber modal interferometer.

A new fiber-optic pH sensor based on a thin-core fiber modal interferometer with electrostatic self-assembled nanocoating is presented. After inserting a segment of thin-core fiber into a standard single-mode fiber, high-order cladding modes are excited and interfere with the core mode to form an in-fiber modal interferometer. The side surface of the sensor is then deposited with poly(allylamine hydrochloride) and poly(acrylic acid) nanocoating by electrostatic self-assembly technique. A fast and linear response is obtained in either acid or alkali solution (in the pH range 2.5 to 10) with resolution of 0.013 pH unit.