Standalone Stretchable Biophysical Sensing System Based on Laser Direct Write of Patterned Porous Graphene/Co3O4 Nanocomposites.

Skin-interfaced wearable sensors can continuously monitor various biophysical and biochemical signals for health monitoring and disease diagnostics. However, such devices are typically limited by unsatisfactory and unstable output performance of the power supplies under mechanical deformations and human movements. Furthermore, there is also a lack of a simple and cost-effective fabrication technique to fabricate and integrate varying materials in the device system. Herein, we report a fully integrated standalone stretchable biophysical sensing system by combining wearable biophysical sensors, triboelectric nanogenerator (TENG), microsupercapacitor arrays (MSCAs), power management circuits, and wireless transmission modules. All of the device components and interconnections based on the three-dimensional (3D) networked graphene/Co3O4 nanocomposites are fabricated via low-cost and scalable direct laser writing. The self-charging power units can efficiently harvest energy from body motion into a stable and adjustable voltage/current output to drive various biophysical sensors and wireless transmission modules for continuously capturing, processing, and wirelessly transmitting various signals in real-time. The novel material modification, device configuration, and system integration strategies provide a rapid and scalable route to the design and application of next-generation standalone stretchable sensing systems for health monitoring and human-machine interfaces.

In Situ Synthesis of Gold Nanoparticles from Chitin Nanogels and Their Drug Release Response to Stimulation.

In this study, gold nanoparticles (AuNPs) were synthesized in situ using chitin nanogels (CNGs) as templates to prepare composites (CNGs@AuNPs) with good photothermal properties, wherein their drug release properties in response to stimulation by near-infrared (NIR) light were investigated. AuNPs with particle sizes ranging from 2.5 nm to 90 nm were prepared by varying the reaction temperature and chloroauric acid concentration. The photothermal effect of different materials was probed by near-infrared light. Under 1 mg/mL of chloroauric acid at 120 °C, the prepared CNGs@AuNPs could increase the temperature by 32 °C within 10 min at a power of 2 W/cm2. The Adriamycin hydrochloride (DOX) was loaded into the CNGs@AuNPs to investigate their release behaviors under different pH values, temperatures, and near-infrared light stimulations. The results showed that CNGs@AuNPs were pH- and temperature-responsive, suggesting that low pH and high temperature could promote drug release. In addition, NIR light stimulation accelerated the drug release. Cellular experiments confirmed the synergistic effect of DOX-loaded CNGs@AuNPs on chemotherapy and photothermal therapy under NIR radiation.

3D Printing of High Viscosity UV-Curable Resin for Highly Stretchable and Resilient Elastomer.

Elastomers prepared via vat photopolymerizationus ually exhibit unsatisfied mechanical properties owing to their insufficient growth of molecular weight upon UV exposure. Increasing the weight ratio of oligomer in the resin system is an effective approach to enhance the mechanical properties, yet the viscosity of the UV-curable resin increases dramatically; this hinders its printing. In this study, a linear scan-based vat photopolymerization (LSVP) system which can print high-viscosity resins is implemented to 3D print the oligomer-dominated UV-curable resin via a dual-curing mechanism. A polyurethane methacrylate blocking oligomer is first synthesized and then mixed with a commercialized bifunctional oligomer, photoinitiator, and primary amine as a chain extender to prepare high-viscosity UV-curable resin for the LSVP system. The deblocked isocyanate is further crosslinked with a chain extender via thermal treatment to construct a highly entangled polymer chain network. The optimal thermal treatment parameters are investigated, and the resilience of the 3D-printed elastomer is evaluated through continuous tensile loading and unloading tests. Subsequently, complex structured elastomers are printed, exhibiting favorable mechanical durability without defects. The results obtained from this work will provide a reference for preparing elastomeric devices with excellent physical properties and expand the application scope of vat photopolymerization to new fields.

3D printing of ultra-high viscosity resin by a linear scan-based vat photopolymerization system.

The current printing mechanism of the bottom-up vat photopolymerization 3D printing technique places a high demand on the fluidity of the UV-curable resin. Viscous high-performance acrylate oligomers are compounded with reactive diluents accordingly to prepare 3D printable UV-curable resins (up to 5000 cps of viscosity), yet original mechanical properties of the oligomers are sacrificed. In this work, an elaborated designed linear scan-based vat photopolymerization system is developed, allowing the adoption of printable UV-curable resins with high viscosity (> 600,000 cps). Briefly, this is realized by the employment of four rollers to create an isolated printing area on the resin tank, which enables the simultaneous curing of the resin and the detachment of cured part from the resin tank. To verify the applicability of this strategy, oligomer dominated UV-curable resin with great mechanical properties, but high viscosity is prepared and applied to the developed system. It is inspiring to find that high stress and strain elastomers and toughened materials could be facilely obtained. This developed vat photopolymerization system is expected to unblock the bottleneck of 3D printed material properties, and to build a better platform for researchers to prepare various materials with diversiform properties developed with 3D printing.

Bamboo-based magnetic activated carbon for efficient removal of sulfadiazine: Application and adsorption mechanism.

Due to increasing antibiotic pollution in the water environment, green and efficient adsorbents are urgently needed to solve this problem. Here we prepare magnetic bamboo-based activated carbon (MDBAC) through delignification and carbonization using ZnCl2 as activator, resulting in production of an activated carbon with large specific surface area (1388.83 m2 g-1). The influencing factors, such as solution pH, initial sulfadiazine (SD) concentration, temperature, and contact time, were assessed in batch adsorption experiments. The Langmuir isotherm model demonstrated that MDBAC adsorption capacity on SD was 645.08 mg g-1 at its maximum, being higher than majority of previously reported adsorbents. In SD adsorption, the kinetic adsorption process closely followed the pseudo-second kinetic model, and the thermodynamic adsorption process was discovered to be exothermic and spontaneous in nature. The MDBAC exhibited excellent physicochemical stability, facile magnetic recovery and acceptable recyclability properties. Moreover, the synergistic interactions between MDBAC and SD mainly involved electrostatic forces, hydrogen bonding, π-π stacking, and chelation. Within the benefits of low cost, ease of production and excellent adsorption performance, the MDBAC biosorbent shows promising utilization in removing antibiotic contaminants from wastewater.

Codoping g-C3N4 with boron and graphene quantum dots: Enhancement of charge transfer for ultrasensitive and selective photoelectrochemical detection of dopamine.

The development of superior photoelectrochemical (PEC) sensors for biosensing has become a major objective of PEC research. However, conventional PEC-active materials are typically constrained by a weak photocurrent response owing to their limited surface-active sites and high electron-hole recombination rate. Here, a boron and graphene quantum dots codoped g-C3N4 (named GBCN) as PEC sensor for highly sensitive dopamine (DA) detection was fabricated. GBCN exhibited the greatest photocurrent response and PEC activity compared to free g-C3N4 and g-C3N4 doped with boron. The proposed PEC sensor for DA determination exhibited a broad linear range (0.001-800 µM) and a low detection limit (0.96 nM). In particular, a sensitivity up to 10.3771 µA/µM/cm2 was seen in the case of GBCN. The high PEC activity can be attributed to the following factors: (1) the boron and graphene quantum dots co-doping significantly increased the specific surface area of g-C3N4, providing more adsorption sites for DA; (2) the dopants extended the absorption intensity of g-C3N4, red-shifting the absorption from 470 to 540 nm; and (3) the synergism of boron and graphene quantum dots efficiently boosted the photogenerated electrons migration from the conduction band of g-C3N4 to graphene quantum dots, facilitating charge separation. In addition, GBCN also exhibited good anti-interference ability and stability. This research may shed light on the creation of a highly sensitive and selective PEC platform for detecting biomolecules.

Modified Fabrication of Perovskite-Based Composites and Its Exploration in Printable Humidity Sensors.

Organic perovskites are promising optoelectronic semiconductor materials with photoelectric applications. It is known that the luminescence of perovskites is highly sensitive to hydron molecules due to its low moisture resistance of crystal structure, indicating its potential application on humidity-sensing. Herein, a novel perovskite-based compound (PBC) with minimal defects was developed to promote the photoluminescence performance via optimization of the drying method and precursor constitutions. Perovskite materials with good structural integrity and enhanced fluorescence performance up to four times were obtained from supercritical drying. Moreover, the hydrophilic polymer matrix, polyethylene oxide (PEO), was added to obtain a composite of perovskite/PEO (PPC), introducing enhanced humidity sensitivity and solution processibility. These perovskite/PEO composites also exhibited long-term stability and manifold cycles of sensitivity to humidity owing to perovskite encapsulation by PEO. In addition, this precursor solution of perovskite-based composites could be fancily processed by multiple methods, including printing and handwriting, which demonstrates the potential and broaden the applications in architecture decoration, logos, trademarks, and double encryption of anti-fake combined with humidity.

Mussel-Inspired Alternating Copolymer as a High-Performance Adhesive Material Both at Dry and Under-Seawater Conditions.

Marine mussels have the ability to cling to various surfaces at wet or underwater conditions, which inspires the research of catechol-functionalized polymers (CFPs) to develop high-performance adhesive materials. However, these polymeric adhesives generally face the problems of complex synthetic route, and it is still high challenging to prepare CFPs with excellent adhesive performance both at dry and underwater conditions. Herein, a mussel-inspired alternating copolymer, poly(dopamine-alt-2,2-bis(4-glycidyloxyphenyl)propane) (P(DA-a-BGOP)), is synthesized in one step by using commercially available monomers through epoxy-amino click chemistry. The incorporation of polar groups and rigid bisphenol A structures into the polymer backbone enhances the cohesion energy of polymer matrix. The alternating polymer structure endows the polymers with high catechol content and controlled polymer sequence. As a result, P(DA-a-BGOP) exhibits a strong bonding strength as high as 16.39 ± 2.13 MPa on stainless steel substrates after a hot pressing procedure and displays a bonding strength of 1.05 ± 0.05 MPa on glass substrates at an under-seawater condition, which surpasses most commercial adhesives.

3D Printing Mechanically Robust and Transparent Polyurethane Elastomers for Stretchable Electronic Sensors.

Advanced stretchable electronic sensors with a complex structure place higher requirements on the mechanical properties and manufacturing process of the stretchable substrate materials. Herein, three kinds of polyurethane acrylate oligomers were synthesized successfully and mixed with a commercial acrylate monomer (isobornyl acrylate) to prepare photocurable resins with a low viscosity for a digital light processing three-dimensional (3D) printer without custom equipment. Results showed that the resin containing poly(tetrahydrofuran) units (PPTMGA-40) exhibited optimal mechanical properties and shape recoverability. The tensile strength and elongation at break of PPTMGA-40 were 15.7 MPa and 414.3%, respectively. The unprecedented fatigue resistance of PPTMGA-40 allowed it to withstand 100 compression cycles at 80% strain without fracture. The transmittance of PPTMGA-40 reached 89.4% at 550 nm, showing high transparency. An ionic hydrogel was coated on the surface of 3D-printed structures to fabricate stretchable sensors, and their conductivity, transparency, and mechanical performance were characterized. A robust piezoresistive strain sensor with a high strength (∼6 MPa) and a wearable finger guard sensor were fabricated, demonstrating that this hydrogel-elastomer system can meet the requirements of applications for advanced stretchable electronic sensors and expand the usage scope.

Structure-Property Relationship of Stereolithography Resins Containing Polysiloxane Core-Shell Nanoparticles.

Stereolithography (SL) is an additive manufacturing technique for fabricating bulk and delicate objects layer by layer using UV-curable resin. However, epoxy-based photocurable resins used in SL printers are commonly brittle due to the high cross-linking density, thus restricting the widespread adoption of SL. In an effort to overcome this drawback, this paper details an approach of toughening the resulting workpieces by incorporating polysiloxane core-shell nanoparticles (SCSP) into an epoxy-based, photocurable formulation. This approach attempted to attain both thermal stabilities and transparency qualities comparable to that of resin without SCSP. This work systematically analyzed how the shell thickness of the SCSP impacted the final properties of the printed product. Introducing 5% w/w SCSP with a diameter of approximately 132 nm into the resin improved strain at break measured by tensile and flexural tests by 745.5 and 248.6%, respectively, and increased the fracture toughness by 166.3%. Owing to the advantages of toughness, thermal stabilities, transparency, and high accuracy of epoxy-based photocurable resin with SCSP, the 3D printing nanocomposite developed here is capable of preparing a poly(methyl methacrylate) (PMMA)-like workpiece with a commercial SL 3D printer. These results may expand the scope of the application of 3D printing in a wide variety of industries.

Dynamic Imine Bond-Based Shape Memory Polymers with Permanent Shape Reconfigurability for 4D Printing.

Shape memory polymer (SMP)-based 4D printing combines the advantages of SMP and 3D printing to form active materials with delicate structure. Nowadays, studies of SMP-based 4D printing materials mainly focus on cross-linked (meth)acrylate of which the permanent shape cannot be changed for their covalent linkage, limiting the usage of 4D printing materials. In this paper, a novel (meth)acrylate monomer with an aldehyde group (2-(methacryloyloxy)ethyl 4-formylbenzoate, MEFB) and hyperbranched cross-linker (HPASi) are synthesized to build (meth)acrylate systems (IEMSis) with dynamic imine bonds for 4D printing. The flexible chain structure of HPASi significantly enhances the toughness of IEMSis, which is 33-97-fold higher than that of the one without HPASi (IEM). The addition of HPASi also endows IEMSis good shape memory properties, and the shape fixity and shape recovery ratios of them are 97.5-97.6 and 91.4-93.7%, respectively. At the same time, IEMSis can undergo a stress relaxation process by dynamic exchanges of imine bonds under relatively mild conditions without a catalyst to acquire an ability of permanent shape reconfiguration. The shape retention ratio of IEMSi3 is 84.3%. In addition, the 4D-printed structures displayed here indicate that these 4D printing systems have a myriad of potential applications including aerospace structures, soft robotic grippers, smart electron switches, and intelligent packaging, while the reconfigurability shown by IEMSi3 will expand the scope of application fields of 4D printing materials.

Selenium and nitrogen co-doped carbon quantum dots as a fluorescent probe for perfluorooctanoic acid.

Highly fluorescent carbon quantum dots co-doped with selenium and nitrogen  (SeN-CQDs) were fabricated via a one-pot hydrothermal route using selenomethionine as the sole precursor. The SeN-CQDs aggregates have sizes between 30 and 45 nm and display blue fluorescence with a quantum yield of 8% at excitation/emission wavelengths of 350/445 nm. The fluorescence is pH dependent and decreases under acidic conditions. The doping of the CQDs with selenium and nitrogen was proven by X-ray photoelectron spectroscopy (XPS). Fluorescence is selectively quenched by perfluorooctanoic acid (PFOA), and this is accompanied by a decreased fluorescence lifetime. Quenching is not due to aggregation in view of the unaltered sizes of nanoparticles as revealed by TEM and DLS analyses. UV-vis absorption titration suggested the formation of an excited state complex between SeN-CQDs and PFOA, and quenching originates from the internal electron transfer in the excited state complex. The method was used to detect PFOA quantitatively in the linear range of 10-70 µM with a 1.8 µM detection limit. The nanoprobe has a high selectivity for PFOA over potentially interfering molecules. The practicability of the method was ascertained by accurate detection of PFOA in real samples by the standard addition method. The method may be further improved by tuning the interaction between PFOA and SeN-CQDs through optimizing the doping and the surface composition of the SeN-CQDs. Graphical abstract Schematic presentation of a fluorometric method for perfluorooctanoic acid detection by using a selenium and nitrogen co-doped carbon quantum dots as the fluorescent probe.

Hypocholesterolemic effect of capsaicinoids in rats fed diets with or without cholesterol.

The potential mechanism of the hypocholesterolemic effect of capsaicinoids in rats fed with cholesterol-enriched and cholesterol-free diets was determined. Capsaicinoids favorably modified the lipoprotein profile of rats. Capsaicinoids consumption down-regulated the mRNA levels of hepatic 3-hydroxyl-3-methylglutaryl CoA (HMG-CoA) reductase by 0.55-fold and hepatic cholesterol-7α-hydroxylase (CYP7A1) by 0.53-fold in the cholesterol-free diet group (P < 0.05) but up-regulated the CYP7A1 level by 1.38-fold in the cholesterol-enriched diet group (P < 0.05). It also increased the expression levels of ileal bile acid binding protein and apical sodium-dependent bile acid transporter in the ileum, as well as transient receptor potential vanilloid type-1 in the liver and ileum in the different groups. Capsaicinoids reduced the amount of bile acids in feces by -15.97% and contents of the small intestine by -9.64% in the cholesterol-free diet group (P < 0.05) but increased both by 13.06% and 10.20%, respectively, in the cholesterol-enriched diet group. The cholesterol-lowering action of capsaicinoids in the cholesterol-free diet group was attributed to the inhibition of hepatic cholesterol synthesis, whereas that in the cholesterol-enriched diet group was attributed to the stimulation of the conversion of cholesterol to bile acids and the increasing excretions of bile acids in feces.

The hypocholesterolemic effect of capsaicinoids in ovariectomized rats fed with a cholesterol-free diet was mediated by inhibition of hepatic cholesterol synthesis.

Previous studies showed that capsaicinoid supplementation favorably modifies the plasma lipoprotein profile. The present study investigated the effect of capsaicinoids on plasma lipids and gene expressions of key receptors and enzymes involved in cholesterol metabolism in ovariectomized (OVX) rats. OVX rats were fed with a cholesterol-free diet and orally administered 0 mg kg(-1) bw (OVX-CON), 5 mg kg(-1) bw (OVX-LD), 10 mg kg(-1) bw (OVX-MD), and 15 mg kg(-1) bw (OVX-HD) capsaicinoids daily for 28 days. As the capsaicinoids dose increased, body weight gain and concentrations of plasma triglyceride, total cholesterol, and low-density lipoprotein cholesterol, as well as total lipid accumulation were significantly decreased. In addition, the mRNA levels of hepatic 3-hydroxyl-3-methylglutaryl CoA reductase and cholesterol-7α-hydroxylase were down-regulated, whereas those of transient receptor potential vanilloid type-1, ileal apical sodium-dependent bile acid transporter, and intestinal bile acid binding protein were up-regulated. The excretion of small intestinal bile acid contents and fecal bile acid also decreased. These results suggest that capsaicinoids can prevent ovarian hormone deficiency-induced hypercholesterolemia by inhibiting the hepatic cholesterol synthesis.