All-in-One Luminescent Lanthanide Coordination Polymer Nanoprobe for Facile Detection of Protein Kinase Activity.

This study developed a novel luminescent assay for kinase activity using metal-organic coordination polymer nanoparticles (Tb/ATP-Zn) as the probe. Tb/ATP-Zn, self-assembled by adenosine triphosphate (ATP), Zn2+, and Tb3+, is non-luminescent. Protein kinase A (PKA) can catalyze the transformation of ATP within Tb/ATP-Zn nanoparticles to adenosine diphosphate (ADP), which in turn effectively sensitizes the luminescence of Tb3+. Based on this mechanism, Tb/ATP-Zn can realize the facile luminescent "turn-on" sensing of protein kinase activity without the use of external ATP and substrate peptide. Under optimized conditions, the fluorescence intensities of Tb/ATP-Zn at 550 nm are linear with the PKA activity within a range of 0.3-1.5 U·µL-1. The LOD (S/N = 3) of this method is down to 0.001 U·µL-1. The presented assay also features high selectivity, long-term stability, fast response, and convenient operation. Furthermore, Tb/ATP-Zn was successfully employed for monitoring PKA activity in cell lysis solutions. Probe Tb/ATP-Zn is thus expectable to be a powerful tool for the practical study of PKA in relevant biological events.

Dual-Response Ratiometric Electrochemical Microsensor for Effective Simultaneous Monitoring of Hypochlorous Acid and Ascorbic Acid in Human Body Fluids.

Redox homeostasis between hypochlorous acid (HClO/ClO-) and ascorbic acid (AA) significantly impacts many physiological and pathological processes. Herein, we report a new electrochemical sensor for the simultaneous determination of HClO and AA in body fluids. We first coated a carbon fiber microelectrode (CFME) with a three-dimensional nanocomposite consisting of graphene oxide (GO) and carbon nanotubes (CNTs) to fabricate the CFME/GO-CNT electrode. After the electrochemical reduction of GO (ERGO), we integrated a latent 1-(3,7-bis(dimethylamino)-10H-phenothiazin-10-yl)-2-methylpropan-1-one (MBS) electrochemical molecular recognition probe to monitor HClO and employed anthraquinone (AQ) as an internal reference. The compact CFME/ERGO-CNT/AQ + MBS sensor enabled the accurate and simultaneous measurement of HClO and AA with excellent selectivity and sensitivity. Measurements were highly reproducible, and the sensor was stable and exceptionally biocompatible. We successfully detected changes in the redox cycles of HClO and AA in human body fluids. This sensor is a significant advance for the investigation of reactions involved in cellular redox regulation. More importantly, we have devised a strategy for the design and construction of ratiometric electrochemical biosensors for the simultaneous determination of various bioactive species.

Potentiometric analysis of sialic acid with a flexible carbon cloth based on boronate affinity and molecularly imprinted polymers.

An electrochemical platform was proposed for highly sensitive and selective analysis of sialic acid based on molecularly imprinted polymers (MIPs), which were electropolymerized with the monomer molecules of 3-aminophenylboronic acid (ABA) on a carbon cloth (CC) electrode in the presence of template molecules. The fabricated sensor, named the PABA/CC-based MIP electrode, could be used for the detection of sialic acid because the reversible and covalent boronic acid-diol binding was sensitive to the electrochemical potential of the prepared sensor. The utilization of a CC film as the substrate could improve the sensitivity due to its good electrical conductivity and large surface area. Under the optimized conditions, a good relationship between the change in potential and the concentration of sialic acid was obtained in the range from 40 µM to 440 µM with a detection limit of 0.5 µM. The resulting MIP sensor also displayed good selectivity, reproducibility and stability. Moreover, this sensor was successfully applied for the evaluation of the sialic acid level in infant formulas.

Programmable spatial deformation by controllable off-center freestanding 4D printing of continuous fiber reinforced liquid crystal elastomer composites.

Owing to their high deformation ability, 4D printed structures have various applications in origami structures, soft robotics and deployable mechanisms. As a material with programmable molecular chain orientation, liquid crystal elastomer is expected to produce the freestanding, bearable and deformable three-dimensional structure. However, majority of the existing 4D printing methods for liquid crystal elastomers can only fabricate planar structures, which limits their deformation designability and bearing capacity. Here we propose a direct ink writing based 4D printing method for freestanding continuous fiber reinforced composites. Continuous fibers can support freestanding structures during the printing process and improve the mechanical property and deformation ability of 4D printed structures. In this paper, the integration of 4D printed structures with fully impregnated composite interfaces, programmable deformation ability and high bearing capacity are realized by adjusting the off-center distribution of the fibers, and the printed liquid crystal composite can carry a load of up to 2805 times its own weight and achieve a bending deformation curvature of 0.33 mm-1 at 150 °C. This research is expected to open new avenues for creating soft robotics, mechanical metamaterials and artificial muscles.

Controllable preparation of silver-doped hollow carbon spheres and its application as electrochemical probes for determination of glycated hemoglobin.

Silver-doped hollow carbon spheres (Ag@HCS) were firstly introduced as electrochemical probes for glycated hemoglobin (HbA1c) sensing at a molecularly imprinted polymer (MIP)-based carbon cloth (CC) electrode. Herein, Ag@HCS was prepared using one-pot polymerization of resorcinol and formaldehyde with AgNO3 on the SiO2 template, subsequent carbonization, and template removal. Furthermore, poly-aminophenylboronic acid (PABA) as the MIP film was used as a sensing platform for recognition of HbA1c, which captured the Ag@HCS probe by binding of HbA1c with aptamer modified on the probe surface. Due to regular geometry, large specific surface area, superior electrical conductivity, and highly-dispersed Ag, the prepared Ag@HCS probe provided an amplified electrochemical signal based on the Ag oxidation. By use of the sandwich-type electrochemical sensor, the ultrahigh sensitivity of 4.365 µA (µg mL-1)-1 cm-2 and a wide detection range of 0.8-78.4 µg mL-1 for HbA1c detection with a low detection limit of 0.35 µg mL-1 were obtained. Excellent selectivity was obtained due to the specific binding between HbA1c and PABA-based MIP film. The fabricated electrochemical sensing platform was also implemented successfully for the determination of HbA1c concentrations in the serum of healthy individuals.

Development of a novel ratiometric electrochemical sensor for monitoring ß-galactosidase in Parkinson's disease model mice.

Rapid, simple, accurate and highly sensitive detection of enzymes is essential for early screening and clinical diagnosis of many diseases. In this study, we report the fabrication of a turn-on ratiometric electrochemical sensor for the in situ determination of ß-Galactosidase (ß-Gal) based on surface engineering and the design of a molecular probe (Pygal) specific for ß-Gal recognition. First, Pygal probe was synthesized and characterized, and then co-assembled with the methylene blue (MB) internal reference probe on the surface of single-wall carbon nanotubes (SWCNT)-modified carbon fiber microelectrode (CFME). The resulting CFME/SWCNT/MB + Pygal sensor is activated in the presence of ß-Gal giving one peak at 0.33 V originating from the oxidation of the product of Pygal enzymatic hydrolysis (PyOH). Another oxidation peak attributed to MB appears simultaneously at -0.28 V allowing the construction of a ratiometric electrochemical sensor for ß-Gal detection with improved sensitivity and accuracy. The sensor showed a linear response to ß-Gal in a wide concentration range from 1.5 to 30 U L-1 and a low detection limit of 0.1 U L-1. Moreover, the sensor demonstrated excellent selectivity against several biologically relevant hydrolases and redox-active molecules. Finally, the combination of excellent electrochemical performance and favorable physicochemical properties of CFME allowed the determination of ß-Gal in the whole blood of Parkinson's Disease (PD) model mice. The workflow reported in this study provides a strategy for the design and development of sensors for the in vivo monitoring of other enzymes important for the early diagnosis of different health issues.

Escape of polymer chains from an attractive channel under electrical force.

The escape of polymer chains from an attractive channel under external electrical field is studied using dynamical Monte Carlo method. Though the escaping process is nonequilibrium in nature, results show that the one-dimensional diffusion theoretical model based on the equilibrium assumption can describe the dependence of the average escaping time (τ(0)) on the polymer-channel interaction (ɛ), the electrical field (E), the chain length (n), and the channel length (L), qualitatively. Results indicate that both ɛ and E play very important roles in the escaping dynamics. For small ɛ, the polymer chain moves out of the channel continuously and quickly. While for large ɛ, the polymer chain is difficult to move out of long channels as it is trapped for a long time (τ(trap)) when the end segment is near the critical point x(C). These results are consistent with the theoretical results for the free energy profiles at small ɛ and large ɛ, respectively. The dependence of x(C) and τ(trap) on ɛ and E are discussed, and specific relations are obtained. The configurational properties of polymer chain are also investigated during the escaping process.

Dentists have a high occupational risk of neck disorders with impact on somatosensory function and neck mobility.

OBJECTIVES: Musculoskeletal disorders (MSDs) in the neck and shoulder region may be associated with significant impairment of quality of life and well-being. The study was to determine the prevalence of painful MSDs in Chinese dentists and evaluate somatosensory function and neck mobility compared with non-dental professional controls. METHODS: One hundred dentists (age: 36.5 ± 9.8 years) and 102 controls (age: 36.2 ± 10.0 years) were recruited between September 2019 and December 2020. The Medical Outcome Study 36-item short-form health survey questionnaire and information of MSDs history were recorded. The cervical range of motion (CROM) with and without pain, and the pressure pain thresholds (PPTs) of the facial and neck muscles were tested. Chi-square test, Mann-Whitney U test and multiple linear regression analysis were used to analyze the data. The factors in the multiple linear regression analysis were occupation, working age, and gender. RESULTS: The prevalence rate of neck pain was significantly higher in dentists (73.0%) compared with the controls (52.0%) (P = .002). The regression models of cervical range of posterior extension, lateral flexion and rotation were statistically significant (P ≤ .001). The regression models of PPTs of the tested facial and neck muscles were statistically significant (P < .001). CONCLUSION: Dentists are at higher risk of neck pain. The bigger cervical range of left rotation of dentists could be related to the working posture. The lower PPTs in dentists may reflect a hypersensitivity in the facial and neck muscles. Preventive measures are needed to reduce occupational hazards in dentists.

Effect of photobiomodulation therapy on painful temporomandibular disorders.

To evaluate the effect of photobiomodulation therapy (PBMT) on painful temporomandibular disorders (TMD) patients in a randomized, double-blinded, placebo-controlled manner. Participants were divided into a masseter myalgia group (n = 88) and a temporomandibular joint (TMJ) arthralgia group (n = 87) according to the Diagnostic Criteria for Temporomandibular Disorders (DC/TMD). Both groups randomly received PBMT or placebo treatment once a day for 7 consecutive days, one session. The PBMT was applied with a gallium-aluminum-arsenide (GaAlAs) laser (wavelength = 810 nm) at pre-determined points in the masseter muscle (6 J/cm2, 3 regions, 60 s) or TMJ region (6 J/cm2, 5 points, 30 s) according to their most painful site. Pain intensity was rated on a 0-10 numerical rating scale (NRS) and pressure pain thresholds (PPT) and mechanical sensitivity mapping were recorded before and after the treatment on day 1 and day 7. Jaw function was assessed by pain free jaw opening, maximum unassisted jaw opening, maximum assisted jaw opening, maximum protrusion and right and left excursion. Data were analyzed with a mixed model analysis of variance (ANOVA). Pain intensity in arthralgia patients decreased over time (P < 0.001) for both types of interventions, however, PBMT caused greater reduction in pain scores than placebo (P = 0.014). For myalgia patients, pain intensity decreased over time (P < 0.001) but without difference between interventions (P = 0.074). PPTs increased in both myalgia (P < 0.001) and TMJ arthralgia patients over time (P < 0.001) but without difference between interventions (P ≥ 0.614). Overall, PBMT was associated with marginally better improvements in range of motion compared to placebo in both myalgia and arthralgia patients. Pain intensity, sensory function and jaw movements improve after both PBMT and placebo treatments in myalgia and arthralgia patients indicating a substantial non-specific effect of PBMT.

A facile and sensitive electrochemical sensor for non-enzymatic glucose detection based on three-dimensional flexible polyurethane sponge decorated with nickel hydroxide.

A novel three-dimensional nickel hydroxide/polyurethane (Ni(OH)2/PU) electrode was prepared by a simple and environmentally friendly method and used for non-enzymatic detection of glucose. The Ni(OH)2/PU electrode was obtained by one-pot hydrothermal method of loading nickel hydroxide on a cheap, easily available and flexible polyurethane sponge, which is facile and energy-saving. The porous structure of the polyurethane sponge provides a large surface area and a rich electrochemical active site for the electrode, which is beneficial to the oxidation reaction of glucose on the surface of the electrode with Ni(OH)2. The Ni(OH)2/PU electrode structure was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The cyclic voltammetry test was used to study the catalytic performance of Ni(OH)2/PU electrode for oxidation of glucose and the chronoamperometry was used to investigate the detection performance of Ni(OH)2/PU electrode on glucose. The results indicate that this non-enzymatic glucose sensor had a high sensitivity of 2845 µA mM-1 cm-2, a low detection limit of 0.32 µM (S/N = 3), a detection range of 0.01-2.06 mM and response time of less than 5 s. In addition, the Ni(OH)2/PU electrode had excellent selectivity, reproducibility and stability and also exhibited effective detection of glucose in fetal bovine serum (FBS). In summary, Ni(OH)2/PU electrode had broad prospects as an excellent candidate for non-enzymatic glucose sensors. The study also opens up a facile and energy-saving approach for preparing three-dimensional (3D) functionalized polymer electrode via hydrothermal method as electrochemical sensors.

"Turn-on" ratiometric electrochemical detection of H2O2 in one drop of whole blood sample via a novel microelectrode sensor.

Oxidative stress plays an important role in the pathogenesis of many diseases, while the exact mechanism that hydrogen peroxide (H2O2) as one of the most abundant reactive oxygen species (ROS) exerts its influence on oxidative stress remains unclear. We developed a novel turn-on ratiometric electrochemical sensor for the detection of H2O2 in blood samples. The electrochemical probe 5-(1,2-dithiolan-3-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pent-anamide (BA) was designed and synthesized for the selective detection of H2O2 via a one-step amide reaction. Meanwhile, Nile Blue A (NB) was optimized as an internal reference molecule, thus enabling accurate quantification of H2O2 in a complex environment. BA and NB were then co-assembled onto a carbon fiber microelectrode (CFME) coated with Au cones. The oxidation peak current ratio between BA and NB demonstrated good linearity with the logarithm of the H2O2 concentration values ranging from 0.5 µM to 400 µM with a low detection limit of 0.02 µM. The developed sensor showed remarkable selectivity against potential interferences in whole blood samples, especially for ascorbic acid, uric acid, and dopamine. In combination with the unique characteristics of CFME, such as a small size and good biocompatibility, the microsensor was used for rapid analysis of one drop of whole blood sample. This sensor not only creates a new platform for the detection of H2O2 in whole blood samples, but also provides a new design strategy of other ROS analysis for early diagnosis of ROS-related diseases, drug discovery processes, and pathological mechanisms.

Effect of attractive polymer-pore interactions on translocation dynamics.

The effect of attractive polymer-pore interaction on the translocation of polymer chain through a nanopore under electric field is studied by using dynamical Monte Carlo method. The translocation dynamics is remarkably influenced by the interaction. The translocation time for chain moving through nanopore is strongly dependent on the interaction. It reaches minimum at a moderate interaction which is found to be roughly independent of electric field as well as chain length. At weak interaction region, chain spends long time to overcome the barrier of the pore entrance, i.e., the chain is trapped at the entrance. While at strong interaction region, chain is difficult to leave the nanopore, that is, the chain is trapped at the exit of nanopore. The phenomenon is discussed from the view of free energy landscape.