Thermosensitive P(AAc-co-NIPAm) Hydrogels Display Enhanced Toughness and Self-Healing via Ion-Ligand Interactions.

Hydrogels containing thermosensitive polymers such as poly(N-isopropylacrylamide) (P(NIPAm)) may contract during heating and show great promise in fields ranging from soft robotics to thermosensitive biosensors. However, these gels often exhibit low stiffness, tensile strength, and mechanical toughness, limiting their applicability. Through copolymerization of P(NIPAm) with poly(Acrylic acid) (P(AAc)) and introduction of ferric ions (Fe3+ ) that coordinate with functional groups along the P(AAc) chains, here a thermoresponsive hydrogel with enhanced mechanical extensibility, strength, and toughness is introduced. Using both experimentation and constitutive modeling, it is found that increasing the ratio of m(AAc):m(NIPAm) in the prepolymer decreases strength and toughness but improves extensibility. In contrast, increasing Fe3+ concentration generally improves strength and toughness with little decrease in extensibility. Due to reversible coordination of the Fe3+ bonds, these gels display excellent recovery of mechanical strength during cyclic loading and self-healing ability. While thermosensitive contraction imbued by the underlying P(NIPAm) decreases slightly with increased Fe3+ concentration, the temperature transition range is widened and shifted upward toward that of human body temperature (between 30 and 40 °C), perhaps rendering these gels suitable as in vivo biosensors. Finally, these gels display excellent adsorptive properties with a variety of materials, rendering them possible candidates in adhesive applications.

Synthesis and Photodynamic Activity of Peri-xanthenoxanthene Derivatives.

Photodynamic therapy (PDT) is a modern cancer therapy. But it is still difficult to obtain ideal photosensitizers. We synthesized six new peri-xanthenoxanthene derivatives rapidly and efficiently using solid-phase carbon-bath microwave irradiation technology, and investigated their in vitro photodynamic antitumor activity with 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Our results showed that all compounds exhibited extremely low dark cytotoxicity and good phototoxicity against four human cancer cell lines. In particular, compound 3c showed the best in vitro PDT activity against Hela cells and Bel-7402 cells with IC50 values of 91 and 74 nmol/L, respectively. Its value of 1-octanol/water partition coefficient (log Kow) was 0.5309, suggesting that it is a promising photosensitizer for PDT due to its low dark cytotoxicity, high phototoxicity, and potential water solubility.

Design, synthesis and biological evaluation of hydroxy- or methoxy-substituted 5-benzylidene(thio) barbiturates as novel tyrosinase inhibitors.

Here a new class of hydroxy- or methoxy-substituted 5-benzylidene(thio)barbiturates were designed, synthesized and their inhibitory effects on the diphenolase activity of mushroom tyrosinase were evaluated. The results showed that several compounds had more potent tyrosinase inhibitory activities than the widely used tyrosinase inhibitor kojic acid (IC50=18.25µM). In particular, 3',4'-dihydroxylated 1e was found to be the most potent inhibitor with IC50 value of 1.52µM. The inhibition mechanism analysis revealed that the potential compounds 1e and 2e exhibited such inhibitory effects on tyrosinase by acting as the irreversible inhibitors. Structure-activity relationships' (SARs) analysis also suggested that further development of such compounds might be of interest.

Nonlinear dynamic separation characteristics of friction pair and experimental analysis.

This paper aims to reduce friction pair erosion of the clutch in the case of continuous shift; the dynamic separation process of the friction pair is investigated. The temperature of the friction pair, friction torque, and separation speed in the separation process are taken as the research objects, and the dynamics simulation model and finite element thermal coupling simulation model of the clutch separation process are established. The nonlinear dynamic separation characteristics of the friction pair are investigated by comparing and analyzing the effects of control parameters such as rotational speed difference, damping ratio, and lubricant viscosity on the friction torque, friction pair separation speed, separation gap, and contact stress during the separation process. The gap recovery coefficient is proposed as a response indicator for observing the separation process in response to the inability to observe the nonlinear dynamic motion of the friction pair during the separation process and to measure the end time of the separation. Finally, the clutch was subjected to a separation test. The results show that the proposed gap recovery coefficient accurately describes the separation process. The simulation model can simulate the clutch's separation and predict the trend of separation parameters.

Kinematic Behavior of an Untethered, Small-Scale Hydrogel-Based Soft Robot in Response to Magneto-Thermal Stimuli.

Fruit fly larvae, which exist widely in nature, achieve peristaltic motion via the contraction and elongation of their bodies and the asymmetric friction generated by the front and rear parts of their bodies when they are in contact with the ground. Herein, we report the development of an untethered, magnetic, temperature-sensitive hydrogel-based soft robot that mimics the asymmetric micro-patterns of fruit-fly-larvae gastropods and utilizes cyclic deformation to achieve directional peristaltic locomotion. Due to Néel relaxation losses of nanomagnetic Fe3O4 particles, the hydrogel-based soft robot is capable of converting changes in external alternating magnetic stimuli into contracting and expanding deformation responses which can be remotely controlled via a high-frequency alternating magnetic field (AMF) to realize periodic actuation. Furthermore, the Fe3O4 particles included in the hydrogel-based soft robot cause it to follow a gradient magnetic field in confined liquid environments and can be coupled with AMFs for the targeted release of water-soluble drugs or targeted magnetic hyperthermia therapy (MHT). We believe that such a controlled motion can enable highly targeted drug delivery, as well as vascular disease detection and thrombus removal tasks, without the use of invasive procedures.

Nonlinear Viscoelasticity and Toughening Mechanisms in Nanoclay-PNIPAAm Double Network Hydrogels.

We investigate the mechanical properties of a magnetic temperature-sensitive hydrogel at varying concentrations of covalent and physical cross-linking. The hydrogel consists of covalently cross-linked poly(N-isopropylacrylamide) (PNIPAAm), physically interacting nanoclay particles, and magnetic ferric oxide nanoparticles. The physical nanoclay network exhibits strong viscoplastic behavior, and we find that increasing nanoclay content improves both strength and toughness in the double network materials. We investigate the behavior of the gels using a nonlinear viscoplasticity model with a modified rule of mixtures approach and attribute the observed trends to two factors: (a) the yield-stress behavior of the nanoclay network and (b) load-sharing interactions between the PNIPAAm and the nanoclay. Our findings indicate a strong correlation between the mass ratio of covalent cross-linker used and fractional percolation of the PNIPAAm network.

Locomotion of an untethered, worm-inspired soft robot driven by a shape-memory alloy skeleton.

Soft, worm-like robots show promise in complex and constrained environments due to their robust, yet simple movement patterns. Although many such robots have been developed, they either rely on tethered power supplies and complex designs or cannot move external loads. To address these issues, we here introduce a novel, maggot-inspired, magnetically driven "mag-bot" that utilizes shape memory alloy-induced, thermoresponsive actuation and surface pattern-induced anisotropic friction to achieve locomotion inspired by fly larvae. This simple, untethered design can carry cargo that weighs up to three times its own weight with only a 17% reduction in speed over unloaded conditions thereby demonstrating, for the first time, how soft, untethered robots may be used to carry loads in controlled environments. Given their small scale and low cost, we expect that these mag-bots may be used in remote, confined spaces for small objects handling or as components in more complex designs.

Clinical evaluation of volume of interest imaging combined with metal artifact reduction reconstruction techniques in coiling and stent assisted coiling during neurointerventional procedures.

PURPOSE: Three-dimensional (3D) scans with flat detector angiographic systems are widely used for neurointerventions by providing detailed vascular information. However, its associated radiation dose and streak metal artifact generated by implanted treatment devices remain issues. This work evaluates the feasibility and clinical value of volume of interest imaging combined with metal artifact reduction (VOI+MAR) to generate high quality 3D images with reduced radiation dose and metal artifacts. MATERIAL AND METHODS: Full volume (FV) and VOI scans were acquired in 25 patients with intracranial aneurysms and treated with either endovascular coiling (n=9) or stent assisted coiling (n=16) procedures. FV and VOI scans were reconstructed with conventional syngo DynaCT and VOI +MAR prototype software, respectively. RESULTS: Quantitative evaluation results demonstrated that compared with standard FV syngo DynaCT images, overall image quality was improved in the VOI+MAR reconstructed images, with streak metal artifacts considerably reduced or even removed; details of soft tissue in the vicinity of the metal devices was well preserved or recovered in the majority of cases. Radiation dose to patients calculated by dose area product was found to be significantly reduced using VOI scans. CONCLUSION: This study confirmed the feasibility of using VOI+MAR prototype software to achieve high image quality of a small volume of clinical interest and to reduce radiation dose. This technique has potential to improve patient safety and treatment outcomes.

Nur77 promotes cerebral ischemia-reperfusion injury via activating INF2-mediated mitochondrial fragmentation.

Mitochondrial fragmentation drastically regulates mitochondrial homeostasis in brain illness. However, the role of mitochondrial fragmentation in cerebral ischemia-reperfusion (IR) injury remains unclear. Nur77, a regulator of mitochondrial homeostasis, is associated with heart and liver IR injury, but its effects on mitochondrial function in cerebral IR injury has not been studied intensively. The aim of our study is to explore whether cerebral IR injury is modulated by Nur77 via modification of mitochondrial homeostasis. Our results indicated that Nur77 was upregulated in reperfused brain tissues. Genetic ablation of Nur77 reduced infarction area and promoted neuron survival under IR burden. Biochemical analysis demonstrated that Nur77 deletion protected mitochondrial function, attenuated mitochondrial oxidative stress, preserved mitochondrial potential, and blocked mitochondria-related cell apoptosis. In addition, we illustrated that Nur77 mediated mitochondrial damage via evoking mitochondrial fragmentation that occurred through increased mitochondrial fission and decreased fusion. Besides, our results also demonstrated that Nur77 controlled mitochondrial fragmentation via upregulating INF2 in a manner dependent on the Wnt/ß-catenin pathway; inhibition of the Wnt pathway abrogated the protective effect of Nur77 deletion on reperfused-mediated neurons. Altogether, our study highlights that the pathogenesis of cerebral IR injury is associated with Nur77 activation followed by augmented mitochondrial fragmentation via an abnormal Wnt/ß-catenin/INF2 pathway. Accordingly, Nur77-dependent mitochondrial fragmentation and the Wnt/ß-catenin/INF2 axis may represent novel therapeutic targets to reduce cerebral IR injury.

Optical behaviors of conjugated-chain compounds containing benzene and furan units.

Thirteen conjugated-chain compounds which contain benzene and furan units were prepared, their optical behaviors, including UV-vis absorption coefficient (epsilon), absorption wavelengths (lambdaa), fluorescence emission wavelengths (lambdae), and quantum yields (Phi) were measured. Meanwhile, their LUMO and HOMO energy were determined by cyclic voltammetry and their second-order polarizations (betaxxx) values were determined by solvatochromic method, respectively. The results showed that this kind of compounds possess a shorter lambdaa (320-365 nm) and performance a higher Phi values, especially for 2aa, 2ab, 2ac and 2bb, their Phi values are all more than 90%. These compounds, except 2db, showed a higher betaxxx values in DMSO, especially for 2dc (75.77x10(-30) m5 C-1) and 2dd (83.32x10(-30) m5 C-1), than that 10-methyl-acridone (6.578x10(-30) m5 C-1) or 10-benzylacridone (6.845x10(-30) m5 C-1) in DMSO did, and second harmonic generation value of 10-methylacridone and 10-benzylacridone in powder are, respectively, 1.381 and 1.861 times of that value of urea. The betaxxx values and Phi values determined for these compounds in this work were lower than these values which were desired in the original work, this phenomena was explained from their molecular structures. This work confirmed that as these compounds performance shorter lambdaa and higher Phi values, they could be good blue-color optical materials for some fields, such as OLED materials, two-photo absorption materials, fluorescent dyes.

Three-dimensional image fusion of CTA and angiography for real-time guidance during neurointerventional procedures.

AIM: To evaluate the accuracy of three-dimensional (3D) images from two modalities-CT angiography (CTA) and digital subtraction angiography (DSA). Additionally, to explore the value of using preprocedural CTA for real-time guidance during neurointerventional procedures. MATERIALS AND METHODS: 25 patients with CTA-confirmed cerebral arterial lesions were enrolled. For 12 of these patients, 3D DSA images of the contrast medium-enhanced target vessel were acquired during the intervention and registered with the preprocedurally acquired CTA images for evaluation of the accuracy of image fusion, focusing on the target vessel and the lesion. For the other 13 patients, a low-dose non-contrast 3D angiographic scan was performed. The preprocedurally acquired CTA image was then registered with the coordinate of angiography and overlaid onto the live fluoroscopic image to provide interventional guidance. RESULTS: Based on visual inspection by two experienced physicians and quantitative evaluation, excellent accuracy in the 3D registration of the CTA and DSA was achieved for all 12 patients examined. Additionally, CTA could be used successfully to guide the interventional procedures, including both diagnostic DSA and stent treatment. The radiation dose and contrast medium use were compared with those used by conventional interventional procedures and both were found to be significantly reduced. CONCLUSIONS: 3D CTA and angiographic image fusion was approved as highly accurate for neurovasculature. Additionally, using the fusion technique to guide interventional procedures enhanced the workflow, and required much less radiation exposure and contrast medium use, thus helping to reduce potential risks and increase treatment safety.

LED based on alternating benzene-furan oligomers.

A series of conjugated-chain compounds which contain two furan units and more than three other aromatic ring units were synthesized by two different methods, their UV-visible absorption coefficient (ε), maximum absorption wavelengths (λa), fluorescence emission wavelengths (λe), stokes shift and quantum yields (Φ) were determined, the relationships between the molecular structures and the effects of spectral behaviors were discussed. Meanwhile, the excitation spectrum and emission spectrum of 2b and 2d in solid and in ethyl acetate were respectively recorded, the thermal stability of 2b and 2d was evaluated, and the fluorescence emission behaviors of two light emitting diodes, fabricated with 2b and 2d as phosphors, were investigated. The results showed that most of target compounds can perform high fluorescence emission ability, compounds 2b and 2d can perform higher thermal stability under 350°C and they are suitable for making light emitting diode as phosphors, the light emitting diodes fabricated with 2b and 2d can show higher fluorescence emission ability. Therefore, those compounds are worthy of further being developed as fluorescent emission materials.

CBCT-based 3D MRA and angiographic image fusion and MRA image navigation for neuro interventions.

Digital subtracted angiography (DSA) remains the gold standard for diagnosis of cerebral vascular diseases and provides intraprocedural guidance. This practice involves extensive usage of x-ray and iodinated contrast medium, which can induce side effects. In this study, we examined the accuracy of 3-dimensional (3D) registration of magnetic resonance angiography (MRA) and DSA imaging for cerebral vessels, and tested the feasibility of using preprocedural MRA for real-time guidance during endovascular procedures.Twenty-three patients with suspected intracranial arterial lesions were enrolled. The contrast medium-enhanced 3D DSA of target vessels were acquired in 19 patients during endovascular procedures, and the images were registered with preprocedural MRA for fusion accuracy evaluation. Low-dose noncontrasted 3D angiography of the skull was performed in the other 4 patients, and registered with the MRA. The MRA was overlaid afterwards with 2D live fluoroscopy to guide endovascular procedures.The 3D registration of the MRA and angiography demonstrated a high accuracy for vessel lesion visualization in all 19 patients examined. Moreover, MRA of the intracranial vessels, registered to the noncontrasted 3D angiography in the 4 patients, provided real-time 3D roadmap to successfully guide the endovascular procedures. Radiation dose to patients and contrast medium usage were shown to be significantly reduced.Three-dimensional MRA and angiography fusion can accurately generate cerebral vasculature images to guide endovascular procedures. The use of the fusion technology could enhance clinical workflow while minimizing contrast medium usage and radiation dose, and hence lowering procedure risks and increasing treatment safety.

Synthesis and optical behaviors of 2-(9-phenanthrenyl)-, 2-(9-anthryl)-, and 2-(1-pyrenyl)-1-alkylimidazole homologues.

Eight 2-(9-phenanthrenyl)-, 2-(9-anthryl)- and 2-(1-pyrenyl)-1-alkyl-benzimidazole compounds, three 2-(9-anthryl)-1-alkylphenanthroimidazole compounds and five 4,5-diphenyl-1-alkyl-2-(9-anthryl)imidazole compounds were synthesized by alkylation reactions of the corresponding benzimidazole, phenanthroimidazole or imidazole compounds. 2-(10-Bromo-9-anthryl)-1-alkyl-benzimidazole compounds were prepared by bromination reaction of 2-(9-anthryl)-1-alkylbenzimidazole compounds. All the synthesized compounds were characterized by elemental analysis, (1)H NMR, (13)C NMR, MS or HRMS; their absorption coefficients (epsilon), maximum absorption lambda(amax), fluorescence emission maximum lambda(em), Stokes shifts and fluorescence quantum yields (Phi(F)) in ethyl acetate were determined; their fluorescent lifetimes (T(1) and T(2)) were measured in ethyl acetate and in solid state, respectively. The crystal structure of 2-(9-anthryl)-1-n-butyl-4,5-diphenylimidazole (12a) was determined to be triclinic, space group P-1 types, using single crystal X-ray crystallography technique. The results showed that these compounds exhibited moderate fluorescence-emission abilities and higher solubility in most organic solvents than their corresponding starting materials. The relationships between the optical behaviors and structures for these compounds were discussed.