Topographical transition of submicron pillar array of azo molecular glass induced by circularly polarized light.

The well-aligned submicron patterns on surfaces have attracted wide attention from scientific curiosity to practical applications. Understanding their formation and transition is highly desirable for efficient manufacture of the patterns for many usages. Here, we report a unique observation on self-organized topographical transition of submicron pillar array of an azo molecular glass, induced by irradiation with circularly polarized light. During gradual erasure of the patterns upon exposure to the light, which is a property of this material, a new set of pillars unexpectedly emerge with new one in middle of each triangle cell of the original array. The highly regular pillar array with triple area density is formed and finally stabilized in the process, as revealed by thorough investigation reported here. This unusual observation and its rationalization will be of benefit for deep understanding of the light-matter interaction and can be expected to be applied in different areas.

Praeruptorin A reduces metastasis of human hepatocellular carcinoma cells by targeting ERK/MMP1 signaling pathway.

Praeruptorin A (PA) is one of the active ingredients found in the dried root of Peucedanum praeruptorum Dunn, has been reported to possess anticancer effects against various types of cancer. However, the effect of PA on human hepatocellular carcinoma (HCC) remains uncleared. In this study, our results indicated that PA did not induce cytotoxicity or alter cell cycle distribution in human HCC cells (Huh-7, SK-Hep-1, and PLC/PRF/5 cells). Instead, PA inhibited the migration and invasion of human HCC cells while downregulating the expression of matrix metalloproteinase-1 (MMP1) and activating the extracellular signal-regulated kinase (ERK) signaling pathways. Furthermore, blocking the ERK signaling pathway through siERK restored the expression of MMP1 and the invasive ability of PA-treated HCC cells. In conclusion, our results demonstrate the antimetastatic activity of PA against human HCC cells, supporting its potential as a therapeutic agent of HCC treatments.

Mussel-like Surface Adhesion and Photoinduced Cooperative Deformation of Janus Particles.

This study focused on mussel-like surface adhesion and photoinduced cooperative deformation of a unique type of Janus particles (JPs), composed of an isosorbide-based molecular glass bearing push-pull type azo chromophore (IAC-4) and a 2,6-pyridinedicarboxamide-containing poly(dimethylsiloxane) oligomer (H2pdca-PDMS). The JPs were obtained by the solvent evaporation method in an aqueous medium with the dispersed phase of a solution of IAC-4 and H2pdca-PDMS in dichloromethane (DCM). The JP formation and its mechanism were investigated by electron microscopy, in situ optical microscopy, and theoretical analysis. The results showed that the Janus structures form through gradual segregation between the two components in the droplets induced by the evaporation of DCM, which follows the ternary phase diagrams calculated according to Flory-Huggins theory. In the following stage, the gradual coalescence of small domains in droplets is controlled by dynamic factors. After being deposited on a substrate, the JPs exhibit unidirectional adhesion with the H2pdca-PDMS parts spreading on the substrate, while the IAC-4 parts orientate away from the substrate. The mussel-like adhesion is caused by the interfacial interaction of H2pdca-PDMS with the hard surfaces (i.e., glass and silicon substrates) and its strong ability to spread and wet the surfaces to increase the contact area with the surfaces. Upon irradiation with linearly and circularly polarized laser beams at 488 nm, respectively, a series of unique surface morphologies are observed because of the photoinduced deformation of the IAC-4 parts along the electric vibration direction of the polarized light and the cooperative deformation of the H2pdca-PDMS parts of the JPs. The cooperative deformation reveals the strong interfacial interaction and cohesiveness between the IAC-4 and the H2pdca-PDMS phases in JPs. No peeling-off from the substrate is observed after the large-scale deformation, which also indicates the strong adhesion of the JPs on the substrate surfaces. This study not only demonstrates the mussel-like adhesion and unique cooperative deformation behavior but also supplies new insights into the interfacial interaction in JPs as well as that with hard surfaces, thus opening a new avenue for surface modification and functionalization.

Exploring the Origin of Phase-Transformation Kinetics of CsPbI3 Perovskite Nanocrystals Based on Activation Energy Measurements.

Perovskite α-CsPbI3 nanocrystals (NCs) with a high fluorescence quantum yield (QY) typically undergo a rapid phase transformation to a low-QY δ-CsPbI3 phase, thus limiting their optoelectronic applications. In this study, organic molecule hexamethyldisilathiane (HMS) is used as a unique surfactant to greatly enhance the stability of the cubic phase of CsPbI3 NCs (HMS-CsPbI3) under ambient conditions. The reaction kinetics of the phase transformation of CsPbI3 NCs are systemically investigated through in situ photoluminescence (PL), X-ray diffraction, and transmission electron microscope (TEM) measurements under moisture. The activation energy of HMS-CsPbI3 NCs is found to be 14 times larger than that of CsPbI3 NCs capped by olyelamine (OLA-CsPbI3 NCs). According to density functional theory calculations, the bonding between HMS and CsPbI3 NCs is stronger than that between OLA and CsPbI3 NCs, preventing the subsequent phase transformation. Our study presents a clear pathway for achieving highly stable CsPbI3 NCs for future applications.

Tailoring Nanohole Plasmonic Resonance with Light-Responsive Azobenzene Compound.

Metal-based nanohole structures, featuring a continuous matrix and discrete voids, have seen a wide spectrum of practical applications, ranging from plasmonic sensing to extraordinary optical transmission. It would not be uncommon to pursue further enhancement of their optical tunability, and incorporation with other functional materials offers an intriguing lead. In this study, the first step involves colloidal lithography fabrication of gold-based, short-range ordered nanohole structures on a glass substrate with varying geometrical parameters. Plasmonic resonance in optical waveband is readily achieved from the coupling between bonding surface plasmons and nanohole lattices. Resonant features observed in transmission measurements could also be well reproduced both from numerical simulations as well as theoretical calculations based on the grating coupling mechanism. With the introduction of a thin layer of azobenzene compound by spin-coating comes the critical transformation that not only alters optical performances by impacting the surface environment but also bestows the structures with light responsiveness. After 488 nm of laser irradiation, it is observed that the structures underwent cross polarization conversion, which could be attributed to the photoalignment behavior from trans-cis isomerization within the azobenzene layer, yielding further optical tunability with the linearly polarized probe light compared to that in the preirradiated state. The tuning of plasmonic resonances through light stimuli paves a noncontacting path for achieving desired optical responses with potentially high spatial and temporal resolution. This work may serve as a fountainhead for future efforts on optically tailorable photonic devices associated with nanohole plasmonics.

Shaping monodispersed azo molecular glass microspheres using polarized light.

Azo molecular glass (IAC-4) microspheres with a monodispersed diameter over ten microns were fabricated by microfluidics and unique shape manipulation was achieved based on their fascinating photoinduced deformation behaviour. After irradiation with a polarized laser beam (λ = 488 nm), the IAC-4 microspheres were transformed into uniform mushroom-like particles, and their three-dimensional (3D) asymmetric shapes were precisely manipulated by adjusting the irradiation time and the polarization state of light. By observing the particle morphology in three orthogonal views (top view, front view and side view) by scanning electron microscopy (SEM), the photoinduced deformation behaviour of the ten-micron-sized particles was comprehensively revealed in the 3D space for the first time. It was observed that the photoinduced deformation asymmetrically occurred on the upper part of the microspheres due to the strong optical absorption of the azo chromophores. Besides, the deformation manner of the upper part was decided by the direction of the electric vibration of the refracted light. This work not only depicts a clear picture of the photoinduced deformation behaviour of the ten-micron-sized azo particles upon polarized light irradiation, but also provides a new method to controllably manipulate the particle shape from spheres to complex 3D architectures.

The rat groin flap model redesigned for evaluating treatment effects on ischemia-reperfusion injury.

BACKGROUND: Although there is a wide application of the rat extended groin flap (epigastric skin flap) in studying different clinical issues, inconsistency arises between studies because many parameters of the extended groin flap have not been well defined. MATERIALS AND METHODS: The flap is based on the superficial inferior epigastric vessels, which give into a lateral and a medial branch distally. Herein, three steps were taken to redesign this model: First, the ventral vascular anatomy was visualized through an imaging study to determine the flap borders. Second, different ischemic durations were induced on five groups of Lewis rats (n = 5 in each group) by clamping the femoral artery; group 1 (sham group) received no ischemic insult after elevation and was immediately repositioned, and groups 2, 3, 4, and 5 received 12-, 14-, 16-, and 18-hour ischemia, respectively. Percentage of necrosis area was measured after 5 days. Third, the redesigned groin flap model was tested with the ischemic postconditioning for validation. RESULTS: The flap borders were determined such that both branches of the superficial inferior epigastric vessels were always included to ensure blood supply consistency. As the 14-hour ischemia induced the least variation in necrotic area on rats, it was chosen for further studies. In addition, ischemic postconditioning after 14-hr ischemia resulted in significant reduction of necrosis in this model. CONCLUSIONS: We have redesigned the extended groin flap model with better-defined borders and consistent vascular anatomy. The ischemia duration was calibrated with predictable necrosis pattern and the practicality was demonstrated. With this model, precise assessment of treatment efficacies on ischemia-reperfusion injury could be achieved in future studies.

Janus and Strawberry-like Particles from Azo Molecular Glass and Polydimethylsiloxane Oligomer.

This study investigated Janus and strawberry-like particles composed of azo molecular glass and polydimethylsiloxane (PDMS) oligomer, focusing on controllable fabrication and formation mechanism of these unique structures and morphologies. Two materials, the azo molecular glass (IA-Chol) and PDMS oligomer (H2pdca-PDMS), were prepared for this purpose. The Janus and strawberry-like particles were obtained from the droplets of a dichloromethane (DCM) solution containing both IA-Chol and H2pdca-PDMS, dispersed in water and stabilized by poly(vinyl alcohol). Results show that the structured particles are formed through segregation between the two components induced by gradual evaporation of DCM from the droplets, which is controlled by adding ethylene glycol (EG) into the above dispersion. Without the addition of EG, Janus particles are formed through the full segregation of the two components in the droplets. On the other hand, with the existence of EG in the dispersion, strawberry-like particles instead of Janus particles are formed in the phase separation process. The diffusion of EG molecules from the dispersion medium into the droplets causes the PDMS phase deswelling in the interfacial area due to the poor solvent effect. Caused by the surface coagulation, the coalescence of the isolated IA-Chol domains is jammed in the shell region, which results in the formation of the strawberry-like particles. For the particles separated from the dispersion and dried, the PDMS oligomer phase of the Janus particles can adhere and spread on the substrate to form unique "particle-on-pad" morphology due to its low surface energy and swelling ability, while the strawberry-like particles exist as "standstill" objects on the substrates. Upon irradiation with a linearly polarized laser beam at 488 nm, the azo molecular glass parts in the particles are significantly deformed along the light polarization direction, which show unique and distinct morphologies for these two types of the particles.

The Impact of Surgical Experience on Major Intraoperative Aneurysm Rupture and Their Consequences on Outcome: A Multivariate Analysis of 538 Microsurgical Clipping Cases.

The incidence and associated mortality of major intraoperative rupture (MIOR) in intracranial aneurysm surgery is diverse. One possible reason is that many studies failed to consider and properly adjust the factor of surgical experience in the context. We conducted this study to clarify the role of surgical experience on MIOR and associated outcome. 538 consecutive intracranial aneurysm surgeries performed on 501 patients were enrolled in this study. Various potential predictors of MIOR were evaluated with stratified analysis and multivariate logistic regression. The impact of surgical experience and MIOR on outcome was further studied in a logistic regression model with adjustment of each other. The outcome was evaluated using the Glasgow Outcome Scale one year after the surgery. Surgical experience and preoperative Glasgow Coma Scale (GCS) were identified as independent predictors of MIOR. Experienced neurovascular surgeons encountered fewer cases of MIOR compared to novice neurosurgeons (MIOR, 18/225, 8.0% vs. 50/313, 16.0%, P = 0.009). Inexperience and MIOR were both associated with a worse outcome. Compared to experienced neurovascular surgeons, inexperienced neurosurgeons had a 1.90-fold risk of poor outcome. On the other hand, MIOR resulted in a 3.21-fold risk of unfavorable outcome compared to those without it. Those MIOR cases managed by experienced neurovascular surgeons had a better prognosis compared with those managed by inexperienced neurosurgeons (poor outcome, 4/18, 22% vs. 30/50, 60%, P = 0.013).

3D-assisted quantitative assessment of orbital volume using an open-source software platform in a Taiwanese population.

Orbital volume evaluation is an important part of pre-operative assessments in orbital trauma and congenital deformity patients. The availability of the affordable, open-source software, OsiriX, as a tool for preoperative planning increased the popularity of radiological assessments by the surgeon. A volume calculation method based on 3D volume rendering-assisted region-of-interest computation was used to determine the normal orbital volume in Taiwanese patients after reorientation to the Frankfurt plane. Method one utilized 3D points for intuitive orbital rim outlining. The mean normal orbital volume for left and right orbits was 24.3±1.51 ml and 24.7±1.17 ml in male and 21.0±1.21 ml and 21.1±1.30 ml in female subjects. Another method (method two) based on the bilateral orbital lateral rim was also used to calculate orbital volume and compared with method one. The mean normal orbital volume for left and right orbits was 19.0±1.68 ml and 19.1±1.45 ml in male and 16.0±1.01 ml and 16.1±0.92 ml in female subjects. The inter-rater reliability and intra-rater measurement accuracy between users for both methods was found to be acceptable for orbital volume calculations. 3D-assisted quantification of orbital volume is a feasible technique for orbital volume assessment. The normal orbital volume can be used as controls in cases of unilateral orbital reconstruction with a mean size discrepancy of less than 3.1±2.03% in females and 2.7±1.32% in males. The OsiriX software can be used reliably by the individual surgeon as a comprehensive preoperative planning and imaging tool for orbital volume measurement and computed tomography reorientation.

Nano-composite of poly(L-lactide) and halloysite nanotubes surface-grafted with L-lactide oligomer under microwave irradiation.

In order to improve the bonding between halloysite nanotubes (HNTs) and poly(L-lactide) (PLLA), and hence to increase the mechanical properties of HNTs/PLLA nano-composite, HNTs were surface-grafted with PLLA under microwave irradiation and then blended with PLLA matrix. The optimal conditions for grafting polymerization are: irradiation time of 30 min, microwave power of 30 W and reaction temperature of 130 degrees C. The structure and properties of the surface-grafted HNTs (g-HNTs) were characterized by Fourier transformation infrared (FTIR), thermal gravimetric analysis (TGA), X-ray diffraction (XRD) and dynamic light scattering (DLS). Nano-composites of g-HNTs/PLLA and non-grafted HNTs/PLLA were subsequently evaluated in terms of crystallinity, dispersion, interfacial interaction, mechanical performance and cytocompatibility by polarized optical microscopy (POM), field scanning electron microscope (FESM), tensile testing and cell culture experiment. Results show that the grafted PLLA chains on the surfaces of HNTs, as inter-tying molecules, played an important role in improving the adhesive strength between the nanotubes and the polymer matrix. The enhanced interaction among g-HNTs and PLLA matrix resulted in a better tensile strength and modulus compared to the pristine PLLA and HNTs/PLLA. Cell culture results indicated that g-HNTs promoted both adhesion and proliferation of M3T3 fibroblasts on the g-HNTs/PLLA composite film.