Experimental Investigation of Cavitation Bulk Nanobubbles Characteristics: Effects of pH and Surface-Active Agents.

Nanobubbles (NBs) have a widespread application in antimicrobial activity, wastewater treatment, and ecological restoration due to numerous peculiar characteristics, such as small diameter, long-term stability, and ability to produce hydroxyl radicals. Despite significant applications, only limited comprehensive investigations are available on the role of surfactants and pH in NBs characteristics. Therefore, this study examines the effects of different surfactants (i.e., anionic, cationic, and nonionic) and pH medium on bulk NB formation, diameter, concentration, bubble size distribution (BSD), ζ-potential, and stability. The effect of surfactant at concentrations above and below the critical micelle concentration was investigated. NBs were generated in deionized (DI) water using a piezoelectric transducer. The stability of NBs was assessed by tracking the variation in diameter and concentration over time. In a neutral medium, the diameter of NBs is smaller than in other surfactant or pH mediums. The diameter, concentration, BSD, and stability of NBs are strongly influenced by the ζ-potential rather than the solution medium. BSD curve shifts to a smaller bubble diameter when the magnitude of ζ-potential is high in any solution. In pure water, surfactant, and pH mediums, NBs have existed for a long time. NBs have a shorter life span in environments with a pH ≤ 3. Surfactant adsorption on the surface of NBs increases with increasing surfactant concentration up to a certain limit, beyond which it declines substantially. The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was used to interpret the NBs stability, resulting in a total potential energy barrier that is positive and greater than 45.55 kBT for 6 ≤ pH ≤ 11, whereas for pH < 6, the potential energy barrier essentially vanishes. Moreover, an effort has also been made to explicate the plausible prospect of ion distribution and its alignment surrounding NBs in cationic and anionic surfactants. This study will extend the in-depth investigation of NBs for industrial applications involving NBs.

A Review on Alternating Current Poling for Perovskite Relaxor-PbTiO3 Single Crystals.

With the great success on verifying its effectiveness on relaxor-PbTiO3 (PT) single crystals (SCs), alternating current poling (ACP) has been taking a center as a new domain engineering method in the last few years. Compared with the conventional direct current poling (DCP), ACP enables enhanced piezoelectric and dielectric properties. In this article, research progress in ACP and perspectives are introduced. Initially, optimized conditions of ACP for relaxor-PT SCs and unsolved issues on polycrystalline ceramics and spurious modes are reviewed. Second, the ferroelectric domain size dependence of piezoelectricity associated with ACP is discussed. We hypothesize that a tradeoff between domain and domain wall contributions exists for high piezoelectricity, suggesting an optimum 109° domain wall size, which is presumably dependent on compositions, crystallographic symmetries, and domain configurations. Finally, crystals synthesized by a solid-state crystal growth (SSCG) method are briefly introduced due to their unprecedented piezoelectricity obtained by ACP ( d33  âˆ¼ 5500 pC/N). We hope that this work helps to grasp the current status of ACP and to guide future tasks to be studied.

A Review of Lead Perovskite Piezoelectric Single Crystals and Their Medical Transducers Application.

Piezoelectric materials have been developed since early 1900s and many research had been conducted on the composition and process to obtain higher piezoelectric constants ( d33 ). Within composition research, lead perovskite relaxor piezoelectric single crystals (SCs) of Pb(Mg1/3Nb2/3)O3-lead titanate PbTiO3 type have been actively studied since 1990s because of their outstanding pC/N compared with those of the conventional Pb(Zr,Ti)O3 ceramics. A major driving force of these SC research has been promoted by mass production of ultrasound transducers and array probes for medical diagnostic systems since early 2000s. However, higher d33 material and process research for these ultrasound devices are almost saturated. In this review article, we present a brief overview of the history, current situation, and future perspective of piezoelectric SCs. The authors believe that the main research in the next century is high d33 SCs with a high composition uniformity and low-energy SC growth methods, such as solid-state SC growth, low-loss SC transducer manufacturing technique, and improved poling process. This is a big technical challenge for all the scientists; however, the relatively large market of medical ultrasound has been expanded year by year, and we hope that the community is motivated to solve such technical problems in the near future.

Effects of Starter Defect on Energy Release Rate of Three-Point End-Notch Flexure Tested Unidirectional Carbon Fiber Reinforced Polymer Composite.

The mechanics of damage and fracture process in unidirectional carbon fiber reinforced polymer (CFRP) composites subjected to shear loading (Mode II) were examined using the experimental method of the three-point end-notch flexure (3ENF) test. The CFRP composite consists of [0o]16 with an insert film in the middle plane for a starter defect. A 3ENF test sample with a span of 50 mm and interface delamination crack length of 12.5 mm was tested to yield the load vs. deformation response. A sudden load drop observed at maximum force value indicates the onset of delamination crack propagation. The results are used to extract the energy release rate, GIIC, of the laminates with an insert film starter defect. The effect of the starter defect on the magnitude of GIIC was examined using the CFRP composite sample with a Mode II delamination pre-crack. The higher magnitude of GIIC for the sample with insert film starter defect was attributed to the initial straight geometry of the notch/interface crack and the toughness of the resin at the notch front of the fabricated film insert. The fractured sample was examined using a micro-computerized tomography scanner to establish the shape of the internal delamination crack front. Results revealed that the interface delamination propagated in a non-uniform manner, leaving a curved-shaped crack profile.

One-pot synthesis of silane-modified hyaluronic acid hydrogels for effective antibacterial drug delivery via sol-gel stabilization.

A silane-modified hyaluronic acid (HA) hydrogel was prepared using a facile one-pot method with 3-glycidyloxypropyl-trimethoxysilane (GPTMS). The sol-gel route, specifically the self-condensation of the silane, was combined with the HA hydrogel system to modify its network structure. Nuclear magnetic resonance (NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the chemical functionalization of GPTMS. The morphological, rheological properties, and enzymatic degradation of the hydrogels were also evaluated. The sol-gel-stabilized HA hydrogel exhibited superior mechanical properties and biochemical stability as well as excellent biocompatibility without triggering any negative biological effects. Furthermore, an efficient drug-loading strategy is suggested that uses sol-gel encapsulation without the need for any chemical reagents, resulting in sustained release characteristics. Vancomycin was used as a model drug, and enhanced efficacy was demonstrated in antibacterial tests. The proposed approach is expected to have great potential for biomedical applications, and our findings will provide insight into the structure-property relationship of hydrogels.

Precursor Phenomena of Barium Titanate Single Crystals Grown Using a Solid-State Single Crystal Growth Method Studied with Inelastic Brillouin Light Scattering and Birefringence Measurements.

The nature of precursor phenomena in the paraelectric phase of ferroelectrics is one of the main questions to be resolved from a fundamental point of view. Barium titanate (BaTiO3) is one of the most representative perovskite-structured ferroelectrics intensively studied until now. The pretransitional behavior of BaTiO3 single crystal grown using a solid-state crystal growth (SSCG) method was investigated for the first time and compared to previous results. There is no melting process in the SSCG method, thus the crystal grown using a SSCG method have inherent higher levels of impurity and defect concentrations, which is a good candidate for investigating the effect of crystal quality on the precursor phenomena. The acoustic, dielectric, and piezoelectric properties, as well as birefringence, of the SSCG-grown BaTiO3 were examined over a wide temperature range. Especially, the acoustic phonon behavior was investigated in terms of Brillouin spectroscopy, which is a complementary technique to Raman spectroscopy. The obtained precursor anomalies of the SSCG-grown BaTiO3 in the cubic phase were similar to those of other single crystals, in particular, of high-quality single crystal grown by top-seeded solution growth method. These results clearly indicate that the observed precursor phenomena are common and intrinsic effect irrespective of the crystal quality.

Facile strategy involving low-temperature chemical cross-linking to enhance the physical and biological properties of hyaluronic acid hydrogel.

Here, we present a novel strategy to fabricate hyaluronic acid (HA) hydrogels with excellent physical and biological properties. The cross-linking of HA hydrogel by butanediol diglycidyle ether (BDDE) was characterized under different reaction temperatures, and the resulting physical properties (i.e., the storage modulus and swelling ratio) were measured. The ratio between the cross-linking rate (a strengthening effect) and the hydrolysis rate (a weakening effect) was much greater with lower cross-linking temperatures after sufficient cross-linking time, resulting in a noticeably higher storage modulus. As the cross-linking temperature decreased, the formed HA hydrogel structure became denser with smaller pores. Moreover, the introduction of low-temperature HA cross-linking strategy also resulted in an enhanced several important characteristics of HA hydrogels including its enzymatic resistivity and its ability to elicit a cellular response. These results indicate the performance of HA hydrogels can be markedly enhanced without further additives or modifications, which is expected to contribute to the advancement of applications of HA hydrogels in all industrial fields.

Enhancement of bio-stability and mechanical properties of hyaluronic acid hydrogels by tannic acid treatment.

Hyaluronic acid (HA) has been widely investigated because of its excellent biocompatibility and its ability to form hydrogels with various chemical modifications. However, HA hydrogels undergo rapid degradation and exhibit poor mechanical stability under physiological conditions. Tannic acid (TA), a naturally occurring polyphenol found in plants and fruits, has recently attracted interest as a crosslinking agent because of its abundant hydroxyl groups. In this study, we prepared HA hydrogels chemically crosslinked by polyethylene glycol diglycidyl ether (PEGDE) and treated with TA in an attempt to enhance the physical properties of HA hydrogels. TA acts as a physical crosslinker owing to the strong hydrogen bonding between TA and PEGDE, resulting in improved mechanical properties that support both cell attachment and proliferation without any sign of cytotoxicity. The enzymatic stability of the HA-TA hydrogels was significantly enhanced with the addition of TA, which was attributed to the hyaluronidase inhibition activity of TA. Additionally, the antioxidant potential of TA resulted in good resistance to degradation by reactive oxygen species, which can be generated in human tissues.

BOIMPY: Fluorescent Boron Complexes with Tunable and Environment-Responsive Light-Emitting Properties.

A series of air-stable boron complexes 1-5 were prepared by using N-aryl iminopyrrolide ligands. Designed as minimalist structural mimics of the privileged BODIPY motif, these new BOIMPY (BOron complexes of IMinoPYrrolide ligands) fluorophores feature low molecular symmetry that promotes emission from CT-type excited states with large Stokes shifts and little self-quenching. Through comparative studies on the homologous set of compounds 1-4, we have confirmed that a delicate interplay between conformational twisting and donor-acceptor interaction dictates the mechanism of de-excitation, which responds sensitively to solvent polarity as well as protonation states. Over a wide visible spectral range, the structure-dependent light-emitting properties of BOIMPY molecules are well manifested, even in the solid-state. In order to exploit the environment-sensitive nature of CT-type emission, the BOIMPY motif was elaborated further into a bioprobe molecule 5. Live-cell fluorescence imaging studies have established that 5 is localized exclusively at lipid droplets to produce well-resolved staining patterns without affecting cell viability. These findings promise future elaboration of BOIMPY-based functional molecules for applications in biological imaging, chemical sensing, and molecular switching.

Multichromophoric π-Conjugation: Modular Design for Gated and Cascade Energy Transfer.

Multichromophore arrays allow for cascade energy transfer. As an isoelectronic analogue of indacenyl, bis(triazolo)benzene features a fused tricyclic skeleton that rigidly places two π-extended triazoles in close proximity. Such triazole-based fluorophores behave as electronically independent modules in the ground states, but become tightly coupled upon photoexcitation for highly efficient excitation energy transfer (EET) that can be gated by external stimuli. Taking this donor-acceptor fluorophore system a step further, we have designed and implemented a cascade EET. Here, the initial excitation takes part in a circular relay to arrive at the longest-wavelength emitting site as the final destination. Modularly constructed triazoloarenes should serve as versatile platforms for chemically controlled optical signaling.

Self-Growth of Centimeter-Scale Single Crystals by Normal Sintering Process in Modified Potassium Sodium Niobate Ceramics.

In this manuscript, an interesting phenomenon is reported. That is the self-growth of single crystals in Pb-free piezoelectric ceramics. These crystals are several centimeters in size. They are grown without any seed addition through a normal sintering process in modified potassium sodium niobate ceramics. It has been achieved by the composition designed to compensate the Na(+) loss which occurs during the liquid phase sintering. The composition of the crystals is (K0.4925Na(0.4925-x)Ba(0.015+x/2))Nb(0.995+x)O3 [x is determined by the Na(+) loss, due to Na2O volatilization]. These crystals have high piezoelectric voltage coefficients (g33, 131 10(-3)Vm/N), indicating that they are good candidates for piezoelectric sensors and energy harvesting devices. We hope that this report can offer the opportunity for many researchers to have an interest in these crystals.

Ultrasensitive electrochemical detection of engrailed-2 based on homeodomain-specific DNA probe recognition for the diagnosis of prostate cancer.

It is well known that the engrailed-2 (EN2) protein, a biomarker for prostate cancer, strongly binds to a specific DNA sequence (5'-TAATTA-3') to regulate transcription. Based on this intrinsic property, DNA probes with additional flanked sequences were designed and optimized. Various measurements, such as electrophoresis mobility shift assay, surface plasmon resonance, and quantitative fluorescence assay were performed to investigate the feasibility of the DNA probes. Then, the affinities of the DNA probes to the target protein were quantitatively determined using FAM-modified DNA probes and magnetic beads, resulting in dissociation constants ranging from 61.03 to 98.84nM. To develop an early diagnosis platform for prostate cancer, an ultrasensitive electrochemical biosensor based on the electrodeposition of gold nanoparticles was designed. The EN2 protein was quantitatively detected using the electrochemical biosensor, and the calculated detection limit was found to be 5.62fM. Finally, the specificity and applicability of the biosensor were verified using several proteins and an artificial urine medium. The impedance signals increased in the cases of EN2, suggesting that the system exhibited high selectivity to only EN2.

CKD-516 displays vascular disrupting properties and enhances anti-tumor activity in combination with chemotherapy in a murine tumor model.

PURPOSE: CKD-516 is a benzophenone analog in which the B ring is modified by replacement with a carbonyl group. The study assessed CKD-516 as a vascular disrupting agent or anti-cancer drug. METHODS: To assess the effect of S516 on vascularization, we analyzed the effect on human umbilical vein endothelial cells (HUVECs). To determine the inhibition of cell proliferation of S516, we used H460 lung carcinoma cells. The alteration of microtubules was analyzed using immunoblot, RT-PCR and confocal imaging. To evaluate the anti-tumor effects of gemcitabine and/or CKD-516, H460 xenograft mice were treated with CKD-516 (2.5 mg/kg) and/or gemcitabine (40 mg/kg), and tumor growth was compared with vehicle-treated control. For histologic analysis, liver, spleen and tumor tissues from H460 xenograft mice were obtained 12 and 24 h after CKD-516 injection. RESULTS: Cytoskeletal changes of HUVECs treated with 10 nM S516 were assessed by immunoblot and confocal imaging. S516 disrupted tubulin assembly and resulted in microtubule dysfunction, which induced cell cycle arrest (G2/M). S516 markedly enhanced the depolymerization of microtubules, perhaps due to the vascular disrupting properties of S516. Interestingly, S516 decreased the amount of total tubulin protein in HUVECs. Especially, S516 decreased mRNA expression α-tubulin (HUVECs only) and ß-tubulin (HUVECs and H460 cells) at an early time point (4 h). Immunocytochemical analysis showed that S516 changed the cellular microtubule network and inhibited the formation of polymerized microtubules. Extensive central necrosis of tumors was evident by 12 h after treatment with CKD-516 (2.5 mg/kg, i.p.). In H460 xenografts, CKD-516 combined with gemcitabine significantly delayed tumor growth up to 57 % and 36 % as compared to control and gemcitabine alone, respectively. CONCLUSION: CKD-516 is a novel agent with vascular disrupting properties and enhances anti-tumor activity in combination with chemotherapy.

Lactobacillus plantarum HY7712 ameliorates cyclophosphamide-induced immunosuppression in mice.

Lactic acid bacteria (LAB) in fermented foods have attracted considerable attention recently as treatment options for immune diseases, the incidence of which has been increasing worldwide. The ability of 500 strains of LAB, isolated from kimchi, to induce TNF--α production in peritoneal macrophages was investigated. Lactobacillus plantarum HY7712 most strongly induced TNF--α production as well as NF-κB activation. However, HY7712 inhibited NF-κB activation in LPS-stimulated peritoneal macrophages. When HY7712 was orally treated in cyclophosphamide (CP)-immunosuppressed mice for 5 or 15 days, it reversed the body and spleen weights, blood RBC and WBC levels, and splenocyte and bone marrow cells that were reduced by CP. Orally administered HY7712 increased concanavalin A-induced T cell proliferation to 84.5% of the normal group on day 15, although treatment with CP alone markedly reduced it to 53.7% of the normal group. Furthermore, orally administered HY7712 significantly induced the expressions of IL-2 and IFN-γ in ConA-induced splenic cytotoxic T cells of CP-treated mice. Orally administered HY7712 restored the CP-impaired phagocytosis of macrophages in mice. Orally administered HY7712 also restored the cytotoxicity of NK and cytotoxic T cells derived from spleen and bone marrow against YAC-1 in CP-immunosuppressed mice. Based on these findings, orally administered HY7712 may accelerate the recovery of cyclophosphamide-caused immunosuppression, without evident side effects, by immunopotentiating NK and Tc cells, and may provide a mechanistic basis for using HY7712 as an alternative means in lessening chemotherapyinduced immunosuppression in cancer patients.

Arsenic Trioxide as a Vascular Disrupting Agent: Synergistic Effect with Irinotecan on Tumor Growth Delay in a CT26 Allograft Model.

The mechanism of action of arsenic trioxide (ATO) has been shown to be complex, influencing numerous signal transduction pathways and resulting in a vast range of cellular effects. Among these mechanisms of action, ATO has been shown to cause acute vascular shutdown and massive tumor necrosis in a murine solid tumor model like vascular disrupting agent (VDA). However, relatively little is understood about this VDA-like property and its potential utility in developing clinical regimens. We focused on this VDA-like action of ATO. On the basis of the endothelial cell cytotoxicity assay and tubulin polymerization assay, we observed that higher concentrations and longer treatment with ATO reduced the level of α- and ß-tubulin and inhibited the polymerization of tubulin. The antitumor action and quantitative tumor perfusion studies were carried out with locally advanced murine CT26 colon carcinoma grown in female BALB/c mice. A single injection of ATO intraperitoneally displayed central necrosis of the tumor tissue by 24 hours. T1-weighted dynamic contrast-enhanced magnetic resonance image revealed a significant decrease in tumor enhancement in the ATO-treated group. Similar to other VDAs, ATO treatment alone did not delay the progression of tumor growth; however, ATO treatment after injection of other cytotoxic agent (irinotecan) showed significant additive antitumor effect compared to control and irinotecan alone therapy. In summary, our data demonstrated that ATO acts as a VDA by means of microtubule depolymerization. It exhibits significant vascular shutdown activity in CT26 allograft model and enhances antitumor activity when used in combination with another cytotoxic chemotherapeutic agent.

KML001 displays vascular disrupting properties and irinotecan combined antitumor activities in a murine tumor model.

KML001 is sodium metaarsenite, and has shown cytotoxic activity in human tumor cell lines. The anti-cancer mechanism of KML001 involves cancer cell destruction due to DNA damage at the telomeres of cancer cell chromosomes. In this study, we assessed the vascular disrupting properties of KML001 and investigated whether KML001 as VDA is able to increase anti-tumor activity in irinotecan combined treatment. We used a murine model of the CT26 colon carcinoma cell line. CT26 isograft mice treated intraperitoneally with 10 mg/kg KML001 displayed extensive central necrosis of tumor by 24 h. The vascular disrupting effects of KML001 were assessed by dynamic contrast enhanced magnetic resonance imaging. Gadopentetic acid-diethylene triaminepentaacetic acid contrast enhancement was markedly decreased in KML001-treated mice one day after treatment, whereas persistently high signal enhancement was observed in mice injected with saline. Rate constant K(ep) value representing capillary permeability was significantly decreased (p<0.05) in mice treated with KML001. Cytoskeletal changes of human umbilical vein endothelial cells (HUVECs) treated with 10 uM KML001 were assessed by immune blotting and confocal imaging. KML001 degraded tubulin protein in HUVECs, which may be related to vascular disrupting properties of KML001. Finally, in the mouse CT26 isograft model, KML001 combined with irinotecan significantly delayed tumor growth as compared to control and irinotecan alone. These results suggest that KML001 is a novel vascular disrupting agent, which exhibits significant vascular shut-down activity and enhances anti-tumor activity in combination with chemotherapy. These data further suggest an avenue for effective combination therapy in treating solid tumors.

Three-stage binary switching of azoaromatic polybase.

An OFF-ON-OFF-type three-stage binary switching was realized with an azoaniline-based polybase 1. The optical properties of 1 and [1·2H](2+) are essentially indistinguishable to the naked eye but distinctively different from those of [1·H](+) to produce an unusual bell-shaped response as a function of protonation state; the underlying molecular mechanism was unraveled by a combination of experimental and DFT computational studies.

Polycaprolactone-starch blends with corn-based coupling agent: physical properties and in vitro analysis.

In an attempt to improve properties of polycaprolcatone-starch blend, this study uses zein as coupling agent in preparing the blend through a single-step process. Zein, which has affinity to both polar and non-polar groups, is expected to improve miscibility between the blends' constituents and its overall biocompatibility. Mechanical properties of the blend were tested and further characterizations (Fourier transform infrared spectroscopy, thermal properties) were performed to analyze the effect of zein as an addition to the blend's physical properties. The blend's biocompatibility was examined by indirect methods (contact angle and weight gain after immersion in simulated body fluid) and in vitro analysis. No significant effect on the blend's strength and stiffness was caused by adding zein. Hydrophilicity and cell affinity were improved when zein was added. Zein did not perform as a coupling agent that improved miscibility between polycaprolactone and starch, but its addition improved the blend's biocompatibility.

Reactivity-based detection of copper(II) ion in water: oxidative cyclization of azoaromatics as fluorescence turn-on signaling mechanism.

An oxidative cyclization reaction transforms nonemissive azoanilines into highly fluorescent benzotriazoles. We have found that introduction of multiple electron-donating amino groups onto a simple o-(phenylazo)aniline platform dramatically accelerates its conversion to the emissive polycyclic product. Notably, this chemistry can be effected by µM-level concentrations of copper(II) ion in water (pH = 6-8) at room temperature to elicit >80-fold enhancement in the green emission at λ(em) = 530 nm. Comparative kinetic and electrochemical studies on a series of structural analogues have established that the accelerated reaction rates correlate directly with a systematic cathodic shift in the oxidation onset potential of the azo precursors. In addition, single-crystal X-ray crystallographic analysis on the most reactive derivative revealed the presence of a five-membered ring intramolecular hydrogen-bonding network. An enhanced contribution of the quinoid-type resonance in such conformation apparently facilitates the mechanistically required proton transfer step, which, in conjunction with electron transfer at lower oxidation potential, contributes to a rapid cyclization reaction triggered by copper(II) ion in water.

Ratiometric detection of mercury ions in water: accelerated response kinetics of azo chromophores having ethynyl ligand tethers.

The metal-induced intramolecular cyclization reaction of an azo dye was exploited for the colorimetric detection of mercury ions in water. The molecular probe 3 responds selectively to nM-level Hg(II) ions in neutral aqueous solutions.