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.

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.

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.

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.

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.

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.

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.

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.

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.

Torsionally responsive C3-symmetric azo dyes: azo-hydrazone tautomerism, conformational switching, and application for chemical sensing.

An efficient triple azo coupling reaction between anilines and phloroglucinol furnished a series of C(3)-symmetric molecules 7-9 supporting multiple conjugation pathways that converge at the molecular core. A combination of (1)H/(13)C NMR spectroscopy, X-ray crystallography, and density functional theory computational studies provided a coherent picture of the [n,pi]-conjugated molecular core, which is best described as the tris(hydrazone) [rather than tris(azo)] tautomer stabilized by resonance-assisted hydrogen bonding. For a homologous series of compounds, an increase in the torsional angles between the planar molecular core and the peripheral aryl groups results in a systematic blue shift in the low-energy electronic transitions (7, 523 nm; 8, 505 nm; 9, 445 nm in CHCl(3)) that qualitatively correlates with the shrinkage of effective conjugation through structural distortion. Similar spectral shifts could also be induced by amine substrates that interact with the intramolecular hydrogen-bonding network to trigger bond-twisting motions. Specifically, a brief exposure of a thin film of 7 to vapor samples of butyl-, hexyl-, diethyl-, and diisopropylamine resulted in a rapid and reversible color change from pink to dark-orange. Under similar conditions, however, triethylamine did not elicit any detectable color change, despite the fact that it has a significantly higher vapor pressure than n-hexylamine. These findings implicate that the hydrogen-bonding donor ability is a key requirement for the binding-induced conformational switching, which allows for direct naked-eye detection of volatile amines under ambient conditions.

Nano- and microstructure fabrication by using a three-component system.

Two-component amphiphiles based on hydrogen-bonded complexes between terephthaloylbisalanine (H(2)TBA) and dodecylamine (DA) are able to self-assemble into nano- and microsized superstructures in an aqueous solvent. It is possible to modulate the morphology of these self-assembled superstructures by modifying the composition of the complexes, which can be achieved by changing the molar ratio of the two components or by changing the chirality of H(2)TBA. For example, right-handed microhelical ribbon structures were formed with L-TBA(1.0)DA(2.0), whereas in the case of rac-TBA(1.0)DA(2.0), flat ribbonlike structures were observed. Although L-TBA(1.0)DA(1.0) exhibited entangled fibrous structures, rac-TBA(1.0)DA(1.0) exhibited wire structures. Different ratios of H(2)TBA and DA were self-assembled into fiber-, wire-, and tubulelike superstructures, as well as monoclinic, columnar, and lamellar aggregation patterns. The self-assembled superstructures of TBA(x)DA(y) were significantly changed by adding metal ions. Transition metal (Cd(II), Co(II), and Zn(II)) complexes with L-TBA(x)DA(y) self-assembled into rod-, tubule-, wire-, and platelike superstructures. Metal-ion complexes with rac-TBA(x)DA(y) exhibited different superstructures. Our work suggests that it is possible to fabricate a wide variety of nano- and microsized superstructures by using two- and three-component amphiphiles.

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.

Effects of different depths of gap on healing of surgically created coronal defects around implants in dogs: a pilot study.

BACKGROUND: This study investigated the bone growth pattern in surgically created coronal defects with various depths around implants in dogs. METHODS: Four mongrel dogs were used. All mandibular premolars were extracted under general anesthesia and left to heal for 2 months. After ostectomy, bony defects were prepared in test sites, using a stepped drill with a diameter of 6.3 mm and two depths: 2.5 mm (test sites 1 [T1]) and 5.0 mm (test sites 2 [T2]). In the control sites, the implants were placed after ostectomy without any coronal defects. T1, T2, and control sites were prepared in the right and left sides of the mandible. Six implants, 3.3 mm in diameter and 10 mm in length, were placed in each dog; the implants were submerged completely. Two dogs were sacrificed 8 weeks after surgery, and the other two dogs were sacrificed 12 weeks after surgery. The stability of all implants was measured with a resonance frequency analyzer after placement and after sacrifice. All sites were block-dissected for ground sectioning and histologic examination. RESULTS: After 12 weeks of healing, only T2 were not filled fully with bone. At week 8, the mean bone-to-implant contact (BIC) was 47.7% for control, 43.6% for T1, and 22.2% for T2. At week 12, the control BIC was 56.7% and the 2.5-mm defect had a greater BIC (58.8%). However, in the 5-mm defect, the BIC was 35.1%. At insertion, stability was reduced at sites with a greater defect depth. Similar stability was noted in all specimens after 8 and 12 weeks of healing. CONCLUSION: Bone healing between an implant and marginal bone was compromised at sites with a deeper defect when the width of the bone defect was 1.5 mm.

The effect of several dentin desensitizers on shear bond strength of adhesive resin luting cement using self-etching primer.

OBJECTIVES: Dentin desensitizers can inhibit the bonding between dentin and resin cements. This study examined the effect of the previous application of desensitizers on the shear bond strength of one resin cement using self-etching primer to dentin. MATERIALS AND METHODS: One hundred and twenty-five dentin exposed teeth were randomly assigned to four experimental groups and one control group of 25 teeth each. Four dentin desensitizers were applied to the four experimental groups, respectively. The dentin desensitizers used were SuperSeal (Phoenix Dental, Inc., USA), MS-Coat (Sun Medical Co. Ltd, Japan), Gluma (Heraeus Kulzer, Germany), and Copalite Varnish (Cooley & Cooley Ltd, USA). Panavia F (Kuraray Co. Ltd, Tokyo, Japan) was attached to the top of each experimental and control group teeth using an Ultradent testing jig (Ultradent Product, Inc., Utah, USA), and the shear bond strength was measured using a Universal testing machine (Model 6022, Instron Co., Canton, MA, USA). The tooth surface was examined by scanning electron microscopy (SEM, JSM-T2000, JEOL, Tokyo, Japan). RESULTS: The control group showed the greatest shear bond strength (14.74 MPa) followed by SuperSeal (12.33 MPa), Gluma (5.28 MPa), MS-Coat (4.44 MPa) and Copalite Varnishtrade mark (3.14 MPa). There was no significant difference in shear bond strength between the control group and the experimental group treated with Superseal. The shear bond strength in the other experimental groups treated with Gluma, Varnish, and MS-Coat was similar to each other but significantly lower than control or Superseal. SEM showed revealed resin tags in most of the dentinal tubules in the experimental group treated with the Superseal. CONCLUSION: Among the four dentin desensitizers, Superseal was the only one that did not interfere with the process of resin bonding. The other dentin desensitizers that contained a resin ingredient interfered with resin retention.

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.

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.

A hamburger-shaped helical stacking of disk-shaped ligands mediated by silver(II) ions.

We describe a hamburger-shaped helical structure of chiral and achiral C3-symmetric disk-shaped ligands mediated by silver ions.

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.

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.