Optical Force-Induced Chemistry at Solution Surfaces.

When an intense 1,064-nm continuous-wave laser is tightly focused at solution surfaces, it exerts an optical force on molecules, polymers, and nanoparticles (NPs). Initially, molecules and NPs are gathered into a single assembly inside the focus, and the laser is scattered and propagated through the assembly. The expanded laser further traps them at the edge of the assembly, producing a single assembly much larger than the focus along the surface. Amino acids and inorganic ionic compounds undergo crystallization and crystal growth, polystyrene NPs form periodic arrays and disklike structures with concentric circles or hexagonal packing, and Au NPs demonstrate assembling and swarming, in which the NPs fluctuate like a group of bees. These phenomena that depend on laser polarization are called optically evolved assembling at solution surfaces, and their dynamics and mechanisms are elucidated in this review. As a promising application in materials science, the optical trapping assembly of lead halide perovskites, supramolecules, and aggregation-induced emission enhancement-active molecules is demonstrated and future directions for fundamental study are discussed.

From Nanosecond Photochemistry to Optical Force Chemistry: My Journey.

Laser was invented in 1960 and soon introduced to chemistry research. We started time-resolved spectroscopy and photochemistry and initial trial was focused to nanosecond and then picosecond electronic absorption spectroscopy for studying molecular electronic excited states, charge separation in molecular complexes, and intermolecular electron transfer in solution. We considered that not only time-resolved but also space-resolved chemistry would be important for future laser-based chemistry and combined pulsed lasers with optical microscopes. Spectroscopy, photochemistry, ablation, and spatial arrangement of single microparticles and microdroplets in solution were carried out. Further we shifted from micro to nano and opened a new field covering spectroscopy, ablation, phase transition, crystallization, patterning, and fabrication. The progress is summarized and discussed as time-resolved nano spectroscopy, ablation nano dynamics, and optical force chemistry.

Nanoparticle Assembling Dynamics Induced by Pulsed Optical Force.

Femtosecond (fs) laser trapping dynamics is summarized for silica, hydrophobically modified silica, and polystyrene nanoparticles (NPs) in aqueous solution, highlighting their distinct optical trapping dynamics under CW laser. Mutually repulsive silica nanoparticles are tightly confined under fs laser compared to CW laser trapping and, upon increasing laser power, they are ejected from the focus as an assembly. Hydrophobically modified silica and polystyrene (PS) NPs are sequentially ejected just like a stream or ablated, giving bubbles. The ejection and bubbling take place with the direction perpendicular to laser polarization and its direction is randomly switched from one to the other. These characteristic features are interpreted from the viewpoint of single assembly formation of NPs at an asymmetric position in the optical potential. Temporal change in optical forces map is prepared for a single PS NP by calculating scattering, gradient, and temporal forces. The relative contribution of the forces changes with the volume increase of the assembly and, when the pushing force along the trapping pulse propagation overcome the gradient in the focal plane, the assembly undergoes the ejection. Further fs multiphoton absorption is induced for the larger assembly leading to bubble generation. The assembling, ejection, and bubbling dynamics of NPs are characteristic features of pulsed optical force and are considered as a new platform for developing new material fabrication method.

Surface plasmon resonance effect on laser trapping and swarming of gold nanoparticles at an interface.

Laser trapping at an interface is a unique platform for aligning and assembling nanomaterials outside the focal spot. In our previous studies, Au nanoparticles form a dynamically evolved assembly outside the focus, leading to the formation of an antenna-like structure with their fluctuating swarms. Herein, we unravel the role of surface plasmon resonance on the swarming phenomena by tuning the trapping laser wavelength concerning the dipole mode for Au nanoparticles of different sizes. We clearly show that the swarm is formed when the laser wavelength is near to the resonance peak of the dipole mode together with an increase in the swarming area. The interpretation is well supported by the scattering spectra and the spatial light scattering profiles from single nanoparticle simulations. These findings indicate that whether the first trapped particle is resonant with trapping laser or not essentially determines the evolution of the swarming.

Fast-tracking of single emitters in large volumes with nanometer precision.

Multifocal plane microscopy allows for capturing images at different focal planes simultaneously. Using a proprietary prism which splits the emitted light into paths of different lengths, images at 8 different focal depths were obtained, covering a volume of 50x50x4 µm3. The position of single emitters was retrieved using a phasor-based approach across the different imaging planes, with better than 10 nm precision in the axial direction. We validated the accuracy of this approach by tracking fluorescent beads in 3D to calculate water viscosity. The fast acquisition rate (>100 fps) also enabled us to follow the capturing of 0.2 µm fluorescent beads into an optical trap.

Anomalously Large Assembly Formation of Polystyrene Nanoparticles by Optical Trapping at the Solution Surface.

We demonstrated the optical trapping-induced formation of a single large disc-like assembly (∼50 µm in diameter) of polystyrene (PS) nanoparticles (NPs) (100 nm in diameter) at a solution surface. Different from the conventional trapping behavior in solution, the assembly grows from the focus to the outside along the surface and contains needle structures expanding radially in all directions. Upon switching off the trapping laser, the assembly disperses and needle structures disappear, while the highly concentrated domain of the NPs is left for a while. The single assembly is quickly restored by switching on the laser again, where the needle structures are also reproduced but in a different way. When a single 10 µm PS microparticle (MP) is trapped in the NP solution, a single disc-like assembly containing needle structures is similarly prepared outside the MP. Based on backscattering imaging and tracking analyses of the MP at the solution surface, it is proposed that scattering and propagation of the trapping laser from the central part of the NP assembly or the MP lead to this new phenomenon.

Two-Year Results of a Multicenter Prospective Observational Study of the Zenith Spiral-Z Limb Deployed in the External Iliac Artery During Endovascular Aneurysm Repair.

BACKGROUND: Limited data is available on the use of a polyester graft limb with a helical stent configuration deployed in the external iliac artery (EIA) during endovascular aneurysm repair (EVAR), so we prospectively analyzed the efficacy of the Zenith Spiral-Z limb deployed in the EIA.Methods and Results:Patients undergoing EVAR using a Zenith stent-graft and Spiral-Z limb deployed in the EIA were prospectively registered in 24 Japanese institutions from June 2017 to November 2017. In total, 65 patients (74 limbs) (mean age: 77.1±8.0 years, 87.7% men, mean abdominal aortic aneurysm (AAA) diameter: 51.9±7.2 mm, mean iliac artery aneurysm (IAA) diameter: 38.3±10.0 mm) were registered and followed up. The most common reason for deployment in the EIA was a common IAA (43 limbs, 58.1%), and 8 limbs (10.8%) had a bare nitinol stent placed at the Spiral-Z limb. A total of 61 patients (70 limbs) completed a 24-month follow-up. There were 2 Spiral-Z limb stenoses and 1 occlusion, leading to a primary patency of 95.5% and a secondary patency of 100%, at 24 months. Buttock claudication occurred in 24.3% of the limbs treated at 1 month but decreased to 4.3% at 24 months. CONCLUSIONS: Our multicenter prospective study showed that Spiral-Z limb deployed in the EIA was associated with satisfactory results and seems to be a durable option, even in the era of iliac branch devices.

Spatiotemporal Dynamics of Aggregation-Induced Emission Enhancement Controlled by Optical Manipulation.

We present spatiotemporal control of aggregation-induced emission enhancement (AIEE) of a protonated tetraphenylethene derivative by optical manipulation. A single submicrometer-sized aggregate is initially confined by laser irradiation when its fluorescence is hardly detectable. The continuous irradiation of the formed aggregate leads to sudden and rapid growth, resulting in bright yellow fluorescence emission. The fluorescence intensity at the peak wavelength of 540 nm is tremendously enhanced with growth, meaning that AIEE is activated by optical manipulation. Amazingly, the switching on/off of the activation of AIEE is arbitrarily controlled by alternating the laser power. This result means that optical manipulation increases the local concentration, which overcomes the electrostatic repulsion between the protonated molecules, namely, optical manipulation changes the aggregate structure. The dynamics and mechanism in AIEE controlled by optical manipulation will be discussed from the viewpoint of molecular conformation and association depending on the laser power.

Is systolic blood pressure high in patients with acute aortic dissection on first medical contact before hospital transfer?

Acute aortic dissection (AAD) cases are thought to have high blood pressure (BP) on admission; however, little data are available on BP prior to admission. The purpose of this study was to investigate systolic blood pressure (SBP) very early after symptom onset and before hospital transfer in patients with AAD to determine whether SBPs were high, and also whether SBPs were higher or lower compared with SBPs at hospital admission. We obtained results using three-year data derived from the Tokyo Acute Aortic Super Network Database. First, we selected 830 patients with AAD for which the "duration from symptom onset to first medical contact by ambulance crews" (SO-FMC) was within 60 min. We examined the SBPs of such patients. Next, we selected 222 patients with AAD whose SBPs were measured both at FMC, within 15 min after symptom onset, and at hospital admission, and compared SBPs at FMC with those at hospital admission. Among types A (n = 190) and B (n = 117), in patients with an SO-FMC ≤ 15 min, the median SBP was 100 mmHg and 178 mmHg (p < 0.001), respectively; 9% and 50% (p < 0.001) of such patients, respectively, exhibited an SBP ≥ 180 mmHg; and 43% and 10% (p < 0.001) of such patients, respectively, had an SBP < 90 mmHg. Of patients with types A (n = 124) and B (n = 98) AAD whose SBPs were measured both at FMC, within 15 min after symptom onset, and at hospital admission, SBPs at FMC were higher than those at hospital admission for the SBP ≥ 180 mmHg subgroups of both type A (194 mmHg vs. 159 mmHg, p < 0.001) and type B (199 mmHg vs. 186 mmHg, p < 0.001). Approximately 10 min after symptom onset and before hospital transfer, the measured SBPs of many patients with type A AAD were not necessarily high. However, the SBPs of cases with type B AAD were high as previously reported for SBP on admission. In addition, for the subgroup of SBP ≥ 180 mmHg at FMC within 15 min after symptom onset, SBPs at FMC were significantly higher than those at hospital admission for both types A and B; the higher SBP at symptom onset may have been partially associated with being a trigger of AD.

A Single Large Assembly with Dynamically Fluctuating Swarms of Gold Nanoparticles Formed by Trapping Laser.

Laser trapping has been utilized as tweezers to three-dimensionally trap nanoscale objects and has provided significant impacts in nanoscience and nanotechnology. The objects are immobilized at the position where the tightly focused laser beam is irradiated. Here, we report the swarming of gold nanoparticles in which component nanoparticles dynamically interact with each other, keeping their long interparticle distance around the trapping laser focus at a glass/solution interface. A pair of swarms are directionally extended outside the focal spot perpendicular to the linear polarization like a radiation pattern of dipole scattering, while a doughnut-shaped swarm is prepared by circularly polarized trapping laser. The light field is expanded as scattered light through trapped nanoparticles; this modified light field further traps the nanoparticles, and scattering and trapping cooperatively develop. Due to these nonlinear dynamic processes, the dynamically fluctuating swarms are evolved up to tens of micrometers. This finding will open the way to create various swarms of nanoscale objects that interact and bind through the scattered light depending on the properties of the laser beam and the nanomaterials.

[Cardiac Strangulation Induced by Epicardial Pacemaker Leads Causing Heart Failure;Report of a Case].

A 5-year-old girl has a history of epicardial VVI-pacemaker implantation due to congenital heart block at the age of 2 months. Five years later, she developed heart failure at the same time of battery depletion. The chest X-ray indicated the loop formation of the epicardial leads and the echocardiogram demonstrated paradoxical movement of ventricles. The 3-dimensional computed tomography finally revealed strangulation of biventricular apex caused by loop of the leads. She underwent reoperation. Cardiac strangulation was relieved by total removal of the loop and repositioning of right atrial and ventricular electrodes in a gentle curve of the leads. She was discharged and doing well. Cardiac strangulation is a rare, but it can be lethal. Therefore epicardial pacemaker leads should not be positioned around the ventricle with excessive redundancy.

Novel physical chemistry approaches in biophysical researches with advanced application of lasers: Detection and manipulation.

Novel methodologies utilizing pulsed or intense CW irradiation obtained from lasers have a major impact on biological sciences. In this article, recent development in biophysical researches fully utilizing the laser irradiation is described for three topics, time-resolved fluorescence spectroscopy, time-resolved thermodynamics, and manipulation of the biological assemblies by intense laser irradiation. First, experimental techniques for time-resolved fluorescence spectroscopy are concisely explained in Section 2. As an example of the recent application of time-resolved fluorescence spectroscopy to biological systems, evaluation of the viscosity of lipid bilayer membranes is described. The results of the spectroscopic experiments strongly suggest the presence of heterogeneous membrane structure with two different viscosity values in liposomes formed by a single phospholipid. Section 3 covers the time-resolved thermodynamics. Thermodynamical properties are important to characterize biomolecules. However, measurement of these quantities for short-lived intermediate species has been impossible by traditional thermodynamical techniques. Recently, development of a spectroscopic method based on the transient grating method enables us to measure these quantities and also to elucidate reaction kinetics which cannot be detected by other spectroscopic methods. The principle of the measurements and applications to some protein reactions are reviewed. Manipulation and fabrication of supramolecues, amino acids, proteins, and living cells by intense laser irradiation are described in Section 4. Unconventional assembly, crystallization and growth, amyloid fibril formation, and living cell manipulation are achieved by CW laser trapping and femtosecond laser-induced cavitation bubbling. Their spatio-temporal controllability is opening a new avenue in the relevant molecular and bioscience research fields. This article is part of a Special Issue entitled "Biophysical Exploration of Dynamical Ordering of Biomolecular Systems" edited by Dr. Koichi Kato.

Rapid localized crystallization of lysozyme by laser trapping.

Confining protein crystallization to a millimetre size was achieved within 0.5 h after stopping 1 h intense trapping laser irradiation, which shows excellent performance in spatial and temporal controllability compared to spontaneous nucleation. A continuous-wave near-infrared laser beam is tightly focused into a glass/solution interfacial layer of a supersaturated buffer solution of hen egg-white lysozyme (HEWL). The crystallization is not observed during laser trapping, but initiated by stopping the laser irradiation. The generated crystals are localized densely in a circular area with a diameter of a few millimetres around the focal spot and show specific directions of the optical axes of the HEWL crystals. To interpret this unique crystallization, we propose a mechanism that nucleation and the subsequent growth take place in a highly concentrated domain consisting of HEWL liquid-like clusters after turning off laser trapping.

Resonance optical trapping of individual dye-doped polystyrene particles with blue- and red-detuned lasers.

We demonstrate resonance optical trapping of individual dye-doped polystyrene particles with blue- and red-detuned lasers whose energy are higher and lower compared to electronic transition of the dye molecules, respectively. Through the measurement on how long individual particles are trapped at the focus, we here show that immobilization time of dye-doped particles becomes longer than that of bare ones. We directly confirm that the immobilization time of dye-doped particles trapped by the blue-detuned laser becomes longer than that by the red-detuned one. These findings are well interpreted by our previous theoretical proposal based on nonlinear optical response under intense laser field. It is discussed that the present result is an important step toward efficient and selective manipulation of molecules, quantum dots, nanoparticles, and various nanomaterials based on their quantum mechanical properties.

Photocontrolled Supramolecular Assembling of Azobenzene-Based Biscalix[4]arenes upon Starting and Stopping Laser Trapping.

Laser trapping in chemistry covers various studies ranging from single molecules, nanoparticles, and quantum dots to crystallization and liquid-liquid phase separation of amino acids. In this work, a supramolecular assembly of azobenzene-based biscalix[4]arene is generated in ethyl acetate using laser trapping; its nucleation and growth are elucidated. No trapping behavior was observed when a 1064 nm laser beam was focused inside of the solution; however, interesting assembling phenomena were induced when it was shined at the air/solution interface. A single disk having two layers was first prepared at the focal point of ∼1 µm and then expanded to the size of a few tens of micrometers, although no optical force was exerted outside of the focal volume. Upon switching the trapping laser off, needles were generated at the outer layer of the assembly, giving a stable sea urchin-like morphology to the generated assembly. At a 30-50% dilution of the initial solution in ethyl acetate, a mushroom-like morphology was also observed. Laser trapping-induced assembly of azobenzene-based biscalix[4]arene was quite different from the sharp-ellipsoidal aggregates obtained by the spontaneous evaporation of the solution. These trapping phenomena were specifically observed for biscalix[4]arene in the trans conformation of azo-benzene moiety but not for the cis-form, suggesting that the laser trapping of this azobenzene-based biscalix[4]arene is photocontrollable. Dynamics and mechanism of the supramolecular assembling are considered, referring to laser trapping-induced nucleation and liquid-liquid phase separation of amino acids.

Femtosecond-Laser-Enhanced Amyloid Fibril Formation of Insulin.

Femtosecond (fs)-laser-induced crystallization as a novel crystallization technique was proposed for the first time by our group, where the crystallization time can be significantly shortened under fs laser irradiation. Similarly, we have further extended our investigation to amyloid fibril formation, also known as a nucleation-dependence process. Here we demonstrate that the necessary time for amyloid fibril formation can be significantly shortened by fs laser irradiation, leading to favorable enhancement. The enhancement was confirmed by both spectral measurements and direct observations of amyloid fibrils. The thioflavin T fluorescence intensity of laser-irradiated solution increased earlier than that of the control solution, and such a difference was simultaneously revealed by ellipticity changes. At the same time before intensity saturation in fluorescence, the number of amyloid fibrils obtained under laser irradiation was generally more than that in the control solution. Besides, such an enhancement is correlated to the laser power threshold of cavitation bubbling. Possible mechanisms are proposed by referring to fs-laser-induced crystallization and ultrasonication-induced amyloid fibril formation.

Optical Trapping-Formed Colloidal Assembly with Horns Extended to the Outside of a Focus through Light Propagation.

We report optical trapping and assembling of colloidal particles at a glass/solution interface with a tightly focused laser beam of high intensity. It is generally believed that the particles are gathered only in an irradiated area where optical force is exerted on the particles by laser beam. Here we demonstrate that, the propagation of trapping laser from the focus to the outside of the formed assembly leads to expansion of the assembly much larger than the irradiated area with sticking out rows of linearly aligned particles like horns. The shape of the assembly, its structure, and the number of horns can be controlled by laser polarization. Optical trapping study utilizing the light propagation will open a new avenue for assembling and crystallizing quantum dots, metal nanoparticles, molecular clusters, proteins, and DNA.

A Single Spherical Assembly of Protein Amyloid Fibrils Formed by Laser Trapping.

Protein amyloids have received much attention owing to their correlation with serious diseases and to their promising mechanical and optical properties as future materials. Amyloid formation has been conducted by tuning temperature and chemical conditions, so that its nucleation and the following growth are analyzed as ensemble dynamics. A single spherical assembly of amyloid fibrils of cytochrome c domain-swapped dimer was successfully generated upon laser trapping. The amyloid fibrillar structure was confirmed by fluorescence characterization and electron microscopy. The prepared spheres were further manipulated individually in solution to fabricate a three-dimensional microstructure and a line pattern. Amyloid formation dynamics and amyloid-based microstructure fabrication are demonstrated based on direct observation of a single spherical assembly, which foresees a new approach in amyloid studies.

Optically Evolved Assembly Formation in Laser Trapping of Polystyrene Nanoparticles at Solution Surface.

Assembling dynamics of polystyrene nanoparticles by optical trapping is studied with utilizing transmission/reflection microscopy and reflection microspectroscopy. A single nanoparticle assembly with periodic structure is formed upon the focused laser irradiation at solution surface layer and continuously grows up to a steady state within few minutes. By controlling nanoparticle and salt concentrations in the colloidal solution, the assembling behavior is obviously changed. In the high concentration of nanoparticles, the assembly formation exhibits fast growth, gives large saturation size, and leads to dense packing structure. In the presence of salt, one assembly with the elongated aggregates was generated from the focal spot and 1064 nm trapping light was scattered outwardly with directions, while a small circular assembly and symmetrical expansion of the 1064 nm light were found without salt. The present nanoparticle assembling in optical trapping is driven through multiple scattering in gathered nanoparticles and directional scattering along the elongated aggregates derived from optical association of nanoparticles, which dynamic phenomenon is called optically evolved assembling. Repetitive trapping and release processes of nanoparticles between the assembly and the surrounding solution always proceed, and the steady state at the circular assembly formed by laser trapping is determined under optical and chemical equilibrium.

[A Case of Aortoesophageal Fistula Rupture Due to Descending Thoracic Aortic Dissection with Recurrent Colon Cancer during Chemotherapy Containing Bevacizumab].

We report a case of aortoesophageal fistula rupture during the course of chemotherapy following colon cancer resection. The patient was a 77-year-old woman. Following recurrence of cancer of the sigmoid colon, the patient received a course of XELOX plus bevacizumab(Bmab)to treat peritoneal dissemination and lung metastases. She was brought by ambulance to our hospital's emergency department 55 days after the last dose of Bmab, with a chief complaint of hematemesis. Hematolo- gy results showed severe anemia with a hemoglobin level of 4.0 g/dL. Descending thoracic aortic dissection was noted on chest CT with contrast, and the patient was diagnosed with an aortoesophageal fistula rupture. She underwent emergent endovascular chest stent grafting to control the bleeding. Although the ruptured esophagus was a potential source of infection, the patient and family members chose palliative treatment. Therefore, conservative treatment was administered without removing the esophagus. The patient's postoperative course was good; instead of resuming oral intake, the patient was discharged on home IVH 59 days after surgery. Outpatient follow-up continued, but multiple metastases led to gradual worsening of the patient's general condition. She died 168 days after being admitted for surgery.