Orbital-resolved visualization of single-molecule photocurrent channels.

Given its central role in utilizing light energy, photoinduced electron transfer (PET) from an excited molecule has been widely studied1-6. However, even though microscopic photocurrent measurement methods7-11 have made it possible to correlate the efficiency of the process with local features, spatial resolution has been insufficient to resolve it at the molecular level. Recent work has, however, shown that single molecules can be efficiently excited and probed when combining a scanning tunnelling microscope (STM) with localized plasmon fields driven by a tunable laser12,13. Here we use that approach to directly visualize with atomic-scale resolution the photocurrent channels through the molecular orbitals of a single free-base phthalocyanine (FBPc) molecule, by detecting electrons from its first excited state tunnelling through the STM tip. We find that the direction and the spatial distribution of the photocurrent depend sensitively on the bias voltage, and detect counter-flowing photocurrent channels even at a voltage where the averaged photocurrent is near zero. Moreover, we see evidence of competition between PET and photoluminescence12, and find that we can control whether the excited molecule primarily relaxes through PET or photoluminescence by positioning the STM tip with three-dimensional, atomic precision. These observations suggest that specific photocurrent channels can be promoted or suppressed by tuning the coupling to excited-state molecular orbitals, and thus provide new perspectives for improving energy-conversion efficiencies by atomic-scale electronic and geometric engineering of molecular interfaces.

Selective triplet exciton formation in a single molecule.

The formation of excitons in organic molecules by charge injection is an essential process in organic light-emitting diodes (OLEDs)1-7. According to a simple model based on spin statistics, the injected charges form spin-singlet (S1) excitons and spin-triplet (T1) excitons in a 1:3 ratio2-4. After the first report of a highly efficient OLED2 based on phosphorescence, which is produced by the decay of T1 excitons, more effective use of these excitons has been the primary strategy for increasing the energy efficiency of OLEDs. Another route to improving OLED energy efficiency is reduction of the operating voltage2-6. Because T1 excitons have lower energy than S1 excitons (owing to the exchange interaction), use of the energy difference could-in principle-enable exclusive production of T1 excitons at low OLED operating voltages. However, a way to achieve such selective and direct formation of these excitons has not yet been established. Here we report a single-molecule investigation of electroluminescence using a scanning tunnelling microscope8-20 and demonstrate a simple method of selective formation of T1 excitons that utilizes a charged molecule. A 3,4,9,10-perylenetetracarboxylicdianhydride (PTCDA) molecule21-25 adsorbed on a three-monolayer NaCl film atop Ag(111) shows both phosphorescence and fluorescence signals at high applied voltage. In contrast, only phosphorescence occurs at low applied voltage, indicating selective formation of T1 excitons without creating their S1 counterparts. The bias voltage dependence of the phosphorescence, combined with differential conductance measurements, reveals that spin-selective electron removal from a negatively charged PTCDA molecule is the dominant formation mechanism of T1 excitons in this system, which can be explained by considering the exchange interaction in the charged molecule. Our findings show that the electron transport process accompanying exciton formation can be controlled by manipulating an electron spin inside a molecule. We anticipate that designing a device taking into account the exchange interaction could realize an OLED with a lower operating voltage.

[Successful treatment of acute promyelocytic leukemia with all-trans retinoic acid on hemodialysis for acute renal failure].

All-trans retinoic acid (ATRA) is used as standard induction therapy for acute promyelocytic leukemia (APL), but it is contraindicated for patients on hemodialysis. We present a case of a patient with APL on hemodialysis, intubated, and with marked disseminated intravascular coagulation (DIC) who was successfully treated with ATRA. A 49-year-old man was transferred to our hospital and admitted into the intensive care unit due to renal dysfunction, DIC, and pneumonia. Promyelocytes were noted in the peripheral blood, and he was diagnosed with APL after bone-marrow examination. Because of renal dysfunction, only Ara-C was used but with a reduced dose. The patient's condition improved, and he was extubated and withdrawn from dialysis on the 5th day of hospitalization. The patient suffered from APL syndrome during induction therapy, which necessitated ATRA withdrawal and steroid administration. Remission was achieved after induction therapy, and the patient is currently on maintenance therapy. There are few cases of patients with APL on hemodialysis who were treated with ATRA; hence, it is necessary to review the treatment plan for these patients.

Atomic-Scale Photon Mapping Revealing Spin-Current Relaxation.

A nanoscopic understanding of spin-current dynamics is crucial for controlling the spin transport in materials. However, gaining access to spin-current dynamics at an atomic scale is challenging. Therefore, we developed spin-polarized scanning tunneling luminescence spectroscopy (SP STLS) to visualize the spin relaxation strength depending on spin injection positions. Atomically resolved SP STLS mapping of gallium arsenide demonstrated a stronger spin relaxation in gallium atomic rows. Hence, SP STLS paves the way for visualizing spin current with single-atom precision.

Real-space investigation of energy transfer in heterogeneous molecular dimers.

Given its central role in photosynthesis and artificial energy-harvesting devices, energy transfer has been widely studied using optical spectroscopy to monitor excitation dynamics and probe the molecular-level control of energy transfer between coupled molecules. However, the spatial resolution of conventional optical spectroscopy is limited to a few hundred nanometres and thus cannot reveal the nanoscale spatial features associated with such processes. In contrast, scanning tunnelling luminescence spectroscopy has revealed the energy dynamics associated with phenomena ranging from single-molecule electroluminescence, absorption of localized plasmons and quantum interference effects to energy delocalization and intervalley electron scattering with submolecular spatial resolution in real space. Here we apply this technique to individual molecular dimers that comprise a magnesium phthalocyanine and a free-base phthalocyanine (MgPc and H2Pc) and find that locally exciting MgPc with the tunnelling current of the scanning tunnelling microscope generates a luminescence signal from a nearby H2Pc molecule as a result of resonance energy transfer from the former to the latter. A reciprocating resonance energy transfer is observed when exciting the second singlet state (S2) of H2Pc, which results in energy transfer to the first singlet state (S1) of MgPc and final funnelling to the S1 state of H2Pc. We also show that tautomerization of H2Pc changes the energy transfer characteristics within the dimer system, which essentially makes H2Pc a single-molecule energy transfer valve device that manifests itself by blinking resonance energy transfer behaviour.

Anti-Kasha emissions of single molecules in a plasmonic nanocavity.

Kasha's rule generally holds true for solid-state molecular systems, where the rates of internal conversion and vibrational relaxation are sufficiently higher than the luminescence rate. In contrast, in systems where plasmons and matter interact strongly, the luminescence rate is significantly enhanced, leading to the emergence of luminescence that does not obey Kasha's rule. In this work, we investigate the anti-Kasha emissions of single molecules, free-base and magnesium naphthalocyanine (H2Nc and MgNc), in a plasmonic nanocavity formed between the tip of a scanning tunneling microscope (STM) and metal substrate. A narrow-line tunable laser was employed to precisely reveal the excited-state levels of a single molecule located under the tip and to selectively excite it into a specific excited state, followed by obtaining a STM-photoluminescence (STM-PL) spectrum to reveal the energy relaxation from the state. The excitation to higher-lying states of H2Nc caused various changes in the emission spectrum, such as broadening and the appearance of new peaks, implying the breakdown of Kasha's rule. These observations indicate emissions from the vibrationally excited states in the first singlet excited state (S1) and second singlet excited state (S2), as well as internal conversion from S2 to S1. Moreover, we obtained direct evidence of electronic and vibronic transitions from the vibrationally excited states, from the STM-PL measurements of MgNc. The results obtained herein shed light on the energy dynamics of molecular systems under a plasmonic field and highlight the possibility of obtaining various energy-converting functions using anti-Kasha processes.

Chemical Identification and Bond Control of π-Skeletons in a Coupling Reaction.

Highly unsaturated π-rich carbon skeletons afford versatile tuning of structural and optoelectronic properties of low-dimensional carbon nanostructures. However, methods allowing more precise chemical identification and controllable integration of target sp-/sp2-carbon skeletons during synthesis are required. Here, using the coupling of terminal alkynes as a model system, we demonstrate a methodology to visualize and identify the generated π-skeletons at the single-chemical-bond level on the surface, thus enabling further precise bond control. The characteristic electronic features together with localized vibrational modes of the carbon skeletons are resolved in real space by a combination of scanning tunneling microscopy/spectroscopy (STM/STS) and tip-enhanced Raman spectroscopy (TERS). Our approach allows single-chemical-bond understanding of unsaturated carbon skeletons, which is crucial for generating low-dimensional carbon nanostructures and nanomaterials with atomic precision.

Ventricular tachycardia based on cardiac sarcoidosis with a narrow QRS complex, ablated on the left ventricle free-wall.

A septuagenarian female with cardiac sarcoidosis suffered from drug refractory ventricular tachycardia (VT) requiring multiple implantable cardioverter-defibrillator shocks. The QRS complex during the VT was very similar to that during sinus rhythm although the QRS width during the VT (142 ms) was relatively wider than that during sinus rhythm (107 ms). The VT exit was located on the ventricular septum close to the His-bundle recording region. However, the critical pathway of this VT was detected on the anterior free wall of the left ventricle (LV), and a radiofrequency application at that site could terminate the VT. No Purkinje potentials were recorded there during the VT or sinus rhythm. According to the electrophysiological study, 3-D mapping, and the response to the ablation, the critical circuit of the VT was surrounded by a protected area of scar associated with cardiac sarcoidosis. As a result, the VT circuit was connected to the basal septal area close to the His-Purkinje system as an outer loop of the VT circuit. This unique trajectory of the VT might have caused a similar QRS morphology to that of sinus rhythm, and the relatively narrow QRS complex despite the critical isthmus was located on the anterior free wall of the LV.

Many-Body State Description of Single-Molecule Electroluminescence Driven by a Scanning Tunneling Microscope.

Electron transport and optical properties of a single molecule in contact with conductive materials have attracted considerable attention because of their scientific importance and potential applications. With the recent progress in experimental techniques, especially by virtue of scanning tunneling microscope (STM)-induced light emission, where the tunneling current of the STM is used as an atomic-scale source for induction of light emission from a single molecule, it has become possible to investigate single-molecule properties at subnanometer spatial resolution. Despite extensive experimental studies, the microscopic mechanism of electronic excitation of a single molecule in STM-induced light emission has yet to be clarified. Here we present a formulation of single-molecule electroluminescence driven by electron transfer between a molecule and metal electrodes based on a many-body state representation of the molecule. The effects of intramolecular Coulomb interaction on conductance and luminescence spectra are investigated using the nonequilibrium Hubbard Green's function technique combined with first-principles calculations. We compare simulation results with experimental data and find that the intramolecular Coulomb interaction is crucial for reproducing recent experiments for a single phthalocyanine molecule. The developed theory provides a unified description of the electron transport and optical properties of a single molecule in contact with metal electrodes driven out of equilibrium, and thereby, it contributes to a microscopic understanding of optoelectronic conversion in single molecules on solid surfaces and in nanometer-scale junctions.

Single-Molecule Investigation of Energy Dynamics in a Coupled Plasmon-Exciton System.

We investigate the near-field interaction between an isolated free-base phthalocyanine molecule and a plasmon localized in the gap between an NaCl-covered Ag(111) surface and the tip apex of a scanning tunneling microscope. When the tip is located in the close proximity of the molecule, asymmetric dips emerge in the broad luminescence spectrum of the plasmon generated by the tunneling current. The origin of the dips is explained by energy transfer between the plasmon and molecular excitons and a quantum mechanical interference effect, where molecular vibrations provide additional degrees of freedom in the dynamic process.

Predictors and Clinical Outcomes of Transient Responders to Cardiac Resynchronization Therapy.

BACKGROUND: Left ventricular end-systolic volume (LVESV) changes at 6 months and clinical status are useful for assessing responses to cardiac resynchronization therapy (CRT). Regression of the LVESV following CRT has not been described beyond 6 months. This study aimed to assess the proportion, predictors, and clinical outcomes of responders whose LVESVs had regressed. METHODS: We retrospectively analyzed 104 consecutive CRT patients. A responder was defined as a patient with a relative reduction in the LVESV ≥15% at 6 months after CRT. Fifty-six responders participated in this study. A transient responder was defined as a responder without a relative reduction in the LVESV ≥15% at 2 years after CRT or who died of cardiac events during the 24-month follow-up period. RESULTS: Of the 56 responders, 16 (29%) were transient responders. Multivariable logistic regression analysis showed that chronic atrial fibrillation (odds ratio [OR] = 19.2, 95% confidence interval [CI] [1.93, 190], P = 0.012) and amiodarone usage (OR = 60.9, 95% CI [4.18, 886], P = 0.003) were independent predictors of transient responses. Hospitalizations for heart failure were significantly higher among the transient responders than among the lasting responders during a mean follow-up period of 7.6 years (log-rank P < 0.001), and all-cause mortality tended to be higher among the transient responders (log-rank P = 0.093). CONCLUSIONS: One-third of the responders were transient responders at 2 years after CRT, and their long-term prognoses were poor. Careful attention should be paid to maintain the reduction in LVESV especially in patients with chronic AF.

Optimal image reconstruction using multidetector-row computed tomography to facilitate cardiac resynchronization therapy.

Preprocedural recognition of the segment of latest mechanical contraction along with the anatomy of the coronary venous system is important for successful and effective cardiac resynchronization therapy. We present a case of ischemic cardiomyopathy who underwent implantation of a cardiac resynchronization therapy device with a defibrillator, which was facilitated by preprocedural computed tomographic images reconstructed to visualize the left ventricular slab and the coronary venous system simultaneously on the cardiac contour. The present reconstruction method using computed tomography is optimal and feasible method to incorporate the echocardiographic findings into the procedure performed under fluoroscopy appropriately.

Characteristics of Residual Atrial Posterior Wall and Roof-Dependent Atrial Tachycardias after Pulmonary Vein Isolation.

BACKGROUND: Roof-dependent atrial tachycardia (roof AT) sometimes occurs after pulmonary vein isolation (PVI) of atrial fibrillation (AF). This study aimed to investigate the relationship between the anatomy of the residual left atrial posterior wall and occurrence of roof AT. METHODS: A total of 265 patients with AF who underwent PVI were enrolled. After the PVI, induced or recurrent roof AT was confirmed by an entrainment maneuver or activation mapping using a three-dimensional (3D) mapping system. To identify the predictors of roof AT, the minimum distance between both PVI lines (d-PVI) was measured by a 3D mapping system and the anatomical parameters, including the left atrial (LA) diameter, left atrial volume index (LAVi), and shape of the left atrial roof, were analyzed by 3D computed tomography. RESULTS: Roof AT was documented in 11 (4.2%) of 265 patients. A multivariable analysis demonstrated that the d-PVI, Deep V shape of the LA roof, and LAVi were associated with roof AT occurrences (d-PVI: odds ratio: 0.72, confidence interval [CI]: 0.61-0.86, P < 0.001; Deep V shape: odds ratio: 0.19, CI: 0.04-0.82, P = 0.03; LAVi: odds ratio: 1.05, CI: 1.02-1.07, P = 0.001). A receiver-operating characteristic curve analysis yielded an optimal cut-off value of 15.5 mm and 55.7 mL/m2 for the d-PVI and LAVi, respectively. CONCLUSION: The shorter d-PVI at the LA roof, greater LAVi, and Deep V shape were associated with the occurrence of a roof AT.

Psychology in Japan.

The purpose of this article is to provide information about Japan and its psychology in advance of the 31st International Congress of Psychology (ICP), to be held in Yokohama, Japan, in 2016. The article begins with the introduction of the Japanese Psychological Association (JPA), the hosting organization of the ICP 2016, and the Japanese Union of Psychological Associations consisting of 51 associations/societies, of which the JPA is a member. This is followed by a brief description of a history of psychology of Japan, with emphasis on the variation in our approach to psychology in three different periods, that is, the pre- and post-Pacific War periods, and the post-1960 period. Next, the international contributions of Japanese psychology/psychologists are discussed from the point of view of their visibility. Education and training in psychology in Japanese universities is discussed with a final positive remark about the long-awaited enactment of the Accredited Psychologist Law in September, 2015.

The Relationship Between Cardiac Vulnerability and Restitution Properties of the Ventricular Activation Recovery Interval.

INTRODUCTION: The restitution of the action potential duration (APD) is an important contributor to ventricular fibrillation (VF) initiation by a single critically timed ectopic beat. We hypothesized that a steep slope of the activation recovery interval restitution curve was related to the upper limit of vulnerability (ULV). METHODS AND RESULTS: Fifty-four consecutive patients with implantable cardioverter defibrillators (ICDs) implanted between April 2012 and July 2013 were included. At the implantation, pacing from the right ventricular (RV) coil to an indifferent electrode inserted in the ICD pocket was performed, and the unipolar electrograms from the RV coil were simultaneously recorded. We assessed the standard restitution by introducing extra-stimuli, while measuring the activation recovery interval (ARI). Our protocol for the vulnerability test consisted of delivering three 15 J shocks on the T-peak and within ±20 milliseconds of it. If VF was not induced by that procedure, a ULV of ≤15 J was defined. The relationship between the ULV and maximum slope of the restitution curve was analyzed. A restitution curve could finally be obtained in a total of 40 patients. The background characteristics were similar between the two groups. The maximum slope of the restitution curve was steeper in the ULV > 15 J group than ULV ≤ 15 J group (1.55 ± 0.45 vs. 0.91 ± 0.64, P < 0.05). A maximum slope exceeding 1.0 was the optimal point for discriminating patients with a ULV > 15 J from a ULV ≤ 15 J (sensitivity 61.5% and specificity 96.3%). CONCLUSION: The maximum slope of the restitution curve was significantly related to the ULV. High defibrillation threshold patients could be detected by the ARI dynamics.

Atomic-scale luminescence measurement and theoretical analysis unveiling electron energy dissipation at a p-type GaAs(110) surface.

Luminescence of p-type GaAs was induced by electron injection from the tip of a scanning tunnelling microscope into a GaAs(110) surface. Atomically-resolved photon maps revealed a significant reduction in luminescence intensity at surface electronic states localized near Ga atoms. Theoretical analysis based on first principles calculations and a rate equation approach was performed to describe the perspective of electron energy dissipation at the surface. Our study reveals that non-radiative recombination through the surface states (SS) is a dominant process for the electron energy dissipation at the surface, which is suggestive of the fast scattering of injected electrons into the SS.

Supramolecular assembly through interactions between molecular dipoles and alkali metal ions.

Establishing a way to fabricate well-ordered molecular structures is a necessary step toward advancement in organic optoelectronic devices. Here, we propose to use interactions between electric dipoles of molecules and alkali metal ions to form a well-developed homogeneous monolayer of diarylethene molecules on the Cu(111) surface with the aid of NaCl co-deposition. Scanning tunneling microscopy and density functional theory calculation results indicate that the formation of a row-type structure occurs as a result of interactions between the Na(+) ions and the diarylethene molecular dipoles, drastically changing the adsorption configuration from that without Na(+).

Nanoscale thermal imaging of hot electrons by cryogenic terahertz scanning noise microscopy.

Nanoscale thermal imaging and temperature detection are of fundamental importance in diverse scientific and technological realms. Most nanoscale thermometry techniques focus on probing the temperature of lattice or phonons and are insensitive to nonequilibrium electrons, commonly referred to as "hot electrons." While terahertz scanning noise microscopy (SNoiM) has been demonstrated to be powerful in the thermal imaging of hot electrons, prior studies have been limited to room temperature. In this work, we report the development of a cryogenic SNoiM (Cryo-SNoiM) tailored for quantitative hot electron temperature detection at low temperatures. The microscope features a special two-chamber design where the sensitive terahertz detector, housed in a vacuum chamber, is efficiently cooled to ∼5 K using a pulse tube cryocooler. In a separate chamber, the atomic force microscope and the sample can be maintained at room temperature under ambient/vacuum conditions or cooled to ∼110 K via liquid nitrogen. This unique dual-chamber cooling system design enhances the efficacy of SNoiM measurements at low temperatures. It not only facilitates the pre-selection of tips at room temperature before cooling but also enables the quantitative derivation of local electron temperature without reliance on any adjustable parameters. The performance of Cryo-SNoiM is demonstrated through imaging the distribution of hot electrons in a cold, self-heated narrow metal wire. This instrumental innovation holds great promise for applications in imaging low-temperature hot electron dynamics and nonequilibrium transport phenomena across various material systems.

Visualization of Multiple-Resonance-Induced Frontier Molecular Orbitals in a Single Multiple-Resonance Thermally Activated Delayed Fluorescence Molecule.

The spatial distribution and electronic properties of the frontier molecular orbitals (FMOs) in a thermally activated delayed fluorescence (TADF) molecule contribute significantly to the TADF properties, and thus, a detailed understanding and sophisticated control of the FMOs are fundamental to the design of TADF molecules. However, for multiple-resonance (MR)-TADF molecules that achieve spatial separation of FMOs by the MR effect, the distinctive distribution of these molecular orbitals poses significant challenges for conventional computational analysis and ensemble averaging methods to elucidate the FMOs' separation and the precise mechanism of luminescence. Therefore, the visualization and analysis of electronic states with the specific energy level of a single MR-TADF molecule will provide a deeper understanding of the TADF mechanism. Here, scanning tunneling microscopy/spectroscopy (STM/STS) was used to investigate the electronic states of the DABNA-1 molecule at the atomic scale. FMOs' visualization and local density of states analysis of the DABNA-1 molecule clearly show that MR-TADF molecules also have well-separated FMOs according to the internal heteroatom arrangement, providing insights that complement existing theoretical prediction methods.

Phase 1 trial of preoperative, short-course carbon-ion radiotherapy for patients with resectable pancreatic cancer.

BACKGROUND: The authors evaluated the tolerance and efficacy of carbon-ion radiotherapy (CIRT) as a short-course, preoperative treatment and determined the recommended dose needed to reduce the risk of postoperative local recurrence without excess injury to normal tissue. METHODS: Patients radiographically defined with potentially resectable pancreatic cancer were eligible. A preoperative, short-course, dose-escalation study was performed with fixed 8 fractions in 2 weeks. The dose of irradiation was increased by 5% increments from 30 grays equivalents (GyE) to 36.8 GyE. Surgery was to be performed 2 to 4 weeks after the completion of CIRT. RESULTS: The study enrolled 26 patients. At the time of restaging after CIRT, disease progression with distant metastasis or refusal ruled out 5 patients from surgery. Twenty-one of 26 patients (81%) patients underwent surgery. The pattern of initial disease progression was distant metastasis in 17 patients (65%) and regional recurrence in 2 patients (8%). No patients experienced local recurrence. The 5-year survival rates for all 26 patients and for those who underwent surgery were 42% and 52%, respectively. CONCLUSIONS: Preoperative, short-course CIRT followed by surgery is feasible and tolerable without unacceptable morbidity.