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Ultrafast electronic relaxation of nucleobases from ¹ππ* states to the ground state (S0) is considered essential for the photostability of DNA. However, transient absorption spectroscopy (TAS) has indicated that some nucleobases in aqueous solutions create long-lived ¹nπ*/³ππ* dark states from the ¹ππ* states with a high quantum yield of 0.4–0.5. We investigated electronic relaxation in pyrimidine nucleobases in both aqueous solutions and the gas phase using extreme ultraviolet (EUV) time-resolved photoelectron spectroscopy. Femtosecond EUV probe pulses cause ionization from all electronic states involved in the relaxation process, providing a clear overview of the electronic dynamics. The ¹nπ* quantum yields for aqueous cytidine and uracil (Ura) derivatives were found to be considerably lower (

Millimeter-wave band signals have the advantage of a high capacity and have been used in fifth-generation (5G) mobile services. An analog radio over multi-mode fiber (A-RoMMF) employing a directly modulated vertical cavity surface emitting laser is a promising technology for relaying millimeter-wave band signals to its dead area because of the advantages of low latency, low cost, and low power consumption. One of the applications of A-RoMMF is a cascaded intermediate-frequency-over-fiber (IFoF)-based centralized radio access network (C-RAN) mobile fronthaul (MFH) system. We conducted two studies on A-RoMMF to extend the transmission distance and bandwidth to adapt it to the system. First, we evaluated the effect of employing a single-mode vertical cavity surface emitting laser (VCSEL) and a multi-mode VCSEL on the transmission characteristics of A-RoMMF. Next, we evaluated the transmission characteristics of A-RoMMF using a cost-efficient bias-tee consisting of an electrical circuit pattern, the frequency response of which has a slope inverse to that of A-RoMMF at the 28-GHz band, to suppress the channel power difference of two component carrier signals for a wide-bandwidth signal transmission. We conducted these evaluations using A-RoMMF itself and herein demonstrate its adaption to a cascaded IFoF-based C-RAN MFH system at the 28-GHz band. When employing it with a 200-m long multi-mode fiber, the system achieves 400-MHz/CC and two component carrier signal transmissions.

DNA reacts directly with UV light with a wavelength shorter than 300 nm. Although ground surface sunlight includes little of this short-wavelength UV light due to its almost complete absorption by the atmosphere, sunlight is the primary cause of skin cancer. Photosensitization by endogenous substances must therefore be involved in skin cancer development mechanisms. Uric acid is the final metabolic product of purines in humans, and is present at relatively high concentrations in cells and fluids. When a neutral mixed solution of 2'-deoxycytidine, 2'-deoxyguanosine, thymidine, and 2'-deoxyadenosine was irradiated with UV light with a wavelength longer than 300 nm in the presence of uric acid, all the nucleosides were consumed in a uric acid dose-dependent manner. These reactions were inhibited by the addition of radical scavengers, ethanol and sodium azide. Two products from 2'-deoxycytidine were isolated and identified as N4-hydroxy-2'-deoxycytidine and N4,5-cyclic amide-2'-deoxycytidine, formed by cycloaddition of an amide group from uric acid. A 15N-labeled uric acid, uric acid-1,3-15N2, having two 14N and two 15N atoms per molecule, produced N4,5-cyclic amide-2'-deoxycytidine containing both 14N and 15N atoms from uric acid-1,3-15N2. Singlet oxygen, hydroxyl radical, peroxynitrous acid, hypochlorous acid, and hypobromous acid generated neither N4-hydroxy-2'-deoxycytidine nor N4,5-cyclic amide-2'-deoxycytidine in the presence of uric acid. These results indicate that uric acid is a photosensitizer for the reaction of nucleosides by UV light with a wavelength longer than 300 nm, and that an unidentified radical derived from uric acid with a delocalized unpaired electron may be generated.

We present a study using extreme UV (EUV) photoemission spectroscopy of the valence electronic structures of aqueous and methanol solutions using a 10 kHz EUV light source based on high-order harmonic generation and a magnetic bottle time-of-flight electron spectrometer. Two aspects of the observed spectra are highlighted in this study. One is variation of the vertical ionization energy (VIE) for liquids as a function of the solute concentration, which is closely related to surface dipoles at the gas-liquid interface. The experimental results show that the VIE of liquid water increases slightly with increasing concentrations of NaCl and NaI and decreases with NaOH. The VIE of liquid methanol was also found to change slightly with NaI. On the other hand, tetrabutylammonium iodide (TBAI) and butylamine (BA) clearly reduce the VIE for liquid water, which is attributed to the formation of an electric double layer (EDL) by segregated solutes at the gas-liquid interface. As evidence for this, when the pH of an aqueous BA solution is reduced to protonate BA, the VIE shift gradually decreases because the protonated BA moves into the bulk to suppress the influence of the EDL. We computed the surface potentials for these solutions using molecular dynamics simulations, and the results supported our interpretation of the experimental results. Another observation is the variation of the relative energy and shape of individual photoelectron bands for solvents, which is related to alteration of the structure and constituents of the first solvation shell of ionized solvent molecules. All of the solutes cause changes in the photoelectron spectra at high concentration, one of the most prominent of which is the degree of splitting of the 3a1 band for liquid water and the 7a' band for liquid methanol, which are sensitive to hydrogen bonding in the liquids. The 3a1 splitting decreases with the increasing concentration of NaI, NaCl, and NaOH, indicating that Na+ penetrates into the hydrogen-bonding network to coordinate to a nonbonding electron of a water molecule. On the other hand, TBAI and BA cause smaller changes in the 3a1 splitting. Full interpretation of these spectroscopic features awaits extensive quantum chemical calculations and is beyond the scope of this study. However, these results illustrate the strong potential of EUV laser photoemission spectroscopy of liquids for exploration of interfacial and solution chemistry.

The photoisomerization of isolated ethylene (ethene) was observed in real time from the Franck-Condon region in the

We studied nonadiabatic dissociation of CS2 from the 1B2 (1Σu+) state using ultrafast extreme ultraviolet photoelectron spectroscopy. A deep UV (200 nm) laser using the filamentation four-wave mixing method and an extreme UV (21.7 eV) laser using the high-order harmonic generation method were employed to achieve the pump-probe laser cross-correlation time of 48 fs. Spectra measured with a high signal-to-noise ratio revealed clear dynamical features of vibrational wave packet motion in the 1B2 state; its electronic decay to lower electronic state(s) within 630 fs; and dissociation into S(1D2), S(3PJ), and CS fragments within 300 fs. The results suggest that both singlet and triplet dissociation occur via intermediate electronic state(s) produced by electronic relaxation from the 1B2 (1Σu+) state.

Recently, we reported that uric acid and salicylic acid are photosensitizers of the reaction of nucleosides with UV light via radical formation and energy transfer, respectively. In the present study, effects of 45 biologically relevant compounds on nucleoside reactions photosensitized by uric acid and salicylic acid were examined. When a mixed solution of 2'-deoxycytidine, 2'-deoxyguanosine, thymidine, and 2'-deoxyadenosine with uric acid was irradiated with UV light of a wavelength longer than 300 nm, all the nucleosides decreased. The addition of antioxidants suppressed the consumption of nucleosides. When the UV reaction of nucleosides was conducted with salicylic acid, thymidine decreased almost exclusively. Several antioxidants such as ascorbates, thiols, catecholamines

Kynurenic acid, a tryptophan metabolite, acts as antagonist or agonist of several receptors. Hypobromous acid (HOBr) and hypochlorous acid (HOCl) are generated by eosinophils and neutrophils. At inflammation sites, kynurenic acid may encounter HOBr and HOCl to generate products. When kynurenic acid was incubated with HOBr under neutral conditions, kynurenic acid generated a single product almost exclusively. This was identified as 3-bromokynurenic acid. Kynurenic acid reacted with HOCl, generating two products. The major product was identified as 3-chlorokynurenic acid with its oxidative decarboxylation product, 3-chloro-4-hydroxy-2(1H)-quinolinone as a by-product. Free amino acids suppressed the reactions of kynurenic acid with HOBr and HOCl. Taurine suppressed the HOCl reaction but not the HOBr reaction. An eosinophil peroxidase system containing H2O2, NaCl, and NaBr reacted with kynurenic acid, generating 3-bromokynurenic acid under mildly acidic conditions. Although a myeloperoxidase system containing H2O2 and NaCl reacted with kynurenic acid to generate 3-chlorokynurenic acid under mildly acidic conditions, the product was altered to 3-bromokynurenic acid by addition of NaBr to the system. These results suggest that 3-bromokynurenic acid and 3-chlorokynurenic acid may be generated from kynurenic acid at inflammation sites in humans, although their formation will be suppressed by coexistent amino acids.

To increase the number of wireless devices, e.g., mobile or IoT terminals, cryptosystems are essential for secure communications. In this regard, random number generation is crucial because the appropriate function of cryptosystems relies on it to work properly. This paper proposes a true random number generator (TRNG) method capable of working in wireless communication systems. By embedding a TRNG in such systems, no additional analog circuits are required and working conditions can be limited as long as wireless communication systems are functioning properly, making TRNG method cost-effective. We also present some theoretical background and considerations. We next conduct experimental verification, which strongly supports the viability of the proposed method., Comment: We decided to withdraw this paper in order to significantly rewrite this paper

Previously, theoretical calculations on the non-adiabatic dynamics of benzene from the S2 state have indicated that the S2/S1 and S1/S0 conical intersections (CIs) facilitate ballistic nuclear wavepacket motion from S2 to S0 (fast channel) and branching to S1 (slow channel). In this paper, we present time-resolved photoelectron spectra of benzene and its methyl-derivatives (toluene and o-xylene) measured with a vacuum-UV laser, which clearly reveal both the fast and slow channels. The extremely short propagation time of the wavepacket between the two CIs of benzene indicates that the two are in close proximity to each other, while methyl substitution extends the propagation time and decreases the branching ratio into the fast channel. The results suggest that the quasi-degeneracy of the three states in benzene is lifted by the geometrical shifts of the CIs by methyl substitution.

We present condensed-phase first-principles molecular dynamics simulations to elucidate the presence of different electron trapping sites in liquid methanol and their roles in the formation, electronic transitions, and relaxation of solvated electrons (e−met) in methanol. Excess electrons injected into liquid methanol are most likely trapped by methyl groups, but rapidly diffuse to more stable trapping sites with dangling OH bonds. After localization at the sites with one free OH bond (1OH trapping sites), reorientation of other methanol molecules increases the OH coordination number and the trap depth, and ultimately four OH bonds become coordinated with the excess electrons under thermal conditions. The simulation identified four distinct trapping states with different OH coordination numbers. The simulation results also revealed that electronic transitions of e−met are primarily due to charge transfer between electron trapping sites (cavities) formed by OH and methyl groups and that these transitions differ from hydrogenic electronic transitions involving aqueous solvated electrons (e−aq). Such charge transfer also explains the alkyl-chain-length dependence of the photoabsorption peak wavelength and the excited-state lifetime of solvated electrons in primary alcohols.

We describe a magnetic bottle time-of-flight electron spectrometer designed for time-resolved photoemission spectroscopy of a liquid microjet using extreme UV and X-ray radiation. The spectrometer can be easily reconfigured depending on experimental requirements and the energy range of interest. To improve the energy resolution at high electron kinetic energy, a retarding potential can be applied either via a stack of electrodes or retarding mesh grids, and a flight-tube extension can be attached to increase the flight time. A gated electron detector was developed to reject intense parasitic signal from light scattered off the surface of the cylindrically shaped liquid microjet. This detector features a two-stage multiplication with a microchannel plate plus a fast-response scintillator followed by an image-intensified photon detector. The performance of the spectrometer was tested at SPring-8 and SACLA, and time-resolved photoelectron spectra were measured for an ultrafast charge transfer to solvent reaction in an aqueous NaI solution with a 200 nm UV pump pulses from a table-top ultrafast laser and the 5.5 keV hard X-ray probe pulses from SACLA.

Methotrexate is a folate antagonist cytotoxic drug employed in the therapy of cancers and rheumatoid arthritis. Hypobromous acid (HOBr) and hypochlorous acid (HOCl) are generated by eosinophils and neutrophils at inflammation sites. The administered methotrexate may encounter HOBr and HOCl, and react with them to generate products. When methotrexate was incubated with HOBr or HOCl at pH 7.4 and 37°C for 30 min, a single product was generated almost exclusively in each case, identified as 3'-bromomethotrexate for HOBr and 3'-chloromethotrexate for HOCl. When methotrexate was incubated with HOCl in the presence of NaBr, the concentration of 3'-bromomethotrexate increased with decreasing concentration of 3'-chloromethotrexate in a dose-dependent manner with NaBr, probably due to the formation of HOBr. Free amino acids suppressed the reactions of methotrexate with HOBr and HOCl. Taurine suppressed the HOCl reaction but not the HOBr reaction. These results suggest that 3'-bromomethotrexate and 3'-chloromethotrexate may be generated from methotrexate at inflammation sites in humans, although their formation will be suppressed by coexistent amino acids.

Rabin encryption and a secure ownership transfer protocol based on the difficulty of factorization of a public key use a small public exponent. Such encryption requires random number padding. The Coppersmith's shortpad attack works effectively on short padding, thereby allowing an adversary to extract the secret message. However, the criteria for determining the appropriate padding size remains unclear. In this paper, we derived the processing-time formula for the shortpad attack and determined the optimal random-padding size in order to achieve the desired security., We decided to withdraw this paper in order to significantly rewrite this paper

Ultrafast electronic relaxation following 9.3 eV photoexcitation of gaseous acetone was investigated with time-resolved photoelectron imaging spectroscopy. An intense photoionization signal due to a transition from the 41A1(π,π*) state to the D1(π-1) cationic state diminishes within 50 fs, owing to vibrational wave packet motion leaving our observation energy window. Additional photoionization signals were assigned to transitions from Rydberg states with principal quantum numbers of 3-8 to the D0(n-1) cationic state, created by strong vibronic couplings with the bright 41A1(π,π*) state. The deactivation processes of the 41A1(π,π*) and Rydberg states are discussed based on their decay profiles obtained from a time-energy map of photoelectron kinetic energy distributions.

N-Nitrosoproline (NPRO) is known to form endogenously from sodium nitrite and the amino acid proline, and is thought to be non-mutagenic and non-carcinogenic. However, earlier studies in our laboratory showed that irradiated NPRO can be converted directly to a mutagenic compound upon UVA irradiation. We previously investigated the mutagenic spectrum of NPRO on M13mp2 DNA with UVA irradiation, and found a hot spot comprising AT to GC, where there might be a particular photoreaction of adenine residues with NPRO. In the present study, we investigated the reaction of NPRO with 2'-deoxyadenosine (dA) under UVA irradiation, and identified the chemical structures of the photoproducts. Photoproducts from NPRO and dA were isolated and analyzed with HPLC, MS and NMR. (R)-, (S)-2-(2-pyrrolidyl)-2’-deoxyadenosine (P1, P2) and deoxyinosine (dI) were identified from the mixture of dA and NPRO irradiated with UVA. Results suggest that UVA-activated NPRO produces pyrrolidyl cations which react with dA to generate pyrrolidyl-dA adducts. Production of P1 and P2 from irradiated NPRO with dA increased under N2 saturation compared to those under air saturation, while production of P1 and P2 from irradiated solution under O2 saturation was lower compared to that under air. These results suggest that a Type-I mechanism is involved in the photoproduction of P1 and P2. Furthermore, reactive oxygen species generated during photo-reaction in the presence of O2 may act to destroy the activated form of irradiated NPRO to reduce the formation of P1 and P2. The formation of dI in the irradiated mixture of NPRO with dA might mediate NO release from irradiated NPRO.

We present ultrafast photoelectron spectroscopy of the charge-transfer-to-solvent reaction in a segregated TBAI (tetrabutylammonium iodide) molecular layer in aqueous solution. The reaction times and electron binding energies of transient species vary with TBAI concentration from a very low value of 1 × 10

Previously we demonstrated the anti-tumorigenic, anti-mutagenic and anti-inflammatory effects of the juice of Vitis coignetiae (yamabudo), and identified caftaric acid as an anti-mutagenic component from the juice. In the present study, we investigated the isolation of anti-inflammatory components in yamabudo juice supposing that the anti-inflammatory components in yamabudo are also responsible for the anti-tumorigenic activity. The suppressing effect on nitric oxide production in mouse leukemic monocyte with LPS was used as a separation marker. Three components comprising 2,6-dimethoxy-1,4-benzoquinone (DBQ), fertaric acid and caftaric acid were isolated and identified from the juice of V. coignetiae as anti-inflammatory ingredients. Inhibitory effects were found of DBQ on the mutagenicity of dimethylbenzo[a]anthracene, aflatoxin B1, 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2) and amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) in the Ames test. Topical application of DBA significantly inhibited TPA-induced edema of mouse ears. The anti-tumorigenic effect of DBQ on the promotion and initiation stages of mouse skin tumorigenesis was investigated, and topical administration of DBQ on the promotion stage significantly decreased tumor development in mice skin. DBQ is a potential candidate for the chemopreventive effect of V. coignetiae.

The photoinduced ring-opening reaction of 1,3-cyclohexadiene (CHD) to produce 1,3,5-hexatriene (HT) plays an essential role in the photobiological synthesis of vitamin D3 in the skin. This reaction follows the Woodward-Hoffmann rule, and C5-C6 bond rupture via an electronically excited state occurs with conrotatory motion of the end CH2 groups. However, it is noted that the photoexcited S1(π,π*) state of CHD is not electronically correlated with the ground state of HT, and the reaction must proceed via nonadiabatic transitions. In the present study, we have clearly observed the nonadiabatic reaction pathway via the doubly excited state of CHD using ultrafast extreme UV photoelectron spectroscopy. The results indicate that the reaction occurs in only 68 fs and creates product vibrational coherence. Extensive computational simulations support the interpretation of experimental results and provide further insights into the electronic dynamics in this paradigmatic electrocyclic ring-opening reaction.

The structure of the solvated electron in methanol is less studied but more complicated than the one of the hydrated electron. In this condensed-phase first principles molecular dynamics study we reveal the nature of the recently discovered shallow and deep trap states of the excess electron and suggest a more complex picture including four bound cavity states classified by the number of the hydroxy-groups coordinated to the electron, their binding energy gradually increasing with the OH-coordination. The initial shallow bound states are formed via a transient diffusion mechanism, in a trap-seeking fashion, whereas, deeper bound states are formed via a slower methanol molecules reorientation. Despite apparent similarity of the absorption spectrum of the solvated electron in methanol to that in water, the origin of the absorption maximum is drastically different. The previously assumed model of hydrogenic transitions (s-p etc.) as is the case in water does not hold for methanol. Instead, the main bands arise due to the charge-transfer states, promoting the excess electron to the nearby cavity, naturally abundant in this solvent. We propose an alternative simple model to describe electronic states of the solvated electron in methanol: the double square well.

The structure of the solvated electron in methanol is less studied but more complicated than the one of the hydrated electron. In this condensed-phase first principles molecular dynamics study we reveal the nature of the recently discovered shallow and deep trap states of the excess electron and suggest a more complex picture including four bound cavity states classified by the number of the hydroxy-groups coordinated to the electron, their binding energy gradually increasing with the OH-coordination. The initial shallow bound states are formed via a transient diffusion mechanism, in a trap-seeking fashion, whereas, deeper bound states are formed via a slower methanol molecules reorientation. Despite apparent similarity of the absorption spectrum of the solvated electron in methanol to that in water, the origin of the absorption maximum is drastically different. The previously assumed model of hydrogenic transitions (s-p etc.) as is the case in water does not hold for methanol. Instead, the main bands arise due to the charge-transfer states, promoting the excess electron to the nearby cavity, naturally abundant in this solvent. We propose an alternative simple model to describe electronic states of the solvated electron in methanol: the double square well.

A brief overview is presented on ultrafast spectroscopy and imaging of photochemical reactions by highlighting several experimental studies reported in the last five years. A particular focus is placed on new experiments performed using high-order harmonic generation, X-ray free electron lasers, and relativistic electron beams. Exploration of fundamental chemical reaction dynamics using these advanced experimental methodologies is in an early stage, and exciting new research opportunities await in this rapidly expanding and advancing research field. At the same time, there is no experimental methodology that provides all aspects of the electronic and structural dynamics in a single experiment, and investigations using different methodologies with various perspectives need to be considered in a comprehensive manner.

High-resolution photoelectron (PE) spectra of liquid methanol and ethanol were measured using a liquid microjet and He IIα radiation (40.813 eV). The vertical ionization energy and the ionization threshold were determined as 9.70 ± 0.07 and 8.69 ± 0.07 eV for methanol and 9.52 ± 0.07 and 8.52 ± 0.07 eV for ethanol, respectively. Individual photoemission bands observed for the liquids are well correlated with those in PE spectra of the gaseous samples also measured in the present study, except that the liquid band positions were shifted on average by −1.23 eV for methanol and −1.10 eV for ethanol as compared to the gas. The 5a′ and 7a′ bands of liquid methanol exhibit specifically larger broadening than other bands, for which we attempted spectral fitting with two components, similarly with the case of the 3a1 band of liquid water. PE spectra of both liquid and gaseous ethanol are congested partly due to the presence of the trans and gauche isomers; however, the overall band positions are generally in good agreement with predictions based on quantum chemical calculations. Comparison of the measured PE spectra with experimental and simulated X-ray emission spectra indicate that spectral differences in the lowest ionization band of both methanol and ethanol originate from involvement of nuclear dynamics in the X-ray emission process.

We have designed simplified drive circuit for directly modulated VCSEL in the optical transmitter for 28 GHz band RF signal, and evaluated transmission characteristics such as transmission loss, reflection and error vector magnitude (EVM).

This paper deals with a receiver design for 5G operated as secondary radio in spectrum sharing with different radio system. In the scenario, the receiver suffers from asynchronous interference from the primary system which utilize different transmission waveform parameters from 5G, such as sampling rate and symbol duration. The proposed receiver employs successive interference cancellation of the primary system to decode 5G. For realizing asynchronous cancellation with single front end and ADC, the architecture includes sampling rate conversions of the received and replica signal. Computer simulation shows the proposed receiver can improve performance significantly.

Drones are attractive for their consumer usage. They need high quality wireless communication with ground stations to carry out their flight plans. It is necessary to understand the communication quality between drones and base stations. The radio quality of drone flight site also should be understood. This paper proposes to estimate received radio quality of a drone body and a drone flight area. It also evaluates the proposed method using actual measured radio data at a drone flight site. Our evaluation achieved 4 dB error between the estimation and measured values. This paper also presents a service model of our proposed method.

The photoinduced ring-opening reaction of 1,3-cyclohexadiene to produce 1,3,5-hexatriene is a well-known example of the Woodward-Hoffmann rule for stereochemical reactions governed by molecular orbital symmetry, and it plays an essential role in photobiological synthesis of vitamin D3 in the skin. Since the photoexcited 11B state of 1,3-cyclohexadiene is not electronically correlated to the ground state of 1,3,5-hexatriene, the reaction is expected to proceed via non-adiabatic transitions through a doubly excited 21A electronic state. However, spectroscopic observation of this elusive state has been difficult. Here we present the results of a photoelectron spectroscopy study using table-top ultrafast deep and extreme UV lasers, based on filamentation four-wave mixing and high-harmonic generation, which enabled us to arrest the 21A state. It is shown that the ring-opening reaction takes only 60 fs to complete, which is a considerably shorter time than previous experimental and theoretical estimates. The ballistic reaction creates vibrational coherence in the reaction products.

The ultrafast formation, solvation, and geminate recombination of hydrated electrons upon vacuum ultraviolet photoexcitation of liquid water and the static and dynamic scavenging by NO3- are investigated using femtosecond time-resolved photoelectron spectroscopy. The solvation time constant for excess electrons is typical of that for liquid water but increases slightly with increasing excitation energy. The electron survival probability for geminate recombination is found to be much lower than the literature values owing to previously unobserved ultrafast geminate recombination in a period of 5 ps. NO3- induces the ultrafast (static) scavenging of photoexcited electronic states of liquid water and the dynamic scavenging of detached electrons with a reaction rate that is dependent on the excitation energy. The formation of hydrated electrons at 7.7 eV is ascribed to a H-atom-transfer process, but it is plausible that additional formation channels open at higher energies.