NanoPARCEL: a method for controlling cellular behavior with external light

We developed a simple preparation procedure for the protein encapsulated nanoparticle and used the nanoparticle for spatiotemporal activity control of various proteins. We succeeded in the local protein activation within cells by light using the nanoparticle.     

Formal total synthesis of (−)-hamigeran B from a chemo-enzymatically prepared building block with quaternary chiral center

A formal total synthesis of (?)-hamigeran B was achieved in 17 steps from commercially available ethyl 2-oxocyclopentanecarboxylate. Carbonyl reductase-catalyzed asymmetric reduction and the subsequent chemical transformations furnished an enantiomerically pure synthetic intermediate, (R)-5-formyl-2-isopropyl-5-methylcyclopent-1-en-1-yl trifluoromethylsulfonate. Suzuki-Miyaura coupling with Gao's arylboronate [2-(2-formyl-3-methoxy-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane], under PdCl₂(dppf)?CH₂Cl₂ catalysis, and the subsequent cyclization by way of intramolecular reductive SmI₂-mediated 1,2-diol formation provided a tricyclic skeleton with a tetrasubstituted double bond between C-1 and C-9b. Upon hydrogenation of this double bond, the proper stereochemistry of the remaining chiral centers was established. Exclusive addition of the hydrogen atom from the β-face occurred, owing to the shielding of the α-face with a bulky TBS protective group on the C-4 alcohol. The hydrogenation products were transformed into Clive's synthetic precursor for (?)-hamigeran B.     

Generation of high-contrast and high-intensity laser pulses using an OPCPA preamplifier in a double CPA, Ti:sapphire laser system

We demonstrate a high-contrast, high-intensity double chirped-pulse amplification (CPA) Ti:sapphire laser system using an optical parametric chirped-pulse (OPCPA) pre- amplifier. By injecting cleaned microjoule seed pulses into the OPCPA, a temporal contrast greater than 10¹⁰ within picosecond times before the main femtosecond pulse is demonstrated with an output pulse energy of 1.7 J and a pulse duration of 30 fs, corresponding to a peak power of 60 TW at a 10 Hz repetition rate. This system uses a cryogenically-cooled Ti:sapphire final amplifier and generates focused peak intensities in excess of 10²⁰ W/cm².     

Signal quality improvement of holographic data storage using adaptive two-dimensional filter

Holographic data storage is being widely studied for the purpose of developing next-generation large optical memories. A prospective use of this type of memory is in building image archives in large-scale data centers. In particular, demand for energy conservation at data centers, and therefore for holographic data storage, is growing. In holographic data storage, interference between bits occurs owing to wave aberration in the optical system, shrinkage of the medium, and crosstalk noise from neighboring holograms during multiplex recording; as a result of the interference, the reproduced image deteriorates and the bit error rate (BER) increases. In this study, to reduce the BER in both off-axis-type recording and coaxial-type recording, a two-dimensional finite impulse response (FIR) filter is applied to a reproduced image that has been recorded by angle multiplex recording and shift multiplex recording. First, for the optimization of the FIR filter coefficients, the linear minimum mean square error (LMMSE) method is applied; this method optimizes the coefficients by reducing the BER. Furthermore, for evaluating the optimization performance of the LMMSE method, the optimization performance is compared with that of the real-coded genetic algorithm (RCGA), which has the capability to search a wide range of coefficients. The optimization by the LMMSE method has been found to be excellent for off-axis-type recording but not for coaxial-type recording. It is speculated that this is because of the brightness irregularity in the reproduced image, resulting from crosstalk. On the other hand, a marked reduction in the BER is observed using the RCGA, despite the brightness irregularity. In this study, the effectiveness of the LMMSE method for signals recorded by coaxial-type recording, in which large brightness irregularity is expected, is examined using automatic gain control (AGC). It is found that the application of AGC reduces the BER even in the case of coaxial-type recording.     

Isotopic Analysis of tungsten using multiple collector-inductively coupled plasma-mass spectrometer coupled with electrothermal vaporization technique

We have developed a micro-electrothermal vaporization (μETV) device for the multiple collector-ICP-mass spectrometry (μETV-MC-ICPMS) to improve analytical precision in the ¹⁸²W/¹⁸³W and ¹⁸⁴W/¹⁸³W ratio measurements from nanogram quantities of W. The W solution was loaded onto the Re-filament, and the gradual evaporation of W was achieved by controlling the incident current onto the Re filament and D-Glucose. With the W evaporation under the Ar atmosphere, the measured W isotope ratios became erroneous mainly due to the contribution of signal spikes Ala-Arg-Gly-Phy-Tyr. In strike contrast, signal intensity profile became smooth when the He ambient/carrier gas was employed, and this resulted in better precision in the isotope ratio measurements. The measured UV–vis isotope ratio data obtained with present μETV technique were significantly deviated from the ratio data obtained with solution nebulization technique, mainly due to the contribution of the isotope fractionation effect through the evaporation process. Rigorous testing for the correction of the isotope fractionation processes pH–activity curve revealed that the Rayleigh fractionation law, rather than the conventional exponential law, provided the most reliable ratio data (1.851720 ± 0.000018 for ¹⁸²W/¹⁸³W and 2.141248 ± 0.000028 for ¹⁸⁴W/¹⁸³W ratios), which agreed well with the ratio data obtained through the conventional solution nebulization technique (1.851718 ± 0.000039 for ¹⁸²W/¹⁸³W and 2.141248 ± 0.000022 for ¹⁸⁴W/¹⁸³W). Moreover, mass dependency for the mass fractionation law suggested that W was evaporated as oxides (WO₃), rather than the metallic form (W), from the Re filament, and therefore, information concerning the chemical form of the analytes could also be derived by the ETV technique developed in this study. The data presented here demonstrate clearly that the ETV sample introduction technique has a potential to become a sensitive tool for the precise isotope analysis for the MC-ICPMS technique.     

Antioxidant effects of photodegradation product of nifedipine

Recently, increasing evidence suggests that the antihypertensive drug nifedipine acts as a protective agent for endothelial cells, and that the activity is unrelated to its calcium channel blocking. Nifedipine is unstable under light and reportedly decomposes to a stable nitrosonifedipine (NO-NIF). NO-NIF has no antihypertensive effect, and it has been recognized as a contaminant of nifedipine. The present study for the first time demonstrated that NO-NIF changed to a NO-NIF radical in a time-dependent manner when it interacted with human umbilical vein endothelial cells (HUVECs). The electron paramagnetic resonance (EPR) signal of NO-NIF radicals in HUVECs showed an asymmetric pattern suggesting that the radicals were located in the membrane. The NO-NIF radicals had radical scavenging activity for 1,1-diphenyl-2-picrylhydrazyl, whereas neither NO-NIF nor nifedipine did. In addition, the NO-NIF radical more effectively quenched lipid peroxides than NO-NIF or nifedipine. Furthermore, NO-NIF attenuated the superoxide-derived free radicals in HUVECs stimulated with LY83583, and suppressed iron-nitrilotriacetic acid (Fe-NTA)-induced cytotoxicity in rat pheochromocytoma (PC12) cells. Our findings suggest that NO-NIF is a candidate for a new class of antioxidative drugs that protect cells against oxidative stress.