Fluorescence Properties and Exciplex Formation of Emissive Naphthyridine Derivatives: Application as Sensors for Amines

Water-soluble donor–acceptor-type fluorophore 15Nap-Cl having two trifluoromethyl groups and a Cl group on a 1,5-aminonaphthyridine framework was prepared. Fluorophore 15Nap-Cl showed strong solvatochromic fluorescence, and, as the solvent polarity increased, a bathochromic shift was observed accompanied by an increase in the fluorescence quantum yield. In addition, in the presence of amines such as ethylamine, diethylamine, and aniline, further considerable bathochromic shifts in the fluorescence were observed. Density functional calculations identified the source of the fluorescence behavior as exciplex formation between 15-Nap-Cl and the corresponding amine. The fluorescence behavior was exploited to fabricate a sensor that can identify various primary, secondary, and tertiary amines.     

Tin(II)-Based Metal–Organic Frameworks Enabling Efficient,Selective Reduction of CO2 to Formate under Visible Light

Certain metal complexes are known as high-performance CO₂ reduction photocatalysts driven by visible light. However, most of them rely on rare, precious metals as principal components, and integrating the functions of light absorption and catalysis into a single molecular unit based on abundant metals remains a challenge. Metal-organic frameworks (MOFs), which can be regarded as intermediate compounds between molecules and inorganic solids, are potential platforms for the construction of a simple photocatalytic system composed only of Earth-abundant nontoxic elements. In this work, we report that a tin-based MOF enables the conversion of CO₂ into formic acid with a record high apparent quantum yield (9.8 % at 400 nm) and >99 % selectivity without the need for any additional photosensitizer or catalyst. This work highlights a new MOF with strong potential for photocatalytic CO₂ reduction driven by solar energy.     

Making Dimethylamino a Transformable Directing Group by Nickel‐Catalyzed CN Borylation

The dimethylamino (Me₂N) group is arguably the most versatile functional group capable of highly efficient and site‐selective directed aromatic functionalizations at the ortho‐, meta‐, and para‐positions depending on reaction conditions. While the repertoire of Me₂N‐directed reactions is growing at a rapid pace, the lack of a general method to transform this group to other functionalities hampers its wider application in organic synthesis. Here we report nickel‐catalyzed C?N borylations of aryl‐ and benzyl‐dimethylamines that permit the conversion of a huge library of largely underutilized Me₂N‐containing organic molecules into various functional molecules by taking advantage of the wealth of existing C?B functionalization methods.     

Non-synchronous oscillations in four-dimensional nonlinear semelparous Leslie matrix models

In a certain class of semelparous Leslie matrix models, either a positive equilibrium is stable and an invariant set on the boundary of the nonnegative cone is unstable or vice versa generically if the model dimension is two or three. This dynamic dichotomy is expected to be failed in the four-dimensional case. Our study focuses on a semelparous Leslie matrix model with specific nonlinearities and rigorously proves that the dynamic dichotomy does not hold in the four-dimensional case. This result is derived by showing that the four-dimensional semelparous Leslie matrix model can be uniformly persistent with respect to the boundary of the nonnegative cone even if there exists an unstable positive equilibrium. In such a situation, there are no missing age-classes but population oscillation occurs.     

Hydrochlorothiazide Enhances UVA‐Induced DNA Damage

The UVA is currently thought to be carcinogenic because, similar to UVB, it induces the formation of cyclobutane pyrimidine dimers (CPDs). Various drugs have been reported to cause photosensitive drug eruptions as an adverse effect. Although the precise mechanism of photosensitive drug eruption remains to be elucidated, it is generally accepted that free radicals and other reactive molecules generated via UV‐irradiated drugs play important roles in the pathogenesis of photosensitive drug eruptions. The waveband of concern for photo‐reactive drugs is UVA‐visible light, but some extend into the UVB region. We tested whether photosensitive drugs could enhance CPD formation after UVA exposure by using isolated DNA in the presence of several reported photosensitive drugs using high‐performance liquid chromatography. We found that the diuretic agent hydrochlorothiazide (HCT) significantly enhanced the production of TT dimers over a wide range of UVA. Furthermore, we investigated whether UVA plus HCT could enhance CPD production in xeroderma pigmentosum model mice defective in nucleotide excision repair. Immunofluorescence studies showed that CPD formation in the skin significantly increased after 365 nm narrow‐band UVA irradiation in the presence of HCT, compared with that in wild‐type mice. HCT could be used with caution because of its enhancement of UVA‐induced DNA damage.     

Formation of a Ligand‐Assisted Complex of Two RNA Hairpin Loops

The hairpin structure is one of the most common secondary structures in RNA and holds a central position in the stream of RNA folding from a non‐structured RNA to structurally complex and functional ribonucleoproteins. Since the RNA secondary structure is strongly correlated to the function and can be modulated by the binding of small molecules, we have investigated the modulation of RNA folding by a ligand‐assisted formation of loop–loop complexes of two RNA hairpin loops. With a ligand (NCT6), designed based on the ligand binding to the G–G mismatches in double‐stranded DNA, we successfully demonstrated the formation of both inter‐ and intra‐molecular NCT6‐assisted complex of two RNA hairpin loops. NCT6 selectively bound to the two hairpin loops containing (CGG)₃ in the loop region. Native polyacrylamide gel electrophoresis analysis of two doubly‐labeled RNA hairpin loops clearly showed the formation of intermolecular NCT6‐assisted loop–loop complex. Förster resonance energy‐transfer studies of RNA constructs containing two hairpin loops, in which each hairpin was labeled with Alexa488 and Cy3 fluorophores, showed the conformational change of the RNA constructs upon binding of NCT6. These experimental data showed that NCT6 simultaneously bound to two hairpin RNAs at the loop region, and can induce the conformational change of the RNA molecule. These data strongly support that NCT6 functions as molecular glue for two hairpin RNAs.     

Specifications of a neutron exposure accelerator system for biological effects experiments (NASBEE) in NIRS

We developed a neutron irradiation facility, neutron exposure accelerator system for biological effect experiments (NASBEE) for biological studies in National Institute of Radiological Sciences, Japan. Irradiation field of 2 MeV average neutrons generated by a Be(d–n)B reaction is established. Dose uniformity of 240 mm in diameter irradiation field is producible within ±2.5% with a dose rate of 0.87 Gy/h at sample target distance of 1170 mm. Two irradiation rooms, a specific pathogen-free (SPF) conditioned one and a conventional, are now available. Irradiation protocols for in vitro experiments are now established and demonstrated by obtaining a relative biological effectiveness (RBE) of cell inactivation measured to be 3.54 with 10% survival dose (D₁₀).     

RNA Aptamers That Reversibly Bind Photoresponsive Azobenzene‐Containing Peptides

Modulation of biological networks assembled by diverse interactions among biologically active molecules has provided a platform for innovative biotechnologies. Here, we report RNA aptamers that bind to a photoresponsive peptide (KRAzR; Lys‐Arg‐azobenzene‐Arg) containing azobenzene chromophore, which can change its structure by photoirradiation. Aptamers were identified after 10 cycles of an in vitro selection procedure starting with a DNA library containing a 70 nt random region. Surface plasmon resonance (SPR) analysis demonstrated that interactions between aptamers and KRAzR were fully controlled by appropriate photoirradiation to the SPR sensor chip. Upon irradiation of 360 nm on the KRAzR‐immobilized surface, the binding of each aptamer to the surface was significantly decreased. Subsequent photoirradiation of the same surface with 430 nm restored the aptamer binding to the surface. We also observed that direct photoirradiation of the aptamer–peptide complex on a gold surface actively promoted dissociation of the complex. Furthermore, a doped reselection method was applied to acquire structural and sequence information of aptamer 66. From a data analysis of the conserved region and the mutation frequency, we were able to select a plausible secondary structure among three candidates predicted by computational folding simulation.     

Structural and electronic properties of a new molecular conductor, α-(BEDT-TTF)2CsCd(SCN)4

Structural and electronic properties of a new BEDT-TTF based radical cation salt, α-(BEDT-TTF)₂CsCd(SCN)₄, are presented. In the measurements of the electrical resistivity and the magnetic susceptibility, this new α-type salt shows metallic behavior down to low temperature. Measurements of the resistivity under in-plane c-axial strain reveal a newly observed insulating phase, suggesting that α-(BEDT-TTF)₂CsCd(SCN)₄ is placed near an insulating phase which might have close relationships with a superconducting phase realized in α-type salts.