Multifunctionality in Bimetallic LnIII[WV(CN)8]3− (Ln=Gd,Nd) Coordination Helices: Optical Activity,Luminescence, and Magnetic Coupling

Two chiral luminescent derivatives of pyridine bis(oxazoline) (Pybox), (SS/RR)‐iPr‐Pybox (2,6‐bis[4‐isopropyl‐2‐oxazolin‐2‐yl]pyridine) and (SRSR/RSRS)‐Ind‐Pybox (2,6‐bis[8H‐indeno[1,2‐d]oxazolin‐2‐yl]pyridine), have been combined with lanthanide ions (Gd³⁺, Nd³⁺) and octacyanotungstate(V) metalloligand to afford a remarkable series of eight bimetallic CN^?‐bridged coordination chains: {[Ln^III(SS/RR‐iPr‐Pybox)(dmf)₄]₃[W^V(CN)₈]₃}_n ? dmf ? 4 H₂O (Ln=Gd, 1 ‐SS and 1 ‐RR; Ln=Nd, 2 ‐SS and 2 ‐RR) and {[Ln^III(SRSR/RSRS‐Ind‐Pybox)(dmf)₄][W^V(CN)₈]}_n ? 5 MeCN ? 4 MeOH (Ln=Gd, 3 ‐SRSR and 3 ‐RSRS; Ln=Nd, 4 ‐SRSR and 4 ‐RSRS). These materials display enantiopure structural helicity, which results in strong optical activity in the range 200–450 nm, as confirmed by natural circular dichroism (NCD) spectra and the corresponding UV/Vis absorption spectra. Under irradiation with UV light, the Gd^III‐W^V chains show dominant ligand‐based red phosphorescence, with λ_max≈660 nm for 1 ‐(SS/RR) and 680 nm for 3 ‐(SRSR/RSRS). The Nd^III‐W^V chains, 2 ‐(SS/RR) and 4 ‐(SRSR/RSRS), exhibit near‐infrared luminescence with sharp lines at 986, 1066, and 1340 nm derived from intra‐f ⁴F_3/2→⁴I_{9/2,11/2,13/2} transitions of the Nd^III centers. This emission is realized through efficient ligand‐to‐metal energy transfer from the Pybox derivative to the lanthanide ion. Due to the presence of paramagnetic lanthanide(III) and [W^V(CN)₈]^3? moieties connected by cyanide bridges, 1 ‐(SS/RR) and 3 ‐(SRSR/RSRS) are ferrimagnetic spin chains originating from antiferromagnetic coupling between Gd^III (S_Gd=7/2) and W^V (S_W=1/2) centers with J _{1 ‐(SS)}=?0.96(1) cm^?1, J _{1 ‐(RR)}=?0.95(1) cm^?1, J _{3 ‐(SRSR)}=?0.91(1) cm^?1, and J _{3 ‐(RSRS)}=?0.94(1) cm^?1. 2 ‐(SS/RR) and 4 ‐(SRSR/RSRS) display ferromagnetic coupling within their Nd^III‐NC‐W^V linkages.     

Rhodium‐Catalyzed [3+2+2] and [2+2+2] Cycloadditions of Two Alkynes with Cyclopropylideneacetamides

It has been established that a cationic rhodium(I)/H₈‐binap complex catalyzes the [3+2+2] cycloaddition of 1,6‐diynes with cyclopropylideneacetamides to produce cycloheptadiene derivatives through cleavage of cyclopropane rings. In contrast, a cationic rhodium(I)/(S)‐binap complex catalyzes the enantioselective [2+2+2] cycloaddition of terminal alkynes, acetylenedicarboxylates, and cyclopropylideneacetamides to produce spiro‐cyclohexadiene derivatives which retain the cyclopropane rings.     

Direct profiling of the phospholipid composition of adult <Emphasis Type="Italic">Caenorhabditis elegans</Emphasis> using whole-body imaging mass spectrometry

A protocol for the direct analysis of the phospholipid composition in the whole body of adult soil nematode, Caenorhabditis elegans (C. elegans), was developed, which combined freeze-cracking of the exoskeletal cuticle and matrix-assisted laser desorption/ionization-imaging mass spectrometry (MALDI-IMS). Biomolecules in the m/z range from 700 to 900 were more effectively detected in the freeze-cracked than from simple frozen adult nematode bodies. Different distribution of biomolecules was observed in a nematode body when the matrix was applied with a sublimation deposition method. The whole-body IMS technique was applied on genetically deficient mutant C. elegans to combine whole-body lipidomics and genetics, by comparing the fatty acid compositions, especially of the phosphatidylcholine (PC) species, between the wild-type and fat-1 mutants, which lack the gene encoding an n-3 fatty acid desaturase. A significant reduction of PC(20:5/20:5) and PC(20:4/20:5) and a marked increase of PC(20:4/20:4), PC(20:3/20:4), and PC(20:3/20:3) were detected in the fat-1 mutants in positive ion mode. In addition, phospholipid compositions other than PCs were analyzed in negative ion mode. A loss of a possible phosphatidylinositol (PI) with 18:0/20:5 and a compensative accumulation of putative PI(18:0/20:4) were detected in the fat-1 mutants. In conclusion, the whole-body MALDI-IMS technique is useful for the profiling of multiple biomolecules in C. elegans in both intra- and inter-individual levels.     

Water Confined in the Local Field of Ions

Interionic distances are shorter in concentrated ionic solutions, thus instigating the interaction and overlap of hydration shells, as ions become separated by only one or two layers of water molecules. The simultaneous interaction of water with two oppositely charged ions has, so far, only been investigated by computer simulation studies, because the isolated vibrational spectroscopic signature of these molecules remains undetected. Our combined near‐infrared spectroscopic and molecular dynamics simulation studies of alkali halide solutions present a distinct spectral feature, which is highly responsive to depletion of bulk water and merging of hydration shells. The analysis of this spectral feature demonstrates that absorption trends are in good agreement with the law of matching affinities, thus providing the first successful vibrational spectroscopic treatment of this topic. Combined with commonly observed near‐infrared bands, this feature provides a spectral pattern that describes some relevant aspects of ionic hydration.     

Phosphatidylcholine-based nonaqueous photorheological fluids: effect of geometry and solvent

We report a detail study on photoinduced rheological changes in nonaqueous photorheological (PR) fluids obtained with 1,2-diacyl-sn-glycero-3-phosphocholine-based reverse wormlike micelles, 1-palmitoyl-2-oleophosphatidylcholine (POPC)/cyclohexane/H₂O, POPC/isooctane/H₂O, and L-α-dioleophosphatidylcholine (DOPC)/isooctane/H₂O systems. Initially, the mixtures form highly viscoelastic fluids of long, reverse wormlike micelles as confirmed by the rheological measurements. When photosensitive molecule, trans-CA, is added to these mixtures, they exhibit photosensitivity, and the viscoelasticity increases that decreases on UV irradiation. The nature of the substituent on the benzene ring of trans-CA influences the rheology. When hydroxycinnamic acid (HCA) (hydrophilic, ?OH group attached to the benzene ring of CA) is added to DOPC/isooctane/H₂O phase, separation occurs; while with the methoxycinnamic acid (MOCA) and methylcinnamic acid (MCA) (hydrophobic groups, ?OCH₃, and –CH₃ attached to the benzene ring of CA respectively) led to higher viscoelasticity. The study on the effects of position of the substitution on CA reveals the viscosity enhancement is in the order of p-?>?m-?>?o-isomers. The different geometries obtained because of substitution and photoinduced trans-cis isomerisation is responsible for the different rheology as confirmed by the dynamic rheology, the UV absorption, and the ¹H NMR spectrums. The ¹H NMR spectra revealed a change in the solubilization site of CA with irradiation. cis-CA (high solubility in water) is solubilized in the vicinity of water (at the hydrophilic end of DOPC) as compared with trans-CA. This disrupts the 3D networks of reverse wormlike micelles, decreasing the η ₀, plateau modulus, G _0, and relaxation time, τ _R of solution.     

Nonlinear viscoelasticity, percolation and particles dispersibility of PVA/aluminum hydroxide composite gels

We investigated the rheological properties of a composite gel consisting of poly(vinyl alcohol) and aluminum hydroxide particles, and discussed the relation among nonlinear viscoelasticity, percolation and particles dispersibility. The dynamic viscoelastic measurements revealed that the storage modulus at volume fractions ? < 0.04 satisfied with the Krieger-Dougherty equation representing random dispersion of particles. The storage modulus did not show any nonlinear viscoelastic response at ? < 0.04. However, the storage modulus at ? > 0.06 took a value which is far larger than that expected by the equation, indicating heterogeneous distribution of particles. Additionally, the nonlinear viscoelastic response was recognized clearly at ? > 0.06, suggesting a partial contact between particles. The storage modulus at ? > 0.18 showed a further increase satisfied with the percolation theory, therefore, the volume fraction is considered to be the percolation threshold of 3-dimension. Microscopic observations of the gel showed a clear network with a mesh size of few μm that is considered to be a partial network of particles.     

Evolved gas analysis with skimmer interface and ion attachment mass spectrometry for burnout monitoring of organic additives in ceramic processing

A monitoring of the individual pyrolysis of mixed polymer as a binder for ceramic processing was carried out as an application of evolved gas analysis-mass spectrometry (EGA-MS) with a skimmer interface and ion attachment mass spectrometry (IAMS). It could detect characteristic species evolved by the pyrolysis of the organic additives, according to the instrumental advantages as the transmission of the gaseous species with no transformation by the skimmer interface and complete soft ionization for gaseous species by IAMS technique. Further, the pyrolysis behavior of blended polymers as a binder could be monitored individually as EGA curves of characteristic species evolved by the pyrolyses.     

A Fluorescent Probe for Rapid,High-Contrast Visualization of Folate-Receptor-Expressing Tumors In Vivo

Folate receptors (FRs) are membrane proteins involved in folic acid uptake, and the alpha isoform (FR-α) is overexpressed in ovarian and endometrial cancer cells. For fluorescence imaging of FRs in vivo, the near-infrared (NIR) region (650–900 nm), in which tissue penetration is high and autofluorescence is low, is optimal, but existing NIR fluorescent probes targeting FR-α show high non-specific tissue adsorption, and require prolonged washout to visualize tumors. We have designed and synthesized a new NIR fluorescent probe, FolateSiR-1 , utilizing a Si-rhodamine fluorophore having a carboxy group at the benzene moiety, coupled to a folate ligand moiety through a negatively charged tripeptide linker. This probe exhibits very low background fluorescence and afforded a tumor-to-background ratio (TBR) of up to 83 in FR-expressing tumor-bearing mice within 30 min. Thus, FolateSiR-1 has the potential to contribute to the research in the field of biology and the clinical medicine.     

X-ray absorption spectroscopic studies on solid oxide fuel cells and proton-conducting ceramic fuel cells

X-ray absorption spectroscopy (XAS) is one of the best techniques to obtain the information on the electronic and local structures of materials. In the last few decades, XAS becomes a common analytical technique for the investigation of solid oxide fuel cells and proton-conducting ceramic fuel cells. In particular, operando and/or advanced XAS measurements can be recently available with the increased accessibility of synchrotron radiation. In this article, recent trends of solid oxide fuel cell and proton-conducting ceramic fuel cell researches using XAS are overviewed.