Radical-mediated stannylation of vinyl sulfones: access to novel 4′-modified neplanocin A analogues

Synthesis of 4′-substituted (halogeno, phenyl, ethynyl, and cyano) neplanocin A analogues was carried out. A cyclopentenol derivative having a vinylstannane structure was designed as key-intermediate in this study, which was prepared based on radical-mediated sulfur-extrusive stannylation. The resulting stannylated cyclopentenol 15 was successfully condensed with 6-chloropurine through the Mitsunobu reaction, leading to the carbocyclic nucleoside 20. Compound 20 was converted to its adenine counterpart 21 by treatment with NH₃/MeOH, during which the 4′-stannyl group remained intact. The title compounds were prepared by using 21 or the 4′-iodo derivative (22) mostly through the Stille reaction.     

Theoretical study of M(PH3)2 complexes of C60, corannulene (C20H10), and sumanene (C21H12) (M = Pd or Pt). Unexpectedly large binding energy of M(PH3)2(C60)

DFT and MP2 to MP4(SDQ) methods were applied to M(PH3)2(C60), Pt(PH3)2(C20H10), and Pt(PH3)2(C21H12) (M = Pd or Pt, C20H10 = corannulene, and C21H12 = sumanene). The binding energy considerably fluctuates around MP2 and MP3 levels but much less upon going from MP3 to MP4(SDQ) in Pt(PH3)2(C2H4), Pt(PH3)2(C20H10), and Pt(PH3)2(C21H12). Also, the MP4(SDQ) method presents a binding energy similar to that of the CCSD(T) method in Pt(PH3)2(C2H4). Thus, it is likely that the MP4(SDQ) method is useful to evaluate binding energies of these complexes. The binding energies of Pt(PH3)2(C20H10) and Pt(PH3)2(C21H12) are evaluated to be 24.9 and 26.1 kcal/mol, respectively, by the MP4(SDQ) method and only +5.8 and -2.6 kcal/mol, respectively, by the DFT(B3LYP) method. These MP4(SDQ)-calculated binding energies of Pt(PH3)2(C20H10) and Pt(PH3)2(C21H12) are similar to that of Pt(PH3)2(C2H4), which strongly suggests that these complexes can be successfully synthesized. The binding energy of Pt(PH3)2(C60) is evaluated to be 44.8 and 45.5 kcal/mol with the ONIOM(MP4(SDQ):UFF) and ONIOM(MP4(SDQ):B3LYP) methods, respectively, and that of the Pd analogue is evaluated to be 39.9 kcal/mol with the ONIOM(MP4(SDQ):UFF) method, whereas the DFT(B3LYP), DFT(BVP86), and DFT(BPW91) methods provide much smaller binding energies. It is noted that these binding energies are much larger than those of the ethylene, corannulene, and sumanene analogues. This difference is reasonably interpreted in terms that the LUMO of C60 is at much lower energy than those of ethylene, corannulene, and sumanene. We investigated also how to separate the high level and the low level regions in the ONIOM calculation of M(PH3)2(C60) and proposed here the reasonable way to evaluate the binding energy of transition-metal complexes of C60.     

NO-induced activation mechanism of the heme-regulated eIF2alpha kinase

The heme-regulated eukaryotic initiation factor 2alpha (eIF2alpha) kinase (HRI), which is found primarily in reticulocytes, contains an N-terminal heme-binding domain (NT-HBD). Binding of NO to the heme iron of the NT-HBD of HRI activates its eIF2alpha kinase activity, thus inhibiting the initiation of translation in reticulocyte lysate. The EPR spectrum of the NO-bound NT-HBD showed several derivative-shaped lines around g = 2.00, which is one of the well-documented signature patterns of a six-coordinate NO complex with histidine as the axial ligand. This is in sharp contrast to that of another prototypical NO-sensor protein, soluble guanylate cyclase (sGC), in which the NO binding to the heme iron disrupts the iron-histidyl bond forming a five-coordinate NO. The NO-mediated activation of HRI is, therefore, not triggered by the cleavage of the iron-histidyl bond. As evidenced by the resonance Raman spectra, two inactive forms of HRI, the ferrous ligand-unbound and the CO-bound states of the NT-HBD, contain a six-coordinate complex as found for the NO complex, indicating that the replacement of the sixth ligand of the heme iron is not sufficient to trigger the activation of HRI. Because the configuration of liganded NO is different from that of liganded CO, we propose that specific interactions between liganded NO and surrounding amino acid residues, which would not be formed in the CO complex, are responsible for the NO-induced activation of HRI.     

Gravimetric determination of the abundance ratio of zirconium and hafnium, based on the in situ thermal decomposition of K(4)[(Zr,Hf)(C(2)O(4))(4)].5H(2)O

Careful heating of K(4)[(Zr,Hf)(C(2)O(4))(4)].5H(2)O results in a two-step thermal decomposition which can be written as: K(4)[(Zr,Hf(C(2)O(4))(4)].5H(2)O --> K(4)[(Zr,Hf)(C(2)O(4))(4)] --> {2K(2)CO(3)+(Zr,Hf)O(2)}. The weight-ratio of the successive decomposition products depends on the abundance ratio of Zr and Hf, and forms the basis for the present method of gravimetric determination.     

Synthesis of polypropionamide-ureas from N-mesyloxysuccinimide and diamines

A series of polypropionamide-ureas was synthesized by the polymerization of N-mesyloxysuccinimide with diamines in polar aprotic solvents in the presence of acid acceptors. The polymerization proceeded through the formation of ring-opened adducts, followed by elimination and rearrangement yielding β-isocyanatopropionamide derivatives, which in turn were polymerized to afford polypropionamide-ureas. These polymers had inherent viscosities in the range of 0.1–0.2. Polymers having aliphatic chains which were fusible below 240°C were soluble in acidic solvents, whereas those with aromatic residues dissolved in polar aprotic solvents. Marked decomposition of the polyamide-ureas under thermogravimetric analysis generally occurred at around 320°C under nitrogen.     

The synthesis of new azoniathiahelicenes

Synthesis of new azonia derivatives of thia[6]helicene ( 1 ) and thia[7]helicene ( 2 ) is described. The Knoevenagel condensation of 2‐methylbenzothieno[3,2‐a]quinolizinium salt ( 8 ) with appropriate arylaldehydes yielded 2‐(arylvinyl)benzothieno[3,2‐a]quinolizinium salts ( 9 and 10 ), respectively. Photocyclization of 2‐styrylbenzothieno[3,2‐a]quinolizinium salt ( 8 ) gave 7a‐azonia‐5‐thia[6]helicene ( 1 ) in 63% yield. Similarly, 2‐[2‐(2‐naphthyl)vinyl]benzothieno[3,2‐a]quinolizinium salt ( 10 ) afforded 7a‐azonia‐5‐thia[7]helicene ( 2 ) in 56% yield. The complete and unambiguous assignment of their ¹H‐ and ¹³C‐nmr spectra was performed by utilizing two‐dimensional nmr spectroscopic methods.     

Sliding behavior of water droplets on flat polymer surface

Flat films of methyl methacrylate-fluoroalkyl methacrylate copolymers were prepared, and their hydrophobicity was investigated. It was revealed that the F concentration directly affects the static hydrophobicity on the flat polymer surface in a systematic manner. Furthermore, the sliding behavior of a water droplet on these surfaces depends on the static hydrophobicity; the sliding motion changes from constant velocity to constant acceleration with an increase in the water contact angle.     

Experimental and modeling studies of grain size and moisture content effects on radon emanation

Some models have already been developed to explain the effect of moisture content on the radon emanation fraction of soil. For this purpose, “microscopic” soil models, which are easy to deal with mathematically but cannot take grain size into consideration, have been designed. These previous models consist basically of two opposite grain surfaces and pores between the grains. In the present study, in order to study the effect of not only moisture content but also grain size, we present a simple modeling approach based on two “macroscopic” soil models: (1) a single-grain model and (2) a multiple-grain model. The latter model represents a configuration of spherical grains packed in a simple cubic structure. Based on these soil models and general assumptions, the radon emanation fraction was calculated as a function of grain size or moisture content by Monte Carlo simulation. The results for the multiple-grain model show that the radon emanation fraction is markedly increased with grain sizes ranging from 10 to 100 μm and reaches a constant value of 50% when moisture content is 0% and the radium is uniformly distributed on the grain surface. Moreover, a drastic increase is seen at smaller grain sizes with increasing moisture content. From these results, we concluded that the calculation of radon emanation depends greatly on the pore size between a Ra-bearing grain and a neighboring grain. The validity of the model was also evaluated by comparison to experimental data.