NMR and MO Studies on the Molecular Structure of a Fluoranthene-Benzene Complex

Summary. Fluoranthene (FA) forms a 1:1 van der Waals complex with benzene in cyclohexane. The ¹H NMR spectrum of this complex shows that the FA moiety in the complex state has five kinds of hydrogen atoms and that the ¹H NMR peaks assigned to the protons attached to the naphthalene skeleton are largely shifted to higher magnetic field on complex formation with benzene. These observations indicate that the complex takes the structure of C_S symmetry, in which the benzene molecule mainly interacts with the electronic system localized on the naphthalene moiety of FA. The present ab initio calculations reproduce well the ¹H NMR spectral shifts mentioned above and the experimentally predicted C_S structure of the complex. According to the PPP calculations for the electronic absorption spectral changes on the complex formation, the FA-benzene complex is considered to take a sandwich type structure.     

Antihypertensive Effect of Angiotensin‐Converting Enzyme Inhibitory Peptide Obtained from Hen Ovotransferrin

Angiotensin I‐converting enzyme (ACE) inhibitory peptide was isolated from the hen ovotransferrin hydrolysate using chymotryptic hydrolysis by two steps of reverse‐phase high‐performance liquid chromatography. The amino sequence of this novel peptide was identified as Lys‐Val‐Arg‐Glu‐Gly‐Thr‐Thr‐Tyr that inhibited ACE activity in vitro in a concentration‐dependent manner with an effective concentration (IC₅₀) of 102.8 μM. Also, this inhibition was identified as noncompetitive using the Lineweaver‐Burk plot. Moreover, the antihypertensive action of this novel peptide was investigated by an intravenous injection into spontaneously hypertensive rats (SHR). A dose‐dependent reduction of systolic blood pressure by this peptide was observed after 40 min of treatment and it decreased the blood pressure markedly at the maximal dose (1 nmol/mL/kg). The maximal blood pressure lowering activity of this peptide was calculated as 163% of captopril (10 pmol/mL/kg) that was used as positive control. In conclusion, the obtained data suggests that Lys‐Val‐Arg‐Glu‐Gly‐Thr‐Thr‐Tyr has an ability to inhibit ACE activity and decrease the systolic blood pressure in hypertensive animals.     

Selective growth of ag nanowires on Si(111) surfaces by electroless deposition

Electroless deposition of Ag on atomically flat H-terminated Si(111) surfaces in aqueous alkaline solutions containing Ag ions produced two different sizes of Ag nanowires along atomic step edges: (1) a narrow nanowire of 10 nm in width and 0.5 nm in height and (2) a wide nanowire of 35 nm in width and 11 nm in height. The narrow and wide nanowires were formed by immersion in the solutions containing less than 1 ppb and 8 ppm dissolved-oxygen concentrations, respectively. This result indicates that the dissolved oxygen initiates the formation of Ag nucleation sites and that the fabrication method has a possibility of controlling the size of Ag nanowires.     

Rational design of CH/pi interaction sites in a basic resolving agent

A novel synthetic basic resolving agent, cis-1-aminobenz[f]indan-2-ol (ABI), was rationally designed by introducing effective CH/pi interaction sites to cis-1-aminoindan-2-ol (AI), whose chiral recognition ability has been reported from our laboratory. ABI was applicable to a wide variety of racemic arylalkanoic acids and showed moderate to excellent chiral recognition ability, which was obviously higher than that of AI. The fundamental and important role of CH/pi interactions, such as tunable CH(sp(2))/pi and CH(sp(3))/pi interactions, in the chiral recognition by ABI was revealed by X-ray crystallographic study.     

Synthesis of Arenethiolate Complexes of Divalent and Trivalent Lanthanides from Metallic Lanthanides and Diaryl Disulfides: Crystal Structures of [{Yb(hmpa)(3)}(2)(&mgr;-SPh)(3)][SPh] and Ln(SPh)(3)(hmpa)(3) (Ln = Sm, Yb; hmpa = Hexamethylphosphoric Triamide)

A convenient and one-pot synthetic method of lanthanide thiolate compounds was developed. An excess of metallic samarium, europium, and ytterbium directly reacted with diaryl disulfides in THF to give selectively Ln(II) thiolate complexes, [Ln(SAr)(&mgr;-SAr)(thf)(3)](2) (1, Ln = Sm; 2, Ln = Eu; Ar = 2,4,6-triisopropylphenyl), Yb(SAr)(2)(py)(4) (3, py = pyridine), and [{Ln(hmpa)(3)}(2)(&mgr;-SPh)(3)][SPh] (6, Ln = Sm; 7, Ln = Eu; 8, Ln = Yb; hmpa = hexamethylphosphoric triamide). Reaction of metallic lanthanides with 3 equiv of disulfides afforded Ln(III) thiolate complexes, Ln(SAr)(3)(py)(n)()(thf)(3)(-)(n)() (9a, Ln = Sm, n = 3; 9b, Ln = Sm, n = 2; 10, Ln = Yb, n = 3) and Ln(SPh)(3)(hmpa)(3) (11, Ln = Sm; 12, Ln = Eu; 13, Ln = Yb). Thus, Ln(II) and Ln(III) thiolate complexes were prepared from the same source by controlling the stoichiometry of the reactants. X-ray analysis of 8 revealed that 8 has the first ionic structure composed of triply bridged dinuclear cation and benezenethiolate anion [8, orthorhombic, space group P2(1)2(1)2(1) with a = 21.057(9), b = 25.963(7), c = 16.442(8) ?, V = 8988(5) ?(3), Z = 4, R = 0.040, R(w) = 0.039 for 5848 reflections with I > 3sigma(I) and 865 parameters]. The monomeric structures of 11 and 13 were revealed by X-ray crystallographic studies [11, triclinic, space group P&onemacr; with a = 14.719(3), b = 17.989(2), c = 11.344(2) ?, alpha = 97.91(1), beta = 110.30(2), gamma = 78.40(1) degrees, V = 2751.9(9) ?(3), Z = 2, R = 0.045, R(w) = 0.041 for 7111 reflections with I > 3sigma(I) and 536 parameters; 13, triclinic, space group P&onemacr; with a = 14.565(2), b = 17.961(2), c = 11.302(1) ?, alpha = 97.72(1), beta = 110.49(1), gamma = 78.37(1) degrees, V = 2706.0(7) ?(3), Z = 2, R = 0.031, R(w) = 0.035 for 9837 reflections with I > 3sigma(I) and 536 parameters]. A comparison with the reported mononuclear and dinuclear lanthanide thiolate complexes has been made to indicate that the Ln-S bonds weakened by the coordination of HMPA to lanthanide metals have ionic character.     

Essential of Proline and Valine Residues in the Peptide Derived from Lactoferrin for Angiotensin Converting Enzyme Inhibition

We synthesized Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu, the peptide contained in lactoferrin (Lf), to identify the angiotensin converting enzyme (ACE) inhibition. In an attempt to know the structure‐activity relationship of this peptide, we replaced Pro (the third amino acid residues from N‐terminal) or Val (the fourth amino acid residues from N‐terminal) with Ala (neutral amino acid), Glu (acidic amino acid) or Lys (basic amino acid) to produce six peptides. From the in vitro ACE inhibition (IC₅₀) of these synthesized peptides, the original peptide (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu) showed higher ACE inhibition than the replaced six peptides. Thus, replacement of Pro at the third amino acid residues or Val at the fourth position with Ala, Glu or Lys revealed the ACE inhibition to be lower than the original form of Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu. Otherwise, we added one peptide at the C‐terminal of Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu and found both products with an addition of Val (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu‐Val) or Ile (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu‐Ile) showing a lower ACE inhibition than the original one. The ACE inhibitions produced by both replaced peptides were without significance. Also, deletion of the last peptide at the C‐terminal (Leu‐Arg‐Pro‐Val‐Ala‐Ala) failed to produce a marked change of ACE inhibition as compared to the original one. These results suggest that Pro and Val are essential in the peptide for inhibition of ACE activity.     

Synthesis and alpha-glucosidase-inhibiting activity of a new alpha-glucosidase inhibitor, 4-O-alpha-D-glucopyranosylmoranoline and its N-substituted derivatives

Various N-substituted derivatives of 4-O-alpha-D-glucopyranosylmoranoline have been synthesized, and their inhibitory activities against rabbit sucrase and maltase have been measured, as well as their effects on postprandial hyperglycemia in the sucrose-loaded rat, 4-O-alpha-D-Glucopyranosylmoranoline was also shown to have potent hypoglycemic activity in starch-loaded dogs.