Design of polymeric carriers for cancer-specific gene targeting: utilization of abnormal protein kinase Calpha activation in cancer cells

We succeeded in cancer cell specific gene expression by using a polyplex responsive to protein kinase Calpha, which is activated in various types of cancer cells.     

Nernstian adsorbate-like bulk layer of organic radical polymers for high-density charge storage purposes

Redox polymer layers with 2,2,6,6-tetramethylpiperidin-1-oxyl-4-yl (TEMPO) groups showed nernstian adsorbate-like electrochemical behaviors up to submicrometer thicknesses, based on a fast charge propagation within the bulk layer and persistency in electrolyte solutions.     

Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl‐alkylamine Ligands on Spin Crossover Properties

Iron(II) complexes of the type [Fe(L)(NCS)₂] with tetradentate ligands L are well known to show spin crossover properties. However, this behavior is quite sensitive in regard to small changes of the ligand system. Starting from the thoroughly investigated complex [Fe(tmpa)(NCS)₂] [tmpa = tris(2‐pyridylmethyl)amine, also abbreviated as tpa in the literature] we modified the ligand by increasing systematically the chelate ring sizes from 5 to 6 thus obtaining complexes [Fe(pmea)(NCS)₂], [Fe(pmap)(NCS)₂], and [Fe(tepa)(NCS)₂] [pmea = N,N‐bis[(2‐pyridyl)methyl]‐2‐(2‐pyridyl)ethylamine, pmap = N,N‐bis[2‐(2‐pyridyl)ethyl]‐(2‐pyridyl)methylamine, and tepa = tris[2‐(2‐pyridyl)ethyl]amine]. All complexes were structurally characterized and spin crossover properties were investigated using Mößbauer spectroscopy, magnetic measurements, and IR/Raman analyses. The results demonstrated that only the iron complexes with tmpa and pmea showed spin crossover properties, whereas the complexes with the ligands pmap and tepa only formed high spin complexes. Furthermore, DFT calculations supported these findings demonstrating again the strong influence of ligand environment. Herein the effect of increasing the chelate ring sizes in iron(II) isothiocyanato complexes with tetradentate tripyridyl‐alkylamine ligands is clearly demonstrated.     

Biological properties of opioid peptides replacing Tyr at position 1 by 2,6-dimethyl-Tyr.

To understand the effect of the replacement of Tyr residue at position 1 in opioid peptides by 2,6-dimethyl-Tyr (Dmt) on the biological property, chiral (D or L) Dmt1 analogs of Leu-enkephalin (Enk) and Tyr-D-Arg-Phe-beta Ala-NH2 (YRFB) were synthesized and their enzymatic stabilities, in vitro bioactivities and receptor binding affinities compared with those of parent peptides. [L-Dmt1]Enk (1) exhibited 4-fold higher stability against aminopeptidase-M and possessed dramatically increased activities in guinea pig ilium (GPI) (187-fold) and mouse vas deferens (MVD) (131-fold) assays, and in rat brain receptor binding assays (356-fold at mu receptor and 46-fold at delta receptor) as compared to Enk. [L-Dmt1]YRFB (3) also exhibited increased activities in GPI (46-fold) and MVD (177-fold) assays, and in the binding assays (69-fold at mu receptro and 341-fold at delta receptor) as compared to the parent peptide. [D-Dmt1]Enk (2) and [D-Dmt1]YRFB (4) exhibited activities with diminished or lesser potency than the parent peptide in all assays. These results indicate that there is a tendency for mu affinity to be enhanced more than delta affinity with introduction of L-Dmt into delta ligand peptide (Enk), and for delta affinity to be enhanced more than mu affinity in case of mu ligand peptide (YRFB), resulting in reduced receptor selectivities at the receptors.     

Ion polarisation-assisted hydrogen-bonded ferroelectrics in liquid crystalline domains

An alkylamide-substituted (−NHCOC₁₀H₂₁) hydrogen-bonded dibenzo[18]crown-6 derivative (1) was prepared to stabilise the ionic channel structure in a discotic hexagonal columnar (Col_h) liquid crystal. The introduction of simple M⁺X⁻ salts such as Na⁺PF₆⁻ and K⁺I⁻ into the ionic channel of 1 enhanced the ionic conductivity of the Col_h phase of the M⁺·(1)·X⁻ salts, with the highest ionic conductivity reaching ∼10⁻⁶ S cm⁻¹ for K⁺·(1)·I⁻ and Na⁺·(1)·PF₆⁻ at 460 K, which was approximately 5 orders of magnitude higher than that of 1. The introduction of non-ferroelectric 1 into the ferroelectric N,N′,N′′-tri(tetradecyl)-1,3,5-benzenetricarboxamide (3BC) elicited a ferroelectric response from the mixed Col_h phase of (3BC)_x(1)_1−x with x = 0.9 and 0.8. The further doping of M⁺X⁻ into the ferroelectric Col_h phase of (3BC)_0.9(1)_0.1 enhanced the ferroelectric polarisation assisted by ion displacement in the half-filled ionic channel for the vacant dibenzo[18]crown-6 of (3BC)_0.9[(M⁺)_0.5·(1)·(X⁻)_0.5]_0.1.

An alkylamide-substituted (−NHCOC₁₀H₂₁) hydrogen-bonded dibenzo[18]crown-6 derivative (1) was prepared to stabilise the ionic channel structure in a discotic hexagonal columnar (Col_h) liquid crystal.     

Stereoregulation in cationic polymerization by designed Lewis acids. II. Effects of alkyl vinyl ether structure

Stereoregulation in the cationic polymerization of various alkyl vinyl ethers was investigated with bis[(2,6‐diisopropyl)phenoxy]titanium dichloride ( 1 ; catalyst) in conjunction with the HCl adduct of isobutyl vinyl ether as an initiator in n‐hexane at −78 °C. The tacticities depended on the substituents of the monomers. Isobutyl and isopropyl vinyl ethers gave highly isotactic polymers (mm = 83%), whereas tert‐butyl and n‐butyl vinyl ethers resulted in lower isotactic contents (mm ∼ 50%) similar to those for TiCl₄, a conventional Lewis acid, thus indicating that the steric bulkiness of the substituents was not the critical factor in stereoregulation. A statistical analysis revealed that the high isospecificity was achieved not by the chain end but by the catalyst 1 or the counteranion derived therefrom. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1060–1066, 2001     

Thermotropic Liquid Crystalline Polymers Having Five‐Membered Heterocycles as Mesogens, 7. Synthesis and Photoluminescent Properties of Semi‐Rigid Thermotropic Liquid Crystalline Polyesters Based on a Quaterphenyl Analog of 2,2′‐Bis(1,3,4‐thiadiazole)

New semi‐rigid thermotropic liquid crystalline (LC) polyesters composed of a quaterphenyl analogue of 2,2′‐bis(1,3,4‐thiadiazole) were synthesized by high‐temperature solution polycondensation of a dioxydiundecanol derivative of 5,5′‐diphenyl‐2,2′‐bis(1,3,4‐thiadiazole) with four diacyl chlorides, whose structures were characterized by FT‐IR and ¹³C NMR spectroscopy, as well as elemental analysis. Differential scanning calorimetry (DSC) measurements and texture observations using polarizing microscopy displayed that all the polyesters form stable enantiotropic smectic and/or nematic LC phases. Solution and solid state absorption and fluorescence spectra indicated that the polyesters show absorption maxima arising from the 2,2′‐bis(1,3,4‐thiadiazole) moiety and emit bluish green light, the Stokes shifts being 129 nm in solution and 60–64 nm in the solid state. Band gap energies of the polyesters calculated from the solid state absorption spectra were 2.67–2.82 eV.     

Calculation of hydration free energy for a solute with many atomic sites using the RISM theory: A robust and efficient algorithm

We have developed an algorithm for solving the reference interaction site model (RISM) equations for water near a solute molecule with many atomic sites (interaction sites). It is a hybrid of the Newton–Raphson and Picard methods and is judiciously constructed. Various considerations are given so that the computer time can be saved as much as possible. The robustness and high efficiency of the algorithm has been demonstrated for calculating hydration free energies of Met-enkephalin (a peptide with 75 sites) with different conformations. The Jacobian matrix is treated as part of the input data, and it has been found that the same matrix can be used for a considerably large set of different conformations of the solute molecule. © 1997 John Wiley & Sons, Inc. J Comput Chem 18: 1320–1326, 1997