Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis,Structure, and Properties

Novel pyrene‐fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17‐hexakis(2,6‐dimethylphenoxy)‐22,25‐diaza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz‐pyrene)(OC₈H₉)₆] ( 1 ) and 2,3,9,10‐tra(2,6‐dimethylphenoxy)‐15,18,22,25‐traza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz‐pyrene)₂(OC₈H₉)₄] ( 2 ) were isolated for the first time. These unsymmetrical pyrene‐fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene‐fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X‐ray diffraction analysis of 1 , representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene.     

Sulfono‐γ‐AApeptides as a New Class of Nonnatural Helical Foldamer

Foldamers offer an attractive opportunity for the design of novel molecules that mimic the structures and functions of proteins and enzymes including biocatalysis and biomolecular recognition. Herein we report a new class of nonnatural helical sulfono‐γ‐AApeptide foldamers of varying lengths. The crystal structure of the sulfono‐γ‐AApeptide monomer S6 illustrates the intrinsic folding propensity of sulfono‐γ‐AApeptides, which likely originates from the bulkiness of tertiary sulfonamide moiety. The two‐dimensional solution NMR spectroscopy data for the longest sequence S1 demonstrates a 10/16 right‐handed helical structure. Optical analysis using circular dichroism further supports well‐ defined helical conformation of sulfono‐γ‐AApeptides in solution containing as few as five building blocks. Future development of sulfono‐γ‐AApeptides may lead to new foldamers with discrete functions, enabling expanded application in chemical biology and biomedical sciences.     

One-pot Synthesis,Crystal Structures and Antimicrobial Activities of Two New 1,4-Disubstituted 1,2,3-Triazole-4-Carboxylates

Two new 1,4-disubstituted 1,2,3-triazoles-4-carboxylates were synthesized via click reaction. Compound 1a was synthesized by the interaction of 6-nitro-tetrazolo[1.5-a]-pyridine with ethyl propynoate at room temperature in the presence of Cu(OAc)2 as a catalyst and THF as solvent. Compound 1b was also synthesized by the same manner except that tert-butyl propionate, instead of ethyl propynoate, was used. The compounds were characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. Compound 1a(C10H9N5O4) crystallizes in the triclinic system, space group P1 with a = 5.0894(9), b = 8.9834(13), c = 13.089(2) ?, α= 83.041(7), β= 80.256(7), γ=87.296(8)°, V = 585.24(16)?3, Z = 2, Mr = 263.22, crystal size(mm) = 0.37 × 0.20 ×0.18,(I 2σ(I)) = 8557, 2493, 1229, Rint = 0.057. Compound 1b(C12H13N5O4) crystallizes in the monoclinic system, space group P21/c with a = 6.8854(5), b = 21.783(2), c = 9.3986(8) ?,β = 93.239(4)°, V = 1407.4(2)?3, Z = 4, Mr = 291.27, crystal size(mm) = 0.38 × 0.22 × 0.20,(I 2σ(I)) = 11842, 3172, 1866, Rint = 0.047. Antimicrobial assay results showed that the title compounds display excellent activities to different bacterial and fungal strains.     

Synthesis and Crystal Structure of a Novel 14,20-Annulated Pentacyclic Steroid 17(S)-Methyl-13β-hydroxyl-14(R),20(S)-epoxy-pregn-4-en-3-one

The title compound 17(S)-methyl-13β-hydroxyl-14(R),20(S)-epoxy-pregn-4-en-3-one was synthesized by an improved tandem reaction, and its structure was determined by IR, NMR, HR MS and X-ray single-crystal diffraction. The crystal belongs to orthorhombic, space group P212121 with a = 10.55248(15), b = 12.14700(16), c = 14.56841(18) ?, V = 1867.39(4) ?3, Z = 4, Dc= 1.175 g/cm3, μ= 0.604 mm-1, F(000) = 720, the final R = 0.0400 and w R = 0.1072 for 3610 observed reflections with I 2σ(I).     

Functional zinc(II) phthalocyanines bearing Schiff base complexes as oxidation catalysts for bleaching systems

Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications. Bleach catalysts provide cost‐effective, energy‐saving and environmentally friendly bleach systems yielding perfect stain removal at lower temperatures. This comparative study is based on the synthesis of bis[bis(salicylhydrazonephenoxy)manganese(III)] phthalocyaninatozinc(II) ( 2 ), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) ( 3 ) and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) ( 4 ) as tri‐nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes 2 , 3 , 4 was performed through the reaction of a Schiff base‐substituted phthalocyanine using MnCl₂?4H₂O, CoCl₂?6H₂O or FeCl₃?6H₂O salts in basic condition in dimethylformamide. Fourier transform infrared, ¹H NMR, ¹³C NMR, UV–visible, inductively coupled plasma optical emission and mass spectra were applied to characterize the prepared compounds. The bleach performances of the three phthalocyanine compounds 2 , 3 , 4 were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts 2 , 3 , 4 /H₂O₂ combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts 2 , 3 , 4 exhibited better bleaching performance at 25 °C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright © 2015 John Wiley & Sons, Ltd.     

Controllable tomography phase microscopy

Tomography phase microscopy (TPM) is a new microscopic method that can quantitatively yield the volumetric 3D distribution of a sample׳s refractive index (RI), which is significant for cell biology research. In this paper, a controllable TPM system is introduced. In this system a circulatory phase-shifting method and piezoelectric ceramic are used which enable the TPM system to record the 3D RI distribution at a more controllable speed, from 1 to 40 fps, than in the other TPM systems reported. The resolution of the RI distribution obtained by this controllable TPM is much better than that in images recorded by phase contrast microscopy and interference tomography microscopy. The realization of controllable TPM not only allows for the application of TPM to the measurement of kinds of RI sample, but also contributes to academic and technological support for the practical use of TPM.     

Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification

A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH₂ groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m² g^?1. The material also possesses good CO₂ (8 wt %) and H₂ (1.87 wt %) adsorption capabilities.     

A DFT study of 5-fluorouracil adsorption on the pure and doped BN nanotubes

The electronic and adsorption properties of the pristine, Al-, Ga-, and Ge-doped BN nanotubes interacted with 5-fluorouracil molecule (5-FU) were theoretically investigated in the gas phase using the B3LYP density functional theory (DFT) calculations. It was found that the adsorption behavior of 5FU molecule on the pristine (8, 0) and (5, 5) BNNTs are electrostatic in nature. In contrast, the 5FU molecule (O-side) implies strong adsorption on the metal-doped BNNTs. Our results indicate that the Ga-doped presents high sensitivity and strong adsorption with the 5-FU molecule than the Al- and Ge-doped BNNTs. Therefore, it can be introduced as a carrier for drug delivery applications.     

Synthesis and comparative study on polyetherimides from isomeric 4,4′-isopropylidenediphenoxy bis(phthalic anhydride)s

Two isomers of commercial 4,4′-(4,4′-isopropylidenediphenoxy) bis(phthalic anhydride) (4,4′-BPADA), that is, 3,4′-(4,4′-isopropylidenediphenoxy) bis(phthalic anhydride) (3,4′-BPADA) and 3,3′-(4,4′-isopropylidenediphenoxy) bis(phthalic anhydride) (3,3′-BPADA), were synthesized through aromatic nucleophilic substitution from nitrophthalonitrile and bisphenol A. 3,4′-BPADA was first synthesized from two intermediates, that is, 3-(4-[4-hydroxyphenylisopropylidene] phenoxy) phthalonitrile (3-BPADN) and 3,4′-(4,4′-isopropylidenediphenoxy) bis(phthalonitrile) (3,4′-BPATN). The corresponding three series of polyetherimides (PEIs) were prepared with two representative aromatic diamines (4,4′-oxydianiline and m-phenylenediamine (m-PDA)) via two-step procedure and chemical imidization. Isomeric polyimides showed T_gs from 206 to 256°C in nitrogen and T_d5%s from 488 to 511°C in argon, good mechanical properties (tensile moduli of 2.3–3.3 GPa, tensile strengths of 70–96 MPa, and elongations at break of 3.2%–5.1%), and good solubility. With the introduction of 3-substituted phthalimide unit, PEIs displayed higher T_g values, lower strengths and elongations, better solubility and larger d-spacings. The rheological properties of thermoplastic polyimide resins based on the BPADA isomers were investigated, which showed that polyetherimide PEI-3b derived from 3,3′-BPADA and m-PDA had the lowest melt viscosity among the isomers, indicating that the melt processibility had been greatly improved.