Preparation and self-assembly of amphiphilic triblock copolymers with polyrotaxane as a middle block and their application as carrier for the controlled release of Amphotericin B

A kind of novel amphiphilic triblock copolymers containing polyrotaxane (PR) as a central block was synthesized via the ATRP of poly(ethylene glycol) methyl ether methacrylate (PEGMA) initiated with polypseudorotaxanes made from a distal 2-bromopropionyl end-capped Pluronic F127 with a varying amount of β-CDs in the presence of Cu(I)Cl/N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) at 25 °C in aqueous medium. The structure of the resulting copolymers was characterized in detail by ¹H NMR, 2D ROESY NMR, GPC, DSC and WAXD analyses. The degree of polymerization of PEGMA oligomers appeared to be adjustable. As a typical sample, F-30β-CD-60 with a molar feeding ratio of Pluronic F127 to β-CD to PEGMA holding 1:30:60 was found to self-assemble into nano-sized aggregates in water. Its critical aggregation concentration was assessed by fluorescence probe technique. The corresponding hydrodynamic radius and radius of gyration were also determined by dynamic and static light scattering measurements. The transmission electron microscopy images further revealed that the sizes of the polymeric micelles of the selected copolymer were in nano-scale and smaller than those of the blank brush-like block copolymer. These nano-sized particles showed great potential to be used as carrier for the controlled release of Amphotericin B (AmB) holding 8.7% drug-loading content and 87% drug-loading efficiency with the cumulative release profile substantially longer than that of the blank brush-like block copolymer.     

A ferromagnetic linear trinuclear Ni(II)-Schiff base complex supported by phenoxo and cinnamato bridges

A new linear trinuclear nickel(II) complex, [Ni₃(salme)₂(OCn)₄] (Hsalme = 2-[(3-methylamino-propylimino)-methyl]-phenol, OCn = cinnamate), showing weak ferromagnetic coupling (J = 1.8(1) cm⁻¹) through phenoxo and a novel tridentate bridging mode (1κ²OO′:2κO′) of the cinnamate ligand has been synthesized and structurally characterized by X-ray crystallography.     

Preparation and characterization of novel main-chain azobenzene polymers via step-growth polymerization based on click chemistry

A novel α-azide and ω-alkyne A–B type azobenzene monomer, 3′-ethynylphenyl[4-(4-azidobutoxy)phenyl]azobenzene (EAPA), was synthesized and used to generate a novel polymer via step-growth polymerization using 1,3-dipolar cycloaddition reaction under the catalysis of CuSO₄·5H₂O/sodium ascorbate/H₂O (“Click” chemistry). The structure of the resultant main-chain azobenzene polymer, PEAPA, was characterized by GPC, ¹³C NMR, UV–vis and FT-IR spectra. Thermal stability and crystallinity of PEAPA powder were studied by TGA and WAXD. The photo-induced trans–cis isomerization of PEAPA and EAPA in N,N′-dimethyl formamide (DMF) solution was investigated. Furthermore, the thermal cis–trans isomerizations of PEAPA and EAPA were also observed at 60 °C in dark. Thermal stability and trans–cis–trans isomerization behavior of PEAPA was compared with its non-triazole analog, PDHA.     

The electrocatalytic cascade assembling of isatins, malononitrile and N-alkyl barbiturates: An efficient multicomponent approach to the spiro[indole-3,5′-pyrano[2,3-d]pyrimidine] framework

Electrochemically induced catalytic multicomponent transformation of isatins, barbituric acid or N-alkyl barbiturates and malononitrile in alcohols in an undivided cell results in the formation of substituted 7′-amino-2,2′,4′-trioxo-1,1′,2,2′,3′,4′-hexahydrospiro[indole-3,5′-pyrano[2,3-d]pyrimidine]-6′-carbonitriles in 80–95% yields. The developed efficient electrocatalytic approach to corresponding spiro[indole-3,5′-pyrano[2,3-d]pyrimidine] system is beneficial from the viewpoint of diversity-oriented large-scale processes and represents a new example of the ecologically pure synthetic concept for electrocatalytic multicomponent reactions strategy.     

Synthesis and characterization of fluorine–thiophene-based π-conjugated polymers using coupling reaction

A solution processible fluorine–thiophene-based copolymers, namely poly[2,7-bis(4-octyl-2-thienyl)-9,9-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P1), poly[2,7-bis(3-octyl-2-thienyl)-9,9-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P2), poly[2,7-bis(3,3′-dioctyl-5,5′-bithien-2yl)-9,9′-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P3) were synthesized using Suzuki and Stille coupling reaction. The polymers showed weight loss starting around 400 °C indicative of good thermal stability. UV–vis properties and photoluminescence (PL) properties were investigated in toluene. P1, P2 and P3 exhibited the absorption maximum at 450, 428 and 435 nm and their PL spectrum peaked at 587, 559 and 560 nm, respectively. And all polymers, P1, P2 and P3, showed electroluminescence (EL) spectrum peaked at 592, 595 and 607 nm in the range of orange red. The polymers were electrochemically active in oxidation regions. P3 especially showed high oxidation stabilities in 1.17 V vs. Ag/Ag⁺. And P1 and P3 showed higher crystallinity than P2, because they have a repeated unit of 3,3-dialkyl-quaterthiophene.     

Molecular structures and vibrational frequencies for cis-[PdCl2(tmen)] and cis-[Pd(N3)2(tmen)]: A DFT study

Theoretical molecular structures of the complexes cis-[PdCl₂(tmen)] and cis-[Pd(N₃)₂(tmen)] (tmen = N,N,N′,N′-tetramethylethylenediamine) were investigated using B3LYP/DFT method. The calculated molecular parameters, bond distances and angles, revealed a square-planar geometry around the metallic center for both compounds with the azide being linear. The theoretical infrared spectra of C₁ symmetry (electronic state ¹A) of the compounds are in agreement with the experimental data.     

Preparation and swelling properties of superabsorbent nanocomposites based on natural guar gum and organo-vermiculite

Vermiculite (VMT) was modified with cetyl trimethylammonium bromide (CTAB). Superabsorbent nanocomposites were prepared by solution polymerization of natural guar gum (GG), partially neutralized acrylic acid (NaA) and organo-vermiculite (CTA⁺-VMT), ammonium persulfate (APS) as initiator and N,N′-methylene-bis-acrylamide (MBA) as crosslinking agent. FTIR spectra confirmed that NaA had been grafted onto GG and the OH groups of CTA⁺-VMT participated in the polymerization reaction. The intercalated-VMT was exfoliated during polymerization and uniformly dispersed in the GG-g-PNaA matrix. Swelling tests show that CTA⁺-VMT improved swelling and swelling rate more remarkably than VMT, and the nanocomposite exhibited distinct kinetic swelling behavior in NaCl and CaCl₂ solution. Organo-VMT improved the gel strength of the nanocomposite compared to VMT, and the maximum storage modulus of the nanocomposite reached 658 Pa (γ = 0.5%, ω = 100 rad/s).     

Two novel Zn(II) coordination polymers based on trigonal ligand: 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine

Two novel Zn(II) coordination polymers, [Zn₅(pytpy)₈(fum)₄(H₂O)₄(OH)₂]_n · n(CH₃OH) · 2n(H₂O) (1) and [Zn₃(pytpy)₄ (btc)₂]_n · 2n(H₂O) (2) (pytpy = 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine, H₂fum = fumaric acid, H₃btc = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized and structurally characterized. Complex 1 is a 2D layer structure, which is constructed from linear pentanuclear Zn(II) subunits interconnected via bidentate-bridging pytpy ligands and tridentate-bridging fum²⁻ anions. Complex 2 is a 3D network structure, μ₂-pytpy ligands link the layers based on the heart-like hexanuclear subunits to form the 3D network. Both complexes show strong fluorescence emission upon excitation at 310 nm in solid state. Additionally, these two complexes possess great thermal stabilities, especially for 2, the framework is stable up to 350 °C.     

Synthesis and characterization of soluble copoly(arylene ether sulfone phenyl-s-triazine)s containing phthalazinone moieties in the main chain

A series of new poly(arylene ether sulfone phenyl-s-triazine) copolymers containing phthalazinone moieties in the main chain (PPESPs) were prepared by a direct solution polycondensation of 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one (HPPZ) with 2-phenyl-4,6-bi(4-fluorophenyl)-1,3,5-triazine (BFPT) and 4,4′-dichlorodiphenyl sulfone (DCS). Model reactions monitored by HPLC indicated that BFPT had slightly higher reactivity than DCS in nucleophilic displacement reactions. The obtained random copolymers were characterized by FTIR, NMR, elemental analysis and GPC. The presence of sulfone and phthalazinone in the polymer chain results in an improvement in the solubility of poly(arylene ether phenyl-s-triazine)s in common organic solvents, such as N-methylpyrrolidone, N,N-dimethyl acetamide (DMAc), chloroform, sulfolane and pyridine. Thermal analysis reveal that the copolymers exhibit high glass transition temperatures (T_gs) ranging from 271–300 °C, and excellent thermal stability associated with decomposition temperatures for 5% mass-loss exceeding 503 °C. All copolymers are amorphous except PPESP28 as evidenced by WAXD. Their T_gs and solubility increase with an increase in sulfone content in the polymer backbone, while the crystallinity and overall thermal stability appear to decrease. This kind of phthalazinone-based copoly(arylene ether sulfone phenyl-s-triazine)s may be considered a good candidate for using as high-performance structural materials.     

Photooxidation of N,N-bis(3,5-di-tert.-butylsalicylidene)-1,2-diamino hexane-manganese(III) chloride (Jacobsen catalyst) in chloroform

Mn^III(J-salen)Cl (Jacobsen catalyst) with J-salen=N,N^′-bis(3,5-di-tert.-butylsalicylidene)-1,2-diaminocyclohexane dianion in CHCl₃ is photooxidized by the solvent to a Mn^IV(J-salen) complex, presumably Mn^IV(J-salen)Cl₂, with φ=0.002 at λ_irr=333 nm.     

Design of high-toughness polyacrylamide hydrogels by hydrophobic modification

Polyacrylamide (PAAm) hydrogels possessing a very large extensibility at break have been prepared via micellar crosslinking copolymerization of acrylamide monomer and N,N′-methylenebis(acrylamide) crosslinker in the presence of hydrophobic comonomers. N-butyl-, N-hexyl-, N-octyl-, and N,N-dihexylacrylamides were used as the hydrophobes in the hydrogel preparation. Incorporation of hydrophobes with an alkyl chain length x > 4 results in an increase in the loss factor tan δ of hydrogels due to the formation of temporary junction zones inside the gel network. The number N_H of the hydrophobes per hydrophobic block together with the alkyl chain length x of the pendant hydrophobic group were used to tune the loss factor of the hydrogels over two orders of magnitude. Tensile mechanical measurements show that increasing N_H or x also increases the degree of toughness of PAAm hydrogels. Keeping constant the hydrophobe level (20 mol%) at an alkyl chain length x = 6, increasing N_H from 9 to 30 increased the elongation ratio at break from 125 to 250%. Hydrogels exhibiting a high toughness, i.e., about 300% elongation ratio at break were obtained by modification of PAAm network chains with 10 mol% N-octylacrylamide.     

Synthesis and properties of hydrophobically modified acrylamide-based polysulfobetaines

Acrylamide-based, hydrophobically modified polysulfobetaines containing 3-[N-(2-methacroyloylethyl)-N,N-dimethylammonio]-propane sulfonate (DMAPS) and varying amounts of the hydrophobic monomer stearyl methylacrylate (SMA) were synthesized by micellar copolymerization. The basic physico-chemical properties of the synthesized copolymers were studied by means of surface tension, dynamic laser light scattering, and rheological measurements. All the copolymers showed surface activity when the copolymer concentration was above 0.07 wt%. The dynamic laser light scattering measurement revealed that both zwitterionic and hydrophobic associations were important in copolymer aggregation. The rheological properties of the copolymers in aqueous solution depended on the content of hydrophobic monomer, the copolymer concentration and the addition of salt, which were characteristic of hydrophobically modified polyacrylamide and acrylamide-based polyzwitterions. The critical aggregation concentration of the copolymers was in the range of 0.07–0.1 wt%.     

Solvothermal synthesis of 1D and 2D cobalt(II) and nickel(II) coordination polymers with 2,5-dihydroxy-p-benzenediacetic acid

1D cobalt(II) and nickel(II) coordination polymers {[Co(dba)(H₂O)₄] · H₂O}_n (1) and {[Ni(dba)(H₂O)₄] · H₂O}_n (2) (H₂dba = 2,5-dihydroxy-p-benzenediacetic acid) were synthesized under low temperature solvothermal condition. When 4,4′-bipyridine (bpy) was introduced to the synthetic systems of 1 and 2, respectively, two novel 2D coordination polymers {[Co(dba)(bpy)] · 0.5H₂O}_n (3) and [Ni(dba)(bpy)(H₂O)₂]_n (4) with different structures were obtained. All of the compounds were characterized by elemental analysis, FT-IR, UV–Vis spectra and single crystal X-ray diffraction.     

Novel Hg and Mn supramolecular complexes with a versatile building block 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiolate involving in situ ligand formation

Reaction of potassium N′-(pyridine-4-carbonyl)-hydrazinecarbodithioate ([K⁺(H₂L)⁻]) with Hg^II or Mn^II inorganic salt in the presence of 1,10-phenanthroline (phen) or 4,4′-bipyridine (bipy), yields complexes [Hg(pyt)₂(phen)] (1) and {[Mn(pyt)₂(H₂O)₂]·(bipy)·(H₂O)₂}_n (2), in which the pyt ligand (Hpyt = 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol) is obtained by in situ ligand formation from the acyclic precursor [K⁺(H₂L)⁻]. Single crystal X-ray diffraction suggests that the pyt anionic ligands in 1 and 2 behave as thiolate and thione isomers, respectively, and display S- and μ-N_pyridyl, N_oxadiazole-binding fashions. Complex 1 shows a 1-D fishbone-like supramolecular array via strong aromatic stacking interactions between the discrete mononuclear coordination motifs, whereas 2 has a 2-D layered host coordination framework with the inclusion of bipy and water guests in the cavities.     

Bis(4′-phenyl-2,2′:6′,2″-terpyridine)ruthenium(II): Holding the {Ru(tpy)2} embraces at bay

The solid state structure of [Ru(Phtpy)₂][PF₆]₂ · 4MeCN has been determined (Phtpy = 4′-phenyl-2,2′:6′,2″-terpyridine); [Ru(Phtpy)₂]²⁺ cations pack into sheets by virtue of {M(tpy)₂}₂ embraces, and the MeCN solvent molecules are involved in NH–C interactions which prevent the efficient packing of adjacent sheets. Comparisons with related structures lead to some generalizations about packing motifs in salts containing [M(Phtpy)₂]²⁺ or [M(pytpy)₂]²⁺ cations (pytpy = 4′-pyridyl-2,2′:6′,2″-terpyridine).     

Substantially enhancing enzymatic regioselective acylation of 1-β-d-arabinofuranosylcytosine with vinyl caprylate by using a co-solvent mixture of hexane and pyridine

Novozym 435-catalyzed regioselective acylation of 1-β-d-arabinofuranosylcytosine (ara-C) with vinyl caprylate for the preparation of its 5′-O-acyl derivative has been performed in six co-solvent mixtures and three pure polar solvents for the first time. Novozym 435 displayed low activity towards 1-β-d-arabinofuranosylcytosine in pure polar solvents, although those solvents can dissolve the nucleosides well. When a hexane–pyridine co-solvent system was adopted, both the initial rate and the substrate conversion were enhanced markedly. The most suitable co-solvent, initial water activity, reaction temperature and the molar ratio of vinyl caprylate to ara-C were hexane/pyridine (28/72, v/v), 0.03, 40 °C and 15, respectively. Under these conditions, the initial rate, the substrate conversion and the regioselectivity were as high as 99.0 mmol h⁻¹, 98% and >99%, respectively. The product of the Novozym 435-catalyzed reaction was characterized by ¹³C NMR and confirmed to be 5′-O-octanoyl 1-β-d-arabinofuranosylcytosine.     

Self-propagating high-temperature synthesis of cubic niobium nitride under high pressures of nitrogen

Cubic niobium nitrides δ-NbN_x with different x = 0.87–1.015 were prepared by the self-propagating high-temperature synthesis (SHS) under nitrogen pressures of P(N₂) = 48–230 MPa.Nitrogen composition x as a function of P(N₂) was determined in weight gain experiments and compared with that determined by chemical (Kjeldahl) analysis. For powders with different x, the superconducting transition temperature T_c was measured as a function of lattice parameter a. The T_c values were found to grow linearly with increasing a. A maximum value of T_c = 15.0 K for cubic niobium nitride corresponded to a maximum value of a = 4.3901 Å.     

Electrospun nanofibers from ferrocene-containing multiblock copolymers prepared via RAFT polymerization with F127 modified precursor

Electrospun nanofibers from copolymers composed of ferrocene side chains and PEO₁₀₀-PPO₆₅-PEO₁₀₀ (F127) were fabricated in chloroform and N,N–dimethyl formamide solutions (V/V = 95:5) at room temperature. Ferrocene-containing multiblock copolymers (PFcMA_n-F127-PFcMA_n) were synthesized through reversible addition-fragmentation chain transfer polymerization using s-1-dodecyl-s''- (α, α'-dimethyl-α''-acetic acid) trithiocarbonate (DDMAT) modified F127 with 2- (methacryloyloxy) ethyl ferrocencarboxylate (FcMA). The structures of as-obtained chemicals were characterized by FTIR, ¹H NMR, and ¹³C NMR. Additionally, the block copolymers molecular weight and polydispersity were measured using gel permeation chromatography. The electrochemical responsiveness of the polymers was investigated using cyclic voltammetry as well as the thermal stabilities of polymers and precursors were tested through DSC and TGA. The morphologies of electrospun fibers were observed through field emission scanning electronic spectroscopy and a fibrous diameter of 300–1100 nm was obtained. The results indicated that the suitable molecular weight of ferrocene -containing polymer would be processed in nanofibrous.     

A CdSO4-like 3-D framework constructed from monosodium substituted Keggin arsenotungstates and copper(II)-ethylenediamine complexes

A 6⁵·8 CdSO₄-like 3-D framework [Cu(en)₂]₃[α-AsW₁₁NaO₃₉]·2H₂O (1) constructed by monosodium-substituted Keggin arsenotungstates and copper(II)-ethylenediamine complexes (en = ethylenediamine) has been synthesized by reaction of Na₈[α-HAsW₉O₃₄]·11H₂O, CuCl₂·2H₂O and ethylenediamine under hydrothermal conditions and structurally characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. Crystal data for 1: C₁₂H₅₂AsCu₃N₁₂NaO₄₁W₁₁, monoclinic, Cc, a = 20.409(9) Å, b = 16.737(8) Å, c = 16.561(7) Å, β = 104.607(7)°, V = 5474(4) Å³, T = 296(2) K; Z = 4, μ = 24.860 mm⁻¹, GOOF = 1.086, R₁ = 0.0284, wR₂ = 0.0759. To the best of our knowledge, 1 represents the first 6⁵·8 CdSO₄-like 3-D monovacant Keggin arsenotungstate derivative in polyoxometalate chemistry.