4-in-1 Fe3O4/g-C3N4@PPy-DOX nanocomposites: Magnetic targeting guided trimode combinatorial chemotherapy/PDT/PTT for cancer.

At present, cancer has become a major disease threatening human health worldwide. Therefore, developing targeting guided multimode synergetic therapy has become one of the hot spots in current antitumor research and is also a great challenge. Herein, a new Fe3O4/g-C3N4@PPy-DOX nanocomposite containing magnetic iron oxide (Fe3O4) nanoparticles (NPs), lamellar structure of graphite-like carbon nitride (g-C3N4) and polypyrrole (PPy) shell with the loaded anti-tumor drug doxorubicin hydrochloride (DOX) was designed and prepared. The monodisperse Fe3O4 nanoparticles (NPs) with the diameter of 20 nm endowed the nanocomposite with the magnetic targeting ability, reducing damage to normal tissues. It is very interesting that the Fe3O4 NPs also possessed photosensitizer function for photodynamic therapy (PDT). The g-C3N4 sheets as the photocatalysis towards the degradation of water for generating O2 could effectively improve the hypoxia of solid tumors and increase the efficiency of PDT. In addition, PPy has high light-to-heat conversion efficiency, so was chosen for the cancer photothermal therapy (PTT). Finally, an anticancer drug (DOX) was loaded on the nanocomposite because the presence of mesoporous structure. Thus, the prepared Fe3O4/g-C3N4@PPy-DOX nanocomposites exhibit synergetic chemotherapy/PTT/enhanced PDT antitumor effect. This study provides an inspiration for combining targeting and multimodality to improve the anticancer efficiency.

[The structure and properties of metal-free 1, 8, 15, 22-tetrakis (3-pentyloxy) phthalocyanine complex and study of its IR spectra].

Density functional theory calculations were carried out to study the molecular structure, molecular orbital, atomic charge, and infrared spectra of metal-free 1, 8, 15, 22-tetrakis(3-pentyloxy) phthalocyanine using B3LYP method with the 6-31G (d) basis set. The optimized molecular geometry is in good agreement with the result from X-ray deterimination, and the differences between the bond lengths from calculation and X-ray crystallography structure for the framework of phthalocyanine are less than 0.002 nn. It was also found that there is a good consistency between the calculated and experimental IR data. The calculated structure and IR spectra were fairly compared with the X-ray crystallography structure and experimental IR spectra to verify the reliability of employed B3LYP method and 6-31G(d) basis set. It is worth noting that the 3-pentyloxy groups at the alpha position have significant influence on the structure and properties of metal-free pthalocyanine, for example, both the energies of HOMO and LUMO increase, however, the gap between HOMO and LUMO decreases, which results in the decrease of the 1, 8, 15,22-tetrakis(3- pentyloxy)phthalocyanine stability. The important peaks in the IR spectra were also assigned and analyzed in detail according to the calculations.

[Spectroscopic studies on the binding of phenazopyridine hydrochloride and bovine serum albumin].

The binding of phenazopyridine hydrochloride and bovine serum albumin under physiological conditions was studied by spectroscopic method. The quenching mechanism of the fluorescence of bovine serum albumin by phenazopyridine hydrochloride was studied with fluorescence and absorption spectroscopy. The binding constant Kb and the number of binding sites n were determined at different temperatures according to Scatchard equation, and the main binding force was discussed by thermodynamic equations. The effect of the drug on bovine serum albumin conformation was also studied by using synchronous fluorescence spectroscopy. The quenching mechanism of phenazopyridine hydrochloride to bovine serum albumin is static quenching and non-radiation energy transfer. The binding constants Kb at 15, 25 and 37 degrees C are 2.47 x 10(7), 9.15 x 10(6) and 4.36 x 10(6) mol(-1) with one binding site, respectively. The thermodynamic parameters of the reaction are DeltaH = -71.2 kJ x mol(-1), and DeltaS = 124.8 J x mol(-1) x K(-1). Binding phenazopyridine hydrochloride to bovine serum albumin is a spontaneous inter-molecular interaction in which entropy increases and Gibbs free energy decreases. The binding distance r between phenazopyridine hydrochloride and bovine serum albumin is 1.61 nm according to Forster theory of non-radiation energy transfer. The binding force is electrostatic interaction. Phenazopyridine hydrochloride can be deposited and transported by serum protein in vivo. Phenazopyridine hydrochloride does affect the serum protein conformation.

Hydrolysis of p-nitrophenyl picolinate catalyzed by metal complexes of N-alkyl-3,5-bis(hydroxymethyl)-1,2,4-triazole in CTAB micelles.

Two lipophilic ligands containing triazole and hydroxyl groups, N-alkyl(C(n)H(2n+1))-3,5-bis(hydroxymethyl)-1,2,4-triazole (n=10 and 12), were synthesized. Effects of their Cu(II) and Ni(II) complexes on the hydrolysis of p-nitrophenyl picolinate (PNPP) in cetyltrimethylammonium bromide (CTAB) micelles have been investigated kinetically, and some kinetic parameters of the reactions were obtained by employing the ternary complex kinetic model for metallomicellar catalysis. It was found that Cu(II) complexes of these triazole-based ligands showed more effective catalytic activity on the hydrolysis of PNPP than Ni(II) complexes. Also, the apparent first-order rate constants for product formation in the metallomicellar phase (k(N)(')), the association constants between the substrate and the binary complex (K(T)), and the association constants between the metal ion and the ligand (K(M)) increased with an increase in pH value, which may be attributed to an increase in the nucleophilicity of the hydroxyl groups in the ligand or the electrophilicity of the substrate at higher pH. In addition, at constant pH, k(N)(') and K(T) increased with an increase in the hydrocarbon chain length of the ligand, while K(M) decreased.

[Stability of patient bile and study on its influential factors].

The patient bile and its centrifugate were studied by FTIR spectra, UV-Vis spectra, particle size analysis, and zeta potential determination. The result showed that the patient bile was in a heterogenetic and unstable state, and some of the ultramicrons in the patient bile assembled to form precipitate after centrifugalized at different speeds. According to FTIR and UV-Vis spectra, the authors found that the composition of the precipitates was mainly cholesterol, bilirubin, calcium bilirubinate, protein, phospholipid and so on, which was much close to that of the core of patient gallstone. The change in the properties of cholesterol/phospholipid vesicles, and the production of the undissolvable calcium salt in the patient bile had crucial influence on the stability of the patient bile, which played important roles in the core-formation and initial growth of gallstone that were induced by the matrixes such as proteins, phospholipids etc.

[Spectrophotometric simultaneous determination of pyrocatechol, resorcinol and hydroquinone by LM-BP neural network].

By means of artificial neural network and Levenberg Marquardt Back Propagation (LM-BP) train algorithm, the three components of pyrocatechol, resorcinol and hydroquinone were determined simultaneously. The absorption spectra of these three components severely overlap in ultraviolet spectral range. Three wavelengths at 283.5, 279.5 and 276.5 nm were selected for the determination. 25 mixture standard solutions were prepared according to orthogonal projection form L25 (5(6)). Three kinds of components were trained. Mean Squared Error (MSE) reaching minimum value is 0.083 114 3. Meanwhile the contents of pyrocatechol, resorcinol and hydroquinone in six simulation mixture samples were predicted. The relative errors of the three kinds of components were slightly larger under the low concentration condition, and the mean relative error for most analytical results was less than 5%, especially it is satisfactory for the analytical results of pyrocatechol and resorcinol with severely overlapped absorption spectra.

Study on the viscosity of cationic gemini surfactant-nonionic polymer complex in water.

Interactions between a cationic gemini surfactant, 1,2-ethane bis(dimethyldodecylammonium bromide) (designated as 12-2-12), and a nonionic polymer polyvinyl alcohol (PVA) were investigated by means of viscosity and specific conductance. Results show that PVA displays special viscosity behavior in aqueous solutions containing the gemini surfactant 12-2-12, which is due to the molecular interaction of the polymer and the surfactant. It was found that the special viscosity depended on ionization of the surfactant, as well as polymer concentration and surfactant concentration in the nonionic polymer-surfactant system. A theoretical expression for the dependence of the solution viscosity on the ionization of the surfactant micelle was given, and the new equation proved to be in good agreement with the experimental data.

[Photometric determination of cobalt by the formation of a multi-ligand complex of Co(II)-C16H16N2S2O2-DEA].

The new ligand vanillin S-benzyldithocarbazte(HL) and its complex Co(II)-C16H16N2S2O2-DEA was synthesized and characterized by IR, UV-Vis. The optimum color conditions of the complex in 95% ethanol solution(including reaction temperature T, heating time t, and the concentrations of the three components) have been studied by quadratic regression orthogonal design method. According to the quadratic-regression equation, the maximum absorption intensity and optimum color conditions of the complex were calculated. The results were consistent with those gotten by experiment. The influences of common ions on the determination of cobalt and the methods to eliminate the influence are investigated. The maximum absorption peak of the complex is found at 404 nm and molar absorptivity is 5.29 x 10(4) L.mol-1.cm-1. Beer's law is obeyed in the range of 0-20 micrograms.(25 mL)-1 for Co(II). The composition of Co2+ to HL, and DEA in the complex is 1:2:1. The new method was successfully utilized to the determination of cobalt in VB12 and medicine.

[Synthesis, characterization and properties of N,N-dimethylferrocenylmethylhexadecylammonium bromide].

N,N-dimethylferrocenylmethylhexadecylammonium bromide (FC16AB) was synthesized and characterized by the spectra of UV-Visible, FTIR 1H NMR, ESMS, etc. Surface tensions of different concentrations of FC16AB water solution were measured, which shows that FC16AB has good surface activity. The surface pressure-area (pi-A) curves and differentiated pi-A curves of FC16AB on water, Cl-, and SO(4)2- subphases were studied. The results indicate that FC16AB molecules can form the most stable monolayer on the subphase containing Cl-.

[Synthesis and monolayer behaviors of 4-methyl-5-hydroxy-ethyl isothiazole stearic ester].

4-methyl-5-hydroxy-ethyl isothiazole stearic ester (HISE) was synthesized and characterized by FTIR spectroscopy, 1H NMR and MS. The monolayer-forming ability of HISE was studied in subphases with different pH values using isotherms of surface pressure-area per molecule (pi-A). It was observed that the collapse pressure and the film-forming ability of the monolayers of HISE increased gradually as pH values ascended. Research of differentiated pi-A curves (d pi(/dA-A) indicated that there were one or two phase change points during the compressing process, and the incompressibility and the stability of HISE monolayers on alkalescent subphases were better than on acid subphases.

Fabrication of magnetically separable fluorescent terbium-based MOF nanospheres for highly selective trace-level detection of TNT.

In this work, we present novel kinds of Fe3O4@Tb-BTC magnetic metal-organic framework (MOF) nanospheres which possess both magnetic characteristics and fluorescent properties using a layer by layer assembly technique. The structure and morphology of the as-prepared Fe3O4@Tb-BTC were systematically characterized and it was applied in detection of nitroaromatic explosives, such as 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2-nitrotoluene (2-NT), 4-nitrotoluene (4-NT), nitrobenzene (NB) and picric acid (PA). The results indicate that the fluorescence intensity of Fe3O4@Tb-BTC can be quenched by all analytes studied in the present work. Remarkably, the as-synthesized nanospheres exhibit high sensitivity for 2,4,6-trinitrotoluene (TNT) detection with Ksv value of (94 800 M(-1)). Besides, the magnetic nanospheres can be easily recycled, which makes it more convenient for reutilization and friendly to the environment. The results show that it has broad application prospects in the detection of nitroaromatic explosives.

Fabrication of composite photocatalyst g-C3N4-ZnO and enhancement of photocatalytic activity under visible light.

The g-C(3)N(4)-ZnO composite photocatalysts with various weight percents of ZnO were synthsized by a simple calcination process. The photocatalysts were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), UV-vis diffuse reflection spectroscopy (UV-vis), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The PXRD and HR-TEM results show that the composite materials consist of hexagonal wurzite phase ZnO and g-C(3)N(4). The solid-state UV-vis diffuse reflection spectra show that the absorption edge of the composite materials shifts toward the lower energy region and to longer wavelengths in comparison with pure ZnO and g-C(3)N(4). Remarkably, the photocatalytic activity of g-C(3)N(4)-ZnO composites has been demonstrated, via photodegradation of Methyl Orange (MO) and p-nitrophenol experiments. The photocatalytic activity of g-C(3)N(4)-ZnO for photodegradation of Methyl Orange and p-nitrophenol under visible light irradiation was increased by over 3 and 6 times, respectively, to be much higher than that of single-phase g-C(3)N(4), clearly demonstrating a synergistic effect between ZnO and g-C(3)N(4). The concentrations of Zn(2+) in g-C(3)N(4)-ZnO system after a photocatalytic reaction at various reaction times were found to be much lower than those for a ZnO system under the same reaction conditions, indicating that the g-C(3)N(4)-ZnO composite possesses excellent long-term stability for a photocatalytic reaction in aqueous solutions. Furthermore, a synergistic photocatalysis mechanism between ZnO and g-C(3)N(4) was proposed based on the photodegradation results. Such obviously improved performance of g-C(3)N(4)-ZnO can be ascribed mainly to the enhancement of electron-hole separations at the interface of ZnO and g-C(3)N(4).

Microwave-assisted synthesis of highly fluorescent nanoparticles of a melamine-based porous covalent organic framework for trace-level detection of nitroaromatic explosives.

Covalent organic frameworks (COFs) are a new generation of porous materials constructed from light elements linked by strong covalent bonds. Herein we present rapid preparation of highly fluorescent nanoparticles of a new type of COF, i.e. melamine-based porous polymeric network SNW-1, by a microwave-assisted synthesis route. Although the synthesis of SNW-1 has to be carried out at 180°C for 3d under conventional reflux conditions, SNW-1 nanoparticles could be obtained in 6h by using such a microwave-assisted method. The results obtained have clearly demonstrated that microwave-assisted synthesis is a simple yet highly efficient approach to nanoscale COFs or other porous polymeric materials. Remarkably, the as-synthesized SNW-1 nanoparticles exhibit extremely high sensitivity and selectivity, as well as fast response to nitroaromatic explosives such as 2,4,6-trinitrotoluene (TNT), 2,4,6-trinitrophenylmethylnitramine (Tetryl) and picric acid (PA) without interference by common organic solvents, which is due to the nanoscaled size and unique hierarchical porosity of such fluorescence-based sensing material.

Rapid synthesis of flower-like Cu2O architectures in ionic liquids by the assistance of microwave irradiation with high photochemical activity.

A novel and facile protocol for the rapid synthesis of flower-like Cu(2)O architectures is reported in the presence of ionic liquid 1-n-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM]BF(4)) with the assistance of microwave irradiation. The hierarchical structures are assembled from many thin nanosheets with tunable sizes by adjusting the amount of [BMIM]BF(4) in the reaction solution. Noticeably, the flower-like Cu(2)O architectures present a high surface area of 65.77 cm(2) g(-1) with a band gap of about 2.25 eV, and exhibit high and stable photochemical activity for the reduction of Cr(VI) to Cr(III) under visible light irradiation. A reasonable model of an absorption and diffusion-limited aggregation process is proposed for explaining the possible formation mechanism of the flower-like Cu(2)O. The approach described in this study provides a feasible and rapid method to synthesize flower-like Cu(2)O with a hierarchical structure that is ready for application in the fields of photocatalytic hazard pollutants.

Microwave-enhanced synthesis of magnetic porous covalent triazine-based framework composites for fast separation of organic dye from aqueous solution.

A novel type of magnetic porous carbonaceous polymeric material, CTF/Fe(2)O(3) composite (CTF = covalent triazine-based framework), has been synthesized by a facile microwave-enhanced high-temperature ionothermal method. By selecting ZnCl(2) as a reaction medium and the Lewis acid catalyst, and choosing FeCl(3)·6H(2)O as an iron oxide precursor, a series of CTF/Fe(2)O(3) composites with different γ-Fe(2)O(3) contents has been prepared in 60 min. The resulting samples were characterized by the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibration sample magnetometer (VSM), and N(2) sorption-desorption isotherms. The obtained CTF/Fe(2)O(3) composites exhibit high surface areas (930-1149 m(2) g(-1)), and their saturation magnetizations at 300 K vary from 1.1 to 5.9 emu g(-1), depending respectively on different Fe(2)O(3) contents (6.43-12.43 wt%) in the CTF/Fe(2)O(3) composites. The CTF/Fe(2)O(3) composites were applied to remove organic dye from aqueous solution by selecting methyl orange as a model molecule, and both high adsorption capacity (291 mg g(-1), corresponding to 0.889 mmol g(-1)) and fast adsorption kinetics (k(ads) = 4.31 m(2) mg(-1) min(-1)) were observed.

Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water.

The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu(3)(BTC)(2)(H(2)O)(3)](n) (HKUST-1, BTC=benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu(3)(BTC)(2)](n) samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N(2) sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu(3)(BTC)(2)](n) exhibited remarkably high adsorption affinity (K(d)=4.73 × 10(5)mL g(-1)) and high adsorption capacity (714.29 mg g(-1)) for Hg(2+) adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg(2+) under the same condition.

New photocatalysts based on MIL-53 metal-organic frameworks for the decolorization of methylene blue dye.

The photocatalytic decolorization of methylene blue dye in aqueous solution using a novel photocatalyst MIL-53(Fe) metal-organic frameworks was investigated under UV-vis light and visible light irradiation. The effect of electron acceptor H(2)O(2), KBrO(3) and (NH(4))(2)S(2)O(8) addition on the photocatalytic performance of MIL-53(Fe) was also evaluated. The results show that MIL-53(Fe) photocatalyst exhibited photocatalytic activity for MB decolorization both under UV-vis light and visible light irradiation, and the MB decolorization over MIL-53(Fe) photocatalyst followed the first-order kinetics. The addition of different electron acceptors all enhances the photocatalytic performance of MIL-53(Fe) photocatalyst, and the enhanced rate follows the order of H(2)O(2)>(NH(4))(2)S(2)O(8)>KBrO(3) under UV-vis light irradiation, while in the order of (NH(4))(2)S(2)O(8)>H(2)O(2)>KBrO(3) under visible light irradiation. Moreover, MIL-53(Fe) did not exhibit any obvious loss of the activity for MB decolorization during five repeated usages. The photocatalytic activities over MIL-53(M) (M=Al, Fe), the isostructure to MIL-53(Fe), indicate that the metal centers show nil effect on the photocatalytic activity of MIL-53(M) photocatalysts.

Biogenic synthesis of calcium oxalate crystal by reaction of calcium ions with spinach lixivium.

In this paper, we report a biogenic synthesis protocol for preparation of calcium oxalate (CaC2O4, CaOx) crystal at room temperature by a simple protein-mediated reaction of aqueous Ca2+ ions with the C2O4(2-) ions spontaneously released from spinach. The aggregation of calcium oxalate monohydrate (COM) and calcium oxalate dihydrate (COD) with a rod-like morphology was mainly formed in the spinach root lixivium, and the proportion of COM crystal in the aggregation increased with the concentration of Ca2+ ions increasing, however, spindle-shaped crystal was mainly obtained in the spinach leaf lixivium and the content of COM in the product was higher than that obtained in the root lixivium with the similar concentration of Ca2+ ions. COM phase disappeared and only COD crystal with morphology of tetragonal bipyramidal prisms presented in the product when the leaf lixivium was replaced by the leaf broth. The biomolecules such as proteins with molecular weight of 31kDa liberated from the spinach root are negative-charged, which played important roles for the control of CaOx crystal growth in the root lixivium corresponding to the changes of protein secondary structures after reaction with Ca2+ ions. This research was potentially important for unraveling the biomineralization mechanism of CaOx crystal.