Biocompatible tumor-targeted GQDs nanocatalyst for chemodynamic tumor therapy.

To deal with the complex tumor microenvironment (TME), chemodynamic therapy (CDT) has been developed, which uses nanocatalysts simulating peroxidase to convert high concentration hydrogen peroxide (H2O2) into highly toxic hydroxyl radicals (˙OH) in situ and effectively kills tumor cells. Due to the low catalytic activity of traditional nanocatalysts, the present CDT treatment has to be combined with other anti-tumor therapies, which increases the complexity and uncertainty of the treatment. Thus, developing new nanocatalysts with stable and high enzymatic activity is the key point to CDT treatment. Graphene quantum dots (GQDs) are important metal-free catalysts with intrinsic peroxidase-like activity due to their excellent electron transport performance. Here, we prepare a nitrogen-doped GQD (NGOD) nanocatalyst, which displays much higher peroxidase activity than known metal nanocatalysts. The NGQD nanocatalyst is further grafted with RGDS peptide-modified polyethylene glycol (PEG), which guides the nanocatalyst to the tumor area and increases its circulation time in blood. The as-produced RGDS-PEG@NG nanocatalyst displays stable and high peroxidase activity, which achieves the conversion of H2O2 → ˙OH in the TME. Through an in vivo study it has been observed that RGDS-PEG@NGs obviously inhibit tumor growth without combining with other treatment methods and show excellent biocompatibility, which provides a unique idea for the application of GQDs in CDT.

Porous Graphene Oxide Films Prepared via the Breath-Figure Method: A Simple Strategy for Switching Access of Redox Species to an Electrode Surface.

Porous materials can be modified with physical barriers to control the transport of ions and molecules through channels via an external stimulus. Such capability has brought attention toward drug delivery, separation methods, nanofluidics, and point-of-care devices. In this context, gated platforms on which access to an electrode surface of species in solution can be reversibly hindered/unhindered on demand are appearing as promising materials for sensing and microfluidic switches. The preparation of a reversible gated device usually requires mesoporous materials, nanopores, or molecularly imprinted polymers. Here, we show how the breath-figure method assembly of graphene oxide can be used as a simple strategy to produce gated electrochemical materials. This was achieved by forming an organized porous thin film of graphene oxide onto an ITO surface. Localized brushes of thermoresponsive poly(N-isopropylacrylamide) were then grown to specific sites of the porous film by in situ reversible addition-fragmentation chain-transfer polymerization. The gating mechanism relies on the polymeric chains to expand and contract depending on the thermal stimulus, thus modulating the accessibility of redox species inside the pores. The resulting platform was shown to reversibly hinder or facilitate the electron transfer of solution redox species by modulating temperature from the room value to 45 °C or vice versa.

Understanding the selective-sensing mechanism of lysine by fluorescent nanosensors based on graphene quantum dots.

The selectivity of single-amino acid nanosensors is still not well understood. Herein, the factors that govern graphene-based nanomaterials for the selective detection of lysine are reported to guide the design of single-amino acid nanosensors. Graphene quantum dots (GQDs), nitrogen-doped GQDs (N-GQDs), and nitrogen/sulfur co-doped GQDs (N,S-GQDs) were used to sense lysine. The interaction mode and mechanism adjusted selectivity of the zero-dimensional graphene-based quantum dots to lysine ascribe to the solution behavior, molecular size, number of atoms as electron donors in graphene, and driving force. Being a basic amino acid, lysine is protonated with a positive charge below solution pH of 9. It adsorbed on the graphene-based quantum dots via electrostatic attraction, which blocked the internal charge transfer pathway inducing fluorescence enhancement at 420 nm. The protonated ɛ-amine side of lysine is responsible for the course. The small diameter of the lysine of ɛ-amine (<0.35 nm) favored its approach to the quantum dots, resulting in a fluorescence change, which could not be achieved with the larger arginine. The activated sites for interaction with lysine located at the edges of the layers of graphene to reach high selectivity. The N-GQDs and N,S-GQDs are much more sensitive to lysine than the GQDs because they contain nitrogen atoms as electron donors. They had similar linear detection ranges and detection limits, which suggested that the contribution of sulfur for lysine detection was minor. The results of this study provide new insights into the design of GQDs-based single-analyte nanosensors with high selectivity.

A graphene oxide-based fluorescent sensor for recognition of glutamate in aqueous solutions and bovine serum.

A novel fluorescence probe based on graphene-aminofluorescein (GAF) for sensing glutamate is prepared by modifying graphene oxide (GO) with 5-aminofluorescein (AF), and shows high sensitivity and selectivity. The strong fluorescence of the GAF probe is quenched in the presence of glutamate, and the quenching exhibits a good linear relationship with the glutamate concentration within the range of 1-45 mg/L. In bovine serum, the accurate quantitation of glutamate is possible within the range of 6 mg/L to 30 mg/L. At the pH of 3.32 (close to the isoelectric point of glutamate), GAF can selectively detect glutamate in preference to other amino acids. The high sensitivity and specificity of this sensor enable a new method for the detection of glutamate in aqueous solutions and serums.

Chlorine and temperature directed self-assembly of Mg-Ru2(ii,iii) carbonates and particle size dependent magnetic properties.

A series of heterometallic magnesium diruthenium(ii,iii) carbonates, namely K{Mg(H2O)6}2[Ru2(CO3)4Cl2]·4H2O (1), K2[{Mg(H2O)4}2Ru2(CO3)4(H2O)Cl]Cl2·2H2O (2), K[Mg(H2O)5Ru2(CO3)4]·5H2O (3) and K[Mg(H2O)4Ru2(CO3)4]·H2O (4), were synthesized from the reaction of Ru2(CO3)4(3-) and Mg(2+) in aqueous solution. Compound 1 is composed of ionic crystals with the Ru2(CO3)4Cl2(5-) : Mg(H2O)6(2+) : K(+) ratio of 1 : 2 : 1. Compound 2 consists of two dimensional layer structures, in which each octahedral environment Mg(H2O)4(2+) bonds to two [Ru2(CO3)4(H2O)Cl](4-) units in a cis manner forming a neutral square-grid layer {Mg(H2O)4Ru2(CO3)4(H2O)Cl}n. For compound 3, one water molecule of each Mg(H2O)6(2+) is substituted by an oxygen atom of Ru2(CO3)4(3-) forming [Mg(H2O)5Ru2(CO3)4](-), and then the neighboring Ru2 dimers are linked together by the rest of the two oxygen atoms of carbonates to form a layer structure {Mg(H2O)5Ru2(CO3)4}n(n-). In compound 4, the neighboring squared-grid layers {Ru2(CO3)4}n(3n-), similar to those in compound 3, are linked by each octahedral environment Mg(H2O)4(2+) in a cis manner forming the three-dimensional network {Mg(H2O)4Ru2(CO3)4}n(n-). Compound 3 shows ferromagnetic coupling between Ru2 dimers, and a long-range ordering is observed below 3.8 K. Compound 4 displays a magnetic ordering below 3.5 K, and a systematic study of the size-dependent magnetic properties of compound 4 reveals that the coercivity of 4 has been improved with reduced sample particle size from the micrometer to the nanometer scale.

Synthesis and adsorption performance of dithiocarbamate-modified glycidyl methacrylate starch.

The design of chelating polymers with fast complexation of the metal ions is particularly interest. In this work, the dithiocarbamate-modified glycidyl methacrylate starch was synthesized and characterized by FT-IR, (13)C NMR and XRD spectra. Its sorption performance for heavy metals fixation was studied. It was found that the removal process of metal ions involved a fast increase stage followed by a slower stage. There was a higher match between the pseudo-second-order equation and the experimental data. The sorption rate constants were related to the substitution rates of hydrated metal ions in aqueous solutions, showing typical chemisorption. The Langmuir isotherm gave satisfying fits to equilibrium data of metals adsorption. And the capacities followed the sequence Cu(2+)>Cd(2+)>Co(2+)>Zn(2+)>Ni(2+)>Mn(2+), which could be well demonstrated with chelating interaction caused by sulfur atoms. Such understanding provides new insights as how to synthesize and use the dithiocarbamate-based polysaccharides.

Optical turn-on sensor based on graphene oxide for selective detection of D-glucosamine.

By incorporating the well-known fluorophore 8-aminoquinoline into graphene oxide, we have successfully prepared a turn-on fluorescent sensor capable of specific detection of D-glucosamine with a high selectivity and sensitivity. This methodology provides a new concept for the design and development of highly selective and sensitive turn-on optical sensors for selective detection of aminosaccharides and many other biomolecules.

Application of dithiocarbamate-modified starch for dyes removal from aqueous solutions.

The present study shows that the dithiocarbamate-modified starch (DTCS) is a commercially promising sorbent for the removal of anionic dyes from aqueous solutions. It is more effective than activated carbon for this purpose. At the appropriate solution pH of 4, kinetic studies indicate that the sorption of the dyes tends to follow pseudo-first-order equation. The sorption equilibrium is best described by the Langmuir-Freundlich isotherm model at 298 K. The capacities for individual dyes follow the sequence acid orange 7 > acid orange 10 > acid red 18 > acid black 1 > acid green 25, which is consistent with the inverse order of molecular size. The negative enthalpy change for the adsorption process confirms the exothermic nature of adsorption, and a free energy change confirms the spontaneity of the process. The FT-IR spectra and thermogravimetric analyses verify the sorption based on starch-NH(2)(+)CSSH⋯(-)O(3)S-dye electrostatic attraction. The DTCS can be regenerated from the dye loaded DTCS in a weak basic solution containing sodium sulfate.

Behaviors and mechanism of acid dyes sorption onto diethylenetriamine-modified native and enzymatic hydrolysis starch.

In this paper, different starches were modified by diethylenetriamine. The native starch reacted with diethylenetriamine giving CAS, whereas the enzymatic hydrolysis starch was modified by diethylenetriamine producing CAES. Adsorption capacities of CAES for four acid dyes, namely, Acid orange 7 (AO7), Acid orange 10 (AO10), Acid green 25 (AG25) and Acid red 18 (AR18) have been determined to be 2.521, 1.242, 1.798 and 1.570 mmol g(-1), respectively. In all cases, CAES has exhibited higher sorption ability than CAS, and the increment for these dyes took the sequence of AO7 (0.944 mmol g(-1))>AO10 (0.592 mmol g(-1))>AR18 (0.411 mmol g(-1))>AG25 (0.047 mmol g(-1)). Sorption kinetics and isotherms analysis showed that these sorption processes were better fitted to pseudo-second-order equation and Langmuir equation. Chemical sorption mechanisms were confirmed by studying the effects of pH, ionic strength and hydrogen bonding. Thermodynamic parameters of these dyes onto CAES and CAS were also observed and it indicated that these sorption processes were exothermic and spontaneous in nature.

Equilibrium and molecular mechanism of anionic dyes adsorption onto copper(II) complex of dithiocarbamate-modified starch.

The assembly of dyes molecules on metal-polymer complexes is of interest due to their potential applications in photovoltaic cell, separation, and wastewater treatment. In the present work, the interaction of anionic dyes (acid orange 7, acid orange 10, acid green 25, and acid red 18) with the copper(II) complex of dithiocarbamate-modified starch (DTCSCu) was investigated. The sorption studies showed that the interaction mechanism was based on chelating adsorption. The equilibrium data fitted well with Langmuir-Freundlich isotherm, and the capacities followed the order AO7 > AG25 > AR18 > AO10. It was affected by the structure of the dye. The sulfonate groups located on benzene rings favored efficient adsorption. Despite the difference in capacity, the molar n(dye):n(Cu) ratios for acid orange 10, acid red 18, and acid green 25 were approximately 1:2 when the maximum capacities for the dyes were achieved at the optimal pH of 4. It suggested that one dye molecule bound to one dinuclear copper center on DTCSCu. The molar n(dye):n(Cu) ratio for the smallest dye, acid orange 7 (AO7), approached 1:1, demonstrating two AO7 molecules binding to two copper ions of the dinuclear core. The dyes adsorption related to the dinuclear copper core available on the polymer was further verified by electron spin resonance studies. Such interaction resulted in the formation of a ternary dye-metal-polymer complex. The ternary complexes were more stable than DTCSCu, which favored the adsorptions.

Ethylenediamine modified starch as biosorbent for acid dyes.

This work investigated the sorption performance of the ethylenediamine modified starch (CAS) for the removal of acid dyes from aqueous solutions. The influence of pH on adsorption of acid orange 10 (AO10), acid green 25 (AG25) and amido black 10B (AB10B) was evaluated. The sorption kinetics, equilibrium uptake and desorption of the loaded dyes in sodium sulfate solution were studied. It was found that the interaction mechanism was based on electrostatic attraction and hydrogen bonding. The adsorption of AG25 and AB10B followed pseudo-second-order model, whereas AO10 followed both pseudo-first-order and pseudo-second-order models. The best isotherm was Langmuir equation and the capacities followed the sequence AB10B>AG25>AO10. The different behaviors of individual dyes adsorption on CAS were largely dependent on the number of hydrophilic functional groups, which had strong tendency to form hydrogen bonds with the biosorbent. Dye release in sodium sulfate solutions was determined by the salt concentration and nature of dyes.

[Spectra study of a sodion triethylenetetramine-bisdithiocarbamate and its complexes with heavy metal ions].

A sodion triethylenetetramine-bisdithiocarbamate (DTC-TETA) and its complexes with heavy metal ions were investigated by FTIR, UV, FAAS and elemental analysis, respectively. The FTIR spectrum of DTC-TETA showed strong absorption peaks at 1 461-1 388 cm(-1) and 1 174-996 cm(-1) which were attributed to partly double bonds of C-N and C-S, respectively. The UV spectrum of DTC-TETA had two absorption peaks at 265 and 290 nm, assigned to pi-pi* transition of N...C...S radical and nonbonding electron n-pi* transition of S...C...S radical to conjugated system, respectively. The elemental analysis results demonstrated that the mol ratio of C, H, N and S in DTC-TETA was about 2 : 4 : 1 : 1. As for UV spectrum of its complexes with Cu(II), Cd(II), Zn(II) and Ni(II), there were four new absorption peaks at 321, 310, 311 and 325 nm, respectively. Coupled to flow-injection, FAAS determination showed that the complexation performance of Cu2+, Cd2+, Ni2+ and Zn2+ complexes of DTC-TETA was better than that of sodium diethyldithiocarbamate (DDTC).

[Spectra characteristics of an aminated glucose and its complex with Cu(II)].

Characteristics of an aminated glucose and its complex with Cu (II) were investigated by FTIR, 1H-NMR and UV spectroscopy, respectively. Compared with glucose, the FTIR spectrum of an aminated glucose showed a moderate peak at 1 629-1 608 cm(-1) which was attributed to deltaNH vibration, suggesting that glucose reacted with ethylenediamine. The 1H-NMR spectrum of an aminated glucose demonstrated the signal of the C1 hydroxy proton and one of the amino proton at 4. 82-4. 79 ppm, illustrating that the amino of ethylenediamine was substituted for the hydroxy group of C1. As for UV spectra, an aminated glucose did not show absorbance in the ultraviolet region while its complex with Cu(II) had obvious absorption peak at about 236 nm. The complex ratio of the aminated glucose to Cu(II) was about 1 to 1 and the stability constant of its Cu(II) complex was 6.8 x 10(7) L x mol(-1).

Syntheses, structures, and magnetic properties of unusual nonlinear polynuclear copper(II) complexes containing derivatives of 1,2,4-triazole and pivalate ligands.

Novel polynuclear Cu(II) complexes containing derivatives of 1,2,4-trizaole and pivalate ligands, [Cu(3)(mu(3)-OH)(mu-adetrz)(2)(piv)(5)(H(2)O)].6.5H(2)O (1) (adetrz = 4-amino-3,5-diethyl-1,2,4-triazole, piv = pivalate), [Cu(4)(mu(3)-OH)(2)(mu-atrz)(2)(mu-piv)(4)(piv)(2)].2MeOH.H(2)O (2) (atrz = 4-amino-1,2,4-triazole), [Cu(4)(mu(3)-OH)(2)(mu-tbtrz)(2)(mu-piv)(2)(piv)(4)].4H(2)O (3) (tbtrz = 4-tert-butyl-1,2,4-trizaole), and [Cu(4)(mu(3)-O)(2)(mu-admtrz)(4)(admtrz)(2)(mu-piv)(2)(piv)(2)].2[Cu(2)(mu-H(2)O)(mu-admtrz)(piv)(4)].13H(2)O [4 = 4a.2(4b).13H(2)O; admtrz = 4-amino-3,5-dimethyl-1,2,4-triazole], have been prepared and structurally characterized. 1 is an asymmetrical triangular complex containing a [Cu(3)(mu(3)-OH)] core with two Cu---Cu edges spanned by bridging adetrz ligands. 2, 3, and 4a are novel tetranuclear compounds containing a [Cu(4)(mu(3)-O)(2)] or [Cu(4)(mu(3)-OH)(2)] core with Cu---Cu edges spanned by bridging 1,2,4-triazole or pivalate ligands. 4b is a dinuclear compound with one admtrz and one water bridge, and it is the first dinuclear Cu(II) triazole complex with one bridging water molecule. 1 is one of few reported triangular Cu(II) complexes with derivatives of 1,2,4-triazole, while 2, 3, and 4a are the first group of the nonlinear tetranuclear Cu(II) compounds with derivatives of 1,2,4-triazole. Variable-temperature magnetic susceptibility studies on the powder samples of 1-3 reveal the overall antiferromagnetic coupling between Cu(II) ions with J values of -55.6 to -12.8 cm(-1) (1), -216.4 to 0 cm(-1) (2), and -259.8 to 4.8 cm(-1) (3).