Covalent Functionalization of Carbon Nanotube by Tetrasubtituted Amino Manganese Phthalocyanine

The multiwall carbon nanotube (MWCNT) bonded to 2, 9, 16, 23-tetraamino manganese phthalocyanine (TAMnPc) was obtained by covalent functionalization, and its chemical structure was characterized by TEM. The photoconductivity of single-layered photoreceptors, where MWCNT bonded by TAMnPc (MWCNT-b-TAMnPc) served as the charge generation material (CGM), was also studied.

Covalently Bonded Ni Sites in Black Phosphorene with Electron Redistribution for Efficient Metal‑Lightweighted Water Electrolysis

The metal-lightweighted electrocatalysts for water splitting are highly desired for sustainable and economic hydrogen energy deployments,but challengeable.In this work,a low-content Ni-functionalized approach triggers the high capability of black phosphorene(BP)with hydrogen and oxygen evolution reaction(HER/OER)bifunctionality.Through a facile in situ electro-exfoliation route,the ionized Ni sites are covalently functionalized in BP nanosheets with electron redistribution and controllable metal contents.It is found that the as-fabricated Ni-BP electrocatalysts can drive the water splitting with much enhanced HER and OER activities.In 1.0 M KOH electrolyte,the optimized 1.5 wt%Nifunctionalized BP nanosheets have readily achieved low overpotentials of 136 mV for HER and 230 mV for OER at 10 mA cm^(−2).Moreover,the covalently bonding between Ni and P has also strengthened the catalytic stability of the Ni-functionalized BP electrocatalyst,stably delivering the overall water splitting for 50 h at 20 mA cm^(−2).Theoretical calculations have revealed that Ni–P covalent binding can regulate the electronic structure and optimize the reaction energy barrier to improve the catalytic activity effectively.This work confirms that Ni-functionalized BP is a suitable candidate for electrocatalytic overall water splitting,and provides effective strategies for constructing metal-lightweighted economic electrocatalysts.

Covalent functionalization of graphene oxide by 9-(4-aminophenyl)acridine and its derivatives

Graphene/acridine （G-Acr） hybrid structures were synthesized through covalent functionalization of graphene oxide with 9-（4- aminophenyl）acridine （APA） and its derivatives. The G-Act hybrids were characterized by Fourier transform infrared spectroscopy, ultraviolet-visible spectrophotometry, thermal gravimetric analysis and Raman spectroscopy. X-ray photoelectron spectroscopy confirms that the binding energies of APA and its derivatives shifted to higher values, revealing pronounced charge transfer at the interface of graphene and organic molecules.

Covalent functionalization of decellularized tissues accelerates endothelialization

In the field of tissue regeneration,the lack of a stable endothelial lining may affect the hemocompatibility of both synthetic and biological replacements.These drawbacks might be prevented by specific biomaterial functionalization to induce selective endothelial cell(EC)adhesion.Decellularized bovine pericardia and porcine aortas were selectively functionalized with a REDV tetrapeptide at 10^(-5)M and 10^(-6)M working concentrations.The scaffold-bound peptide was quantified and REDV potential EC adhesion enhancement was evaluated in vitro by static seeding of human umbilical vein ECs.The viable cells and MTS production were statistically higher in functionalized tissues than in control.Scaffold histoarchitecture,geometrical features,and mechanical properties were unaffected by peptide anchoring.The selective immobilization of REDV was effective in accelerating ECs adhesion while promoting proliferation in functionalized decellularized tissues intended for blood-contacting applications.

Self-templated covalent functionalization of graphitic surfaces with a quasi-periodic pattern

Patterned covalent functionalization of graphitic surfaces(GSs)is of interest in the development of devices and nanocomposite materials.In contrast to the strategies using external templates or control for realizing patterned covalent functionalization of GSs,here,we present a self-templated strategy by exploiting the synergistic effects of chemical and physical functionalization of GSs.Therefore,a diazonium salt is reduced by potassium iodide(KI)in dimethyl sulfoxide while the solution is in contact with a GS,resulting in its spatially heterogeneous,that is,chemical and physical,functionalization.This heterogeneous functionalization leads to a quasiperiodic pattern of striped corrals with three equivalent orientations in the covalent layer.The formation of the striped corrals is ascribed to physisorbed domains formed by self-assembled N_(2),which is produced in situ during the reduction of the diazonium salt,preventing the covalent functionalization.

Structural and Mechanistic Studies of γ-Fe2O3 Nanoparticle as Capecitabine Drug Nanocarrier

Using density functional theory,noncovalent interactions and four mechanisms of covalent functionalization of capecitabine anticancer drug onto γ-Fe2O3 nanoparticles have been investigated.Quantum molecular descriptors of noncovalent configurations were studied.It was specified that binding of capecitabine onto γ-Fe2O3 nanoparticles is thermodynamically suitable.Hardness and the gap of energy between LUMO and HOMO of capecitabine are higher than the noncovalent configurations,showing the reactivity of capecitabine increases in the presence of γ-Fe2O3 nanoparticles.Capecitabine can bond to γ-Fe2O3 nanoparticles through OH（k1 mechanism）,NH（k2 mechanism）,CO（k3 mechanism） and F（k4 mechanism） groups.The activation energies,activation enthalpies and activation Gibbs free energies of these reactions were calculated.It was specified that the k1 and k2 mechanisms are under thermodynamic control and k3 and k4 under kinetic control.These results could be generalized to other similar drugs.

Mechanistic, Energetic and Structural Aspects of the Adsorption of Carmustine on the Functionalized Carbon Nanotubes

Using density functional theory, noncovalent interactions and two mechanisms of covalent functionalization of drug carmustine with functionalized carbon nanotube（CNT） have been investigated. Quantum molecular descriptors of noncovalent configurations were studied. It was specified that binding of drug carmustine with functionalized CNT is thermodynamically suitable. NTCOOH and NTCOCl can bond to the NH group of carmustine through OH（COOH mechanism） and Cl（COCl mechanism） groups, respectively. The activation energies, activation enthalpies and activation Gibbs free energies of two pathways were calculated and compared with each other. The activation parameters related to COOH mechanism are higher than those related to COCl mechanism, and therefore COCl mechanism is suitable for covalent functionalization. COOH functionalized CNT（NTCOOH） has more binding energy than COCl functionalized CNT（NTCOCl） and can act as a favorable system for carmustine drug delivery within biological and chemical systems（noncovalent）. These results could be generalized to other similar drugs.

Covalent carbene modification of 2D black phosphorus

Black phosphorus(BP)has attracted an ever-growing interest due to its unique anisotropic two-dimensional structure,impressive photoelectronic properties and attractive application potential.However,the tools for bandgap engineering and passivation via covalent modification of BP nanosheets remain limited to diazonium salt and nucleophilic addition methods,so that developing new modification strategies for BP nanosheets is crucial to explore its physical and chemical properties and enrich the toolbox for functionalization.Herein,we report the covalent modification of liquid-phase exfoliated BP nanosheets based on a rational analysis of BP structure.The modification of BP is achieved via carbene,a highly reactive organic mediate.The carbene modification improves the solubility and stability of BP nanosheets.Detailed microscopic and spectroscopic characterizations including infrared spectra,Raman spectra,X-ray photoelectron spectra,SEM and TEM were conducted to provide insights for the reaction.The proof of the existence of covalent bonds between BP nanosheets and organic moieties confirms the successful modification.Moreover,theoretical calculations were conducted to unveil the reaction mechanism of the two different types of bonds and the chemical property of two-dimensional BP.

Structure and Properties of Chemically-reduced Functionalized Graphene Oxide Platelets

Green reduction of graphene oxide(GO) functionalized with 3-aminopropyltriethoxysilane and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride/N-hydroxysuccinimide was performed by using ascorbic acid and sodium bisulfite.The obtained materials were characterized by thermo-gravimetric analysis,transmission electron microscopy.X-ray diffraction,UV-Vis,Fourier transform infrared and Raman spectroscopy techniques.The results indicated a strong dependence of the materials properties such as deoxygenation degree,absorption peak shift,crystallite size and functionalization degree on the functionalization approach and reducing agent.

PREFACE

Hydrogels are classical soft and wet materials that have been extensively studied over the past several decades. Recently, with the development of supramolecular science, nanotechnology and precisely synthetic chemistry, various novel hydrogels have been designed and fabricated, which show emerging applications in tissue engineering, drug delivery, anti-fouling coatings, flexible electronics and soft robotics. Through tailoring their two-dimensional surface structures and three- dimensional networks, unique properties such as ultra-high mechanical strength, responsiveness to various kinds of stimuli, biocompatibility, special wettability and adhesion can be achieved.