Controlled morphogenesis of organic polyhedral nanocrystals from cubes, cubooctahedrons, to octahedrons by manipulating the growth kinetics. 2011

Longtian Kang, and Hongbing Fu, and Xinqiang Cao, and Qiang Shi, and Jiannian Yao
Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China.

Morphological control of organic nanocrystals (ONCs) is important in the fields ranging from specialty chemicals to molecular semiconductors. Although the thermodynamic shape can be readily predicted, most growth morphologies of ONCs are actually determined by kinetic factors and remain poorly understood. On the basis of the reduction of zinc tetraphenylporphyrin perchlorate (ZnTPP(+)ClO(4)(-)) with sodium nitrite (Na(+)NO(2)(-)), we synthesized two series of ONCs of aquozinc tetraphenylporphyrin (ZnTPP·H(2)O), in the presence of either cetyltrimethylammonium bromide (CTAB) or poly(vinyl pyrrolidone) (PVP) as the capping ligands. As the cationic precursors of ZnTPP(+) are separated in the solution phase, smoothly controlled release of ZnTPP·H(2)O building blocks via the reduction reaction facilitates the separation between the nucleation and growth stages during the formation of ONCs and provides a high and tunable supersaturation unavailable by employing conventional crystallization techniques. We found that CTAB mainly serve as the colloidal stabilizer, while selective adhesion of PVP on the {020}s facet alters the crystal habits significantly. In both cases, manipulation of the growth kinetics had been achieved by adjusting the concentration of ZnTPP·H(2)O growth units, and consequently, the supersaturation for the crystallization, thus yielding ONCs with well-controlled sizes and shapes. Remarkably, thermodynamically stable octahedrons have been obtained at high supersaturation in both CTAB and PVP cases.

UI MeSH Term Description Entries
D007700 Kinetics The rate dynamics in chemical or physical systems.
D008024 Ligands A molecule that binds to another molecule, used especially to refer to a small molecule that binds specifically to a larger molecule, e.g., an antigen binding to an antibody, a hormone or neurotransmitter binding to a receptor, or a substrate or allosteric effector binding to an enzyme. Ligands are also molecules that donate or accept a pair of electrons to form a coordinate covalent bond with the central metal atom of a coordination complex. (From Dorland, 27th ed) Ligand
D008665 Metalloporphyrins Porphyrins which are combined with a metal ion. The metal is bound equally to all four nitrogen atoms of the pyrrole rings. They possess characteristic absorption spectra which can be utilized for identification or quantitative estimation of porphyrins and porphyrin-bound compounds. Metalloporphyrin
D008958 Models, Molecular Models used experimentally or theoretically to study molecular shape, electronic properties, or interactions; includes analogous molecules, computer-generated graphics, and mechanical structures. Molecular Models,Model, Molecular,Molecular Model
D008968 Molecular Conformation The characteristic three-dimensional shape of a molecule. Molecular Configuration,3D Molecular Structure,Configuration, Molecular,Molecular Structure, Three Dimensional,Three Dimensional Molecular Structure,3D Molecular Structures,Configurations, Molecular,Conformation, Molecular,Conformations, Molecular,Molecular Configurations,Molecular Conformations,Molecular Structure, 3D,Molecular Structures, 3D,Structure, 3D Molecular,Structures, 3D Molecular
D009930 Organic Chemicals A broad class of substances containing carbon and its derivatives. Many of these chemicals will frequently contain hydrogen with or without oxygen, nitrogen, sulfur, phosphorus, and other elements. They exist in either carbon chain or carbon ring form. Organic Chemical,Chemical, Organic,Chemicals, Organic
D011205 Povidone A polyvinyl polymer of variable molecular weight; used as suspending and dispersing agent and vehicle for pharmaceuticals; also used as blood volume expander. Polvidone,Polyvidon,Polyvinylpyrrolidone,Arufil,Bolinan,Bolinan 40,Crospovidone,Dulcilarmes,Duratears Free,Enterodes,Enterodez,Hypotears,Kollidon,Lacophtal,Lacri-Stulln,Lagrifilm,Liquifilm Lagrimas,Nutrivisc,Oculotect,PVP 40,Periston,Plasdone,Polyplasdone XL,Povidone, Unspecified,Protagens,Protagent,Unifluid,Vidirakt S mit PVP,Vidisic PVP Ophtiole,Wet-Comod,Dulcilarme,Enterode,Hypotear,Polyvidons,Protagen,Unspecified Povidone
D002593 Cetrimonium Compounds Cetyltrimethylammonium compounds that have cationic detergent, antiseptic, and disinfectant activities. They are used in pharmaceuticals, foods, and cosmetics as preservatives; on skin, mucous membranes, etc., as antiseptics or cleansers, and also as emulsifiers. These compounds are toxic when used orally due to neuromuscular blockade. Cetyltrimethylammonium Compounds,Cetrimides,Compounds, Cetrimonium,Compounds, Cetyltrimethylammonium
D003102 Colloids Two-phase systems in which one is uniformly dispersed in another as particles small enough so they cannot be filtered or will not settle out. The dispersing or continuous phase or medium envelops the particles of the discontinuous phase. All three states of matter can form colloids among each other. Hydrocolloids,Colloid,Hydrocolloid
D000077286 Cetrimonium Cetyltrimethylammonium compound whose salts and derivatives are used primarily as topical antiseptics. 1-Hexadecyltrimethylammonium Chloride,CTAB,CTAOH,Cetavlon,Cetrimide,Cetriminium,Cetrimonium Bromide,Cetrimonium Chloride,Cetrimonium Hydroxide,Cetrimonium Iodide,Cetrimonium Methosulfate,Cetrimonium Methyl Sulfate,Cetrimonium Monosulfate,Cetyltrimethylammonium Bromide,Cetyltrimethylammonium Chloride,HTAB Cpd,Hexadecyl Trimethyl Ammonium Bromide,Hexadecyl(trimethyl)azanium,Hexadecyltrimethylammonium Bromide,Hexadecyltrimethylammonium Octylsulfonate,Octylsulfonate, Hexadecyltrimethylammonium

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