Tenacic Acids: A New Class of Tenacious Binders to Metal Oxide Surfaces.

The backbone of 2-hydroxyisophthalic acid was identified as a potential metal oxide anchor because of the perfect alignment of all three of its donor groups for binding to inorganic surfaces. It can therefore be used in the design of organic linkers for metal oxide based hybrid materials. Optimized and scalable methods for the synthesis of 2-hydroxyisophthalic acid (1) and its 5-substituted derivatives: 5-bromo- (2), 5-sulfooxy- (3), 5-hydroxy- (4), and 5-PEG600 (5) are presented. Dynamic light scattering (DLS) demonstrated that compound 2 inhibits Fe(OH)3 precipitation when FeIII aqueous solutions are titrated with NaOH, while similar titrations in the presence of the structurally-related isophthalic and salicylic acids, both missing the third donor group, show turbidity at pHs as low as 2.3 and 3.5, respectively. The adduct synthesized from 4.5 nm γ-Fe2 O3 nanoparticles and 5 is water-, alcohol- and CH2 Cl2 -soluble, and forms stable aqueous colloids in the pH range of 4.4-8.7. Moreover, at a pH close to neutral these colloids survive at 100 °C, demonstrating the high practicality of 2-hydroxyisophthalic acid for nanoparticulate inorganic/organic hybrid material design.

Resonance Energy of an Arene Hydrocarbon from Heat of Combustion Measurements.

A simple experimental method for determination of the resonance energy by measuring the energies of combustion for two isomeric compounds, aromatic 1-tert-butyl-3,5-dimethylbenzene and nonaromatic trans,trans,cis-1,5,9-cyclododecatriene is proposed. Both compounds not only have the same molecular formula, but also contain the same number of sp2 and sp3 carbon atoms. After converting the obtained values into the gas phase heats of combustion and subtracting one value from another, the resulting mean resonance energy of 184 kJ/mol was obtained. The proposed method can be offered as an experiment for an undergraduate physical chemistry lab curriculum.

Synthesis of 5-Substituted Derivatives of Isophthalic Acid as Non-Polymeric Amphiphilic Coating for Metal Oxide Nanoparticles.

In the course of development of novel capping ligands with variable steric factor, which will be used as an organic coating for metal oxide nanoparticles, a base-catalyzed nucleophilic oxirane ring-opening addition reaction between dimethyl 5-hydroxyisophthalate and allyl glycidyl ether was studied. The allyl-terminated 1-1, 1-2 and 1-3 adducts and dihydroxylated derivative of the 1-1 adduct, 5-diglyceroxy isophthalic acid, were synthesized. The latter binds to the surface of 5 nm γ-Fe2O3 nanoparticles in reaction with their surfactant-free diethylene glycol colloids.

Superparamagnetic iron oxide nanoparticles with variable size and an iron oxidation state as prospective imaging agents.

Magnetite nanoparticles in the size range of 3.2-7.5 nm were synthesized in high yields under variable reaction conditions using high-temperature hydrolysis of the precursor iron(II) and iron(III) alkoxides in diethylene glycol solution. The average sizes of the particles were adjusted by changing the reaction temperature and time and by using a sequential growth technique. To obtain γ-iron(III) oxide particles in the same range of sizes, magnetite particles were oxidized with dry oxygen in diethylene glycol at room temperature. The products were characterized by DLS, TEM, X-ray powder diffractometry, TGA, chemical analysis, and magnetic measurements. NMR r(1) and r(2) relaxivity measurements in water and diethylene glycol (for OH and CH(2) protons) have shown a decrease in the r(2)/r(1) ratio with the particle size reduction, which correlates with the results of magnetic measurements on magnetite nanoparticles. Saturation magnetization of the oxidized particles was found to be 20% lower than that for Fe(3)O(4) with the same particle size, but their r(1) relaxivities are similar. Because the oxidation of magnetite is spontaneous under ambient conditions, it was important to learn that the oxidation product has no disadvantages as compared to its precursor and therefore may be a better prospective imaging agent because of its chemical stability.

Research Infrastructure Core Facilities at Research Centers in Minority Institutions: Part I-Research Resources Management, Operation, and Best Practices.

Funded by the National Institutes of Health (NIH), the Research Centers in Minority Institutions (RCMI) Program fosters the development and implementation of innovative research aimed at improving minority health and reducing or eliminating health disparities. Currently, there are 21 RCMI Specialized (U54) Centers that share the same framework, comprising four required core components, namely the Administrative, Research Infrastructure, Investigator Development, and Community Engagement Cores. The Research Infrastructure Core (RIC) is fundamentally important for biomedical and health disparities research as a critical function domain. This paper aims to assess the research resources and services provided and evaluate the best practices in research resources management and networking across the RCMI Consortium. We conducted a REDCap-based survey and collected responses from 57 RIC Directors and Co-Directors from 98 core leaders. Our findings indicated that the RIC facilities across the 21 RCMI Centers provide access to major research equipment and are managed by experienced faculty and staff who provide expert consultative and technical services. However, several impediments to RIC facilities operation and management have been identified, and these are currently being addressed through implementation of cost-effective strategies and best practices of laboratory management and operation.

The metamorphosis of heterometallic trinuclear antiferromagnetic complexes into nano-sized superparamagnetic spinels.

Thermal decomposition of the trinuclear heterometallic oxoacetates [Fe(2)M(µ(3)-O)(CH(3)COO)(6)(H(2)O)(3)] has been used as a single-precursor method for synthesis of the spinel-structured ternary oxides MFe(2)O(4) (M = Mn(II), Co(II), and Ni(II)). This facile process occurring at 320 °C results in the formation of nanocrystalline, (7-20 nm) highly pure stoichiometric ferrites in quantitative yield. The magnetic properties of these nanoparticulate ferrites were studied in the 10-300 K temperature range, revealing superparamagnetic behaviour for the Ni and Mn particles and ferromagnetic behavior for the Co ones at room temperature. Their blocking temperatures follow the order: CoFe(2)O(4) > MnFe(2)O(4) > NiFe(2)O(4).

A Versatile Method of Ambient-Temperature Solvent Removal.

Isolation of heat-sensitive reaction products in post-synthesis workup procedures often requires ambient-or low-temperature solvent removal. In the method demonstrated here, solvent evaporation is driven by the pressure gradient between a distillation flask and a chilled receiver in an evacuated closed system containing a minimal amount of residual noncondensable gas. Using an all-glass apparatus, the method is exemplified by evaporation of solvent samples from a distillation flask containing 50 mL of either dimethylformamide, dimethyl sulfoxide (DMSO), or N-methylpyrrolidone (NMP). The distillation flask is suspended in a water bath at temperatures of 18-28 °C, the evaporated solvent is collected in a receiver chilled with liquid nitrogen, and the entire process is completed in 90-140 min. The practicality of this method is further illustrated on a bench-chemistry scale by DMSO and NMP solvent removal from solutions of benzophenone, monitored by gravimetric and 1H NMR methods. Modification of the demonstrated method to mimic freeze-drying conditions (by reducing heat flow to the distillation flask) can be used for recovery of water-soluble compounds including polymers and biopolymers. We propose the name "cryovap" for this solvent removal method.

Synthesis of ultrasmall magnetic iron oxide nanoparticles and study of their colloid and surface chemistry.

Colloidal nanoparticles of Fe(3)O(4) (4 nm) were synthesized by high-temperature hydrolysis of chelated iron (II) and (III) diethylene glycol alkoxide complexes in a solution of the parent alcohol (H(2)DEG) without using capping ligands or surfactants: [Fe(DEG)Cl(2)](2-) + 2[Fe(DEG)Cl(3)](2-) + 2H(2)O + 2OH(-) → Fe(3)O(4) + 3H(2)DEG + 8Cl(-) The obtained particles were reacted with different small-molecule polydentate ligands, and the resulting adducts were tested for aqueous colloid formation. Both the carboxyl and α-hydroxyl groups of the hydroxyacids are involved in coordination to the nanoparticles' surface. This coordination provides the major contribution to the stability of the ligand-coated nanoparticles against hydrolysis.

Facile Reduction of Tungsten Halides with Nonconventional, Mild Reductants. 2. Four Convenient, High-Yield Solid-State Syntheses of the Hexatungsten Dodecachloride Cluster W(6)Cl(12) and Cluster Acid (H(3)O)(2)[W(6)(&mgr;(3)-Cl)(8)Cl(6)](OH(2))(x)(), Including New Cation-Assisted Ternary Routes.

Tungsten hexachloride was reduced by Hg or Bi at moderately low temperatures ( approximately 350 degrees C) to afford good yields (Hg, 73%; Bi, 85%) of W(6)Cl(12) after conversion of the reduction product to the chloro acid (H(3)O)(2)[W(6)(&mgr;(3)-Cl)(8)Cl(6)](OH(2))(x)(), recrystallization, and thermolysis in vacuo. Antimony was a less effective reductant because of the lower yield of chloro acid (31%) and the substantial quantities of insoluble byproducts found after HCl workup. The yield of (H(3)O)(2)[W(6)(&mgr;(3)-Cl)(8)Cl(6)](OH(2))(x)() from WCl(6) reduction by Sb improved dramatically to 79% with added KCl, while LiCl reduced the yield to only traces. In Bi reduction of WCl(6), the yield of (H(3)O)(2)[W(6)(&mgr;(3)-Cl)(8)Cl(6)](OH(2))(x)() decreased from 86 to 49% upon addition of NaCl, whereas added KCl had no effect on the yield. The Hg-, Bi-, Sb/KCl-, and Bi/KCl-based routes offer substantial experimental advantages over published methods for preparation of (H(3)O)(2)[W(6)(&mgr;(3)-Cl)(8)Cl(6)](OH(2))(x)() and W(6)Cl(12).

Attachment of a hydrophobically modified biopolymer at the oil-water interface in the treatment of oil spills.

The stability of crude oil droplets formed by adding chemical dispersants can be considerably enhanced by the use of the biopolymer, hydrophobically modified chitosan. Turbidimetric analyses show that emulsions of crude oil in saline water prepared using a combination of the biopolymer and the well-studied chemical dispersant (Corexit 9500A) remain stable for extended periods in comparison to emulsions stabilized by the dispersant alone. We hypothesize that the hydrophobic residues from the polymer preferentially anchor in the oil droplets, thereby forming a layer of the polymer around the droplets. The enhanced stability of the droplets is due to the polymer layer providing an increase in electrostatic and steric repulsions and thereby a large barrier to droplet coalescence. Our results show that the addition of hydrophobically modified chitosan following the application of chemical dispersant to an oil spill can potentially reduce the use of chemical dispersants. Increasing the molecular weight of the biopolymer changes the rheological properties of the oil-in-water emulsion to that of a weak gel. The ability of the biopolymer to tether the oil droplets in a gel-like matrix has potential applications in the immobilization of surface oil spills for enhanced removal.

Reactivity of 3d transition metal cations in diethylene glycol solutions. Synthesis of transition metal ferrites with the structure of discrete nanoparticles complexed with long-chain carboxylate anions.

Study of the reactivity of 3d transition metal cations in diethylene glycol solutions revealed several key features that made it possible to develop a new method for synthesis of the nanocrystalline transition metal ferrites. The 3-7 nm particles of [MFe2O4]n[O2CR]m, where M = Mn, Fe, Co, Ni, and Zn, ligated on their surface with long-chain carboxylate anions, have been obtained in an isolated yield of 75-90%. The key features are the following. Complexation of the first-row transition metal cations with diethylene glycol at a presence of alkaline hydroxide is sufficient to enable control over the rate of their hydrolysis. The reaction of hydrolysis leads to the formation of metal oxide nanocrystals in colloidal solution. The nanoparticles growth is terminated by an added long-chain carboxylic acid, which binds to their surface and acts as a capping ligand. The isolated nanocrystalline powders are stable against agglomeration and highly soluble in nonpolar organic solvents.