Photodissociation dynamics of the reaction H2CO-->H+HCO via the singlet (S0) and triplet (T1) surfaces

We have explored the photodissociation dynamics of the reaction H(2)CO+hnu-->H+HCO in the range of 810-2600 cm(-1) above the reaction threshold. Supersonically cooled formaldehyde was excited into selected J(Ka,Kc) rotational states of six vibrational levels (1(1)4(1), 5(1), 2(2)6(1), 2(2)4(3), 2(3)4(1), and 2(4)4(1)) in the A((1)A2) state. The laser induced fluorescence spectra of the nascent HCO fragment provided detailed product state distributions. When formaldehyde was excited into the low-lying levels 1(1)4(1), 5(1), and 2(2)6(1), at E(avail)<1120 cm(-1), the product state distribution can be modeled qualitatively by phase space theory. These dynamics are interpreted as arising from a reaction path on the barrierless S0 surface. When the initial states 2(2)4(3) and 2(3)4(1) were excited (E(avail)=1120-1500 cm(-1)), a second type of product state distribution appeared. This second distribution peaked sharply at low N, Ka and was severely truncated in comparison with those obtained from the lower lying states. At the even higher energy of 2(4)4(1) (E(avail) approximately 2600 cm(-1)) the sharply peaked distribution appears to be dominant. We attribute this change in dynamics to the opening up of the triplet channel to produce HCO. The theoretical height of the barrier on the T1 surface lies between 1700 and 2100 cm(-1) and so we consider the triplet reaction to proceed via tunneling at the intermediate energies and proceed over the barrier at the higher energies. Considerable population was observed in the excited (0,0,1) state for all initial H(2)CO states that lie above the appearance energy. Rotational populations in the (0,0,1) state dropped more rapidly with (N,Ka) than did the equivalent populations in (0,0,0). This indicates that, although individual rotational states are highly populated in (0,0,1), the total v3=1 population might not be so large. Specific population was also measured in the almost isoenergetic Kc and J states. No consistent population preference was found for either asymmetry or spin-rotation component.     

Synthesis and chemistry of N‐arylated pyrano[2,3‐c]pyrazoles

Novel N2‐arylated pyrano[2,3‐c]pyrazol‐6‐ones 2 can be prepared in a selective manner by generating the anion of 1 ( R?H ) with lithium hexamethyldisilazide in DMF and quenching with activated aryl halides. Sterically demanding groups such as phenyl as in 5 reduce reactivity significantly while electronwithdrawing substituents such as trifluoromethyl and phenyl at C4 of the pyranone ring as in 10 and 15 render the pyranone carbonyl particularly susceptible to attack by nucleophiles resulting in ring‐opening to give novel crotonyl derivatives. Proof of structure required a variety of nmr methods involving proton, carbon, and nitrogen nuclei.     

Highly active/selective and adjustable zirconium polymerization catalysts stabilized by aminopyridinato ligands

This paper describes a substantial enhancement of the aminopyridinato ligand stabilized early transition metal chemistry by introducing the sterically very demanding 2,6-dialkylphenyl substituted aminopyridinato ligands derived from (2,6-diisopropylphenyl)-[6-(2,6-dimethylphenyl)-pyridin-2-yl]-amine (1a-H, ApH) and (2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)-pyridin-2-yl]- amine (1b-H, Ap^∗H). The corresponding bis aminopyridinato zirconium dichloro complexes, [Ap₂ZrCl₂] (3a) and [Ap₂^∗ZrCl₂] (3b) and the dimethyl analogues, [Ap₂ZrMe₂] (4a) and [Ap₂^∗ZrMe₂] (4b) (Me = methyl) were synthesized, using standard salt metathesis routes. Single-crystal X-ray diffraction was carried out for the dichloro derivatives. Both zirconium metal centers have a distorted octahedral environment with a cis-orientation of the chloride ligands in 3a and a closer to trans-arrangement in 3b. The dimethyl derivatives are proven to be highly active ethylene polymerization catalysts after activation with [R₂N(Me)H][B(C₆F₅)₄] (R = C₁₆H₃₃-C₁₈H₃₇). During attempted co-polymerizations of α-olefins (propylene) and ethylene high activity and selectivity for ethylene and nearly no co-monomer incorporation was observed. Increasing the steric bulk of the ligand going from (2,6-dimethylphenyl) to (2,4,6-triisopropylphenyl) substituted pyridines, switches the catalyst system from producing long chain α-olefins to polymerization of ethylene in a living fashion. In contrast to the dimethyl complexes only [Ap₂^∗ZrCl₂] in the presence of MAO at elevated temperature gave decent polymerization activity. NMR investigations of the reaction of dichloro complexes with 25 equiv. of MAO or AlMe₃ at room temperature revealed, that [Ap₂ZrCl₂] decomposes under ligand transfer to aluminum and formation of [ApAlMe₂], while [Ap₂^∗ZrCl₂] remains almost unreacted under the same conditions. The aminopyridinato dimethyl aluminum complexes, [ApAlMe₂] (5a) and [Ap^∗AlMe₂] (5b) were synthesized independently and structurally characterized. The aluminum complexes 5a and b show no catalytic activity towards ethylene, when “activated” with[R₂N(Me)H][B(C₆F₅)₄].     

Carbonylative ring opening of terminal epoxides at atmospheric pressure

The carbonylative opening of terminal epoxides under mild conditions has been developed using Co2(CO)8 as the catalyst. Under 1 atm of carbon monoxide and at room temperature in methanol, propylene oxide is converted to methyl 3-hydroxybutanoate in up to 89% yield. This transformation is general for many terminal epoxides bearing alkyl, alkenyl, aryl, alkoxy, chloromethyl, phthalimido, and acetal functional groups. The opening takes place without epimerization at the secondary stereocenter.     

Trisannulated benzene derivatives by Acid catalyzed aldol cyclotrimerizations of cyclic ketones. Methodology development and mechanistic insight

Several factors that contribute to the success of aldol cyclotrimerizations have been clarified as part of an effort to shed light on the inner workings of this century old reaction. The use of 4,7-di-tert-butylacenaphthenone (11) as a mechanistic probe molecule has led to intriguing discoveries about temperature, solvent, and solubility effects. Solvents that are both polarizable and somewhat polar, e.g., o-dichlorobenzene (ODCB), work best for the aromatic ketones examined. Certain Br?nsted acids were found to work better than Lewis acids as catalysts for the archetypal aldol cyclotrimerization of indanone (2) in aprotic solvents, and a strong dependence on the pKa of the acid was observed. A standardized protocol, using p-toluenesulfonic acid monohydrate, is shown to work well in a number of test cases.     

Disubstituted pyridines: the double-coupling approach

A one-pot procedure leading to disubstituted pyridines from the starting dibromopyridines is described. Key features include the ability to couple a range of aryl and even alkenylboronic acids at the 2,3 and/or 2,5 positions with excellent regiocontrol under a standard set of conditions. Further, isolated yields are greatly improved by the use of neutral alumina in place of silica for product purification. Finally, the intrinsic electronic bias of the pyridine ring can be overcome by using a bromoiodopyridine.     

Surface characterizations of spin-coated films of ethylcellulose and hydroxypropyl methylcellulose blends

Films of pure ethylcellulose (EC) and hydroxypropyl methylcellulose (HPMC) polymers and EC/HPMC blends were prepared from solutions by spin coating where isopropyl alcohol (IPA), water, and IPA/water cosolvent were used as solvents. Surface structures of the films were investigated using optical microscopy, atomic force microscopy (AFM), and Raman mapping and spectroscopy. For the films prepared from EC/HPMC blend solutions using the IPA/water cosolvent, different domain structures such as islands or pits and phase separation between EC and HPMC were observed by optical microscopy and AFM. The nature of the polymer components on the surface of the films was identified by Raman mapping and spectroscopy. Experimental results also indicated that polymer composition, solvent, and temperature during spin coating had significant impacts on surface structures of the films.     

Preparation and characterization of poly(lipid)-coated, fluorophore-doped silica nanoparticles for biolabeling and cellular imaging

The fabrication, characterization, and implementation of poly(lipid)-coated, highly luminescent silica nanoparticles as fluorescent probes for labeling of cultured cells are described. The core of the probe is a sol-gel-derived silica nanoparticle, 65-100 nm in diameter, in which up to several thousand dye molecules are encapsulated (Lian, W.; et al. Anal. Biochem. 2004, 334, 135-144). The core is coated with a membrane composed of bis-sorbylphosphatidylcholine, a synthetic polymerizable lipid that is chemically cross-linked to enhance the environmental and chemical stability of the membrane relative to a fluid lipid membrane. The poly(lipid) coating has two major functions: (i) to reduce nonspecific interactions, based on the inherently biocompatible properties of the phosphorylcholine headgroup, and (ii) to permit functionalization of the particle, by doping the coating with lipids bearing chemically reactive or bioactive headgroups. Both functions are demonstrated: (i) Nonspecific adsorption of dissolved proteins to bare silica nanoparticles and of bare nanoparticles to cultured cells is significantly reduced by application of the poly(lipid) coating. (ii) Functionalization of poly(lipid)-coated nanoparticles with a biotin-conjugated lipid creates a probe that can be used to target both dissolved protein receptors as well as receptors on the membranes of cultured cells. Measurements performed on single nanoparticles bound to planar supported lipid bilayers verify that the emission intensity of these probes is significantly greater than that of single protein molecules labeled with several fluorophores.     

Solvent dependent friction force response of polystyrene brushes prepared by surface initiated polymerization

Polystyrene (PS) brushes were prepared on oxide passivated silicon by the surface initiated polymerization (SIP) technique. From an AIBN-type free radical initiator, which was silanized and immobilized on silicon wafers, styrene brushes were directly polymerized and grafted from the surface. The formation of the initiator monolayer and, subsequently, the polymer brush on the surface were monitored by X-ray photoelectron spectroscopy (XPS) and ellipsometry. Friction force measurements were performed by atomic force microscopy (AFM), using a 5 microm SiO2 colloidal sphere tip and under systematically varied solvent environments (nonpolar to polar), to demonstrate the dependence of brush lubricity on solvation. The relative uptake of solvents in the PS brush was determined by quartz crystal microbalance (QCM), and it correlates well with friction data. It is surmised that, in poor solvent environments, the polymer brush exists in a collapsed conformation, giving rise to the higher observed friction response.     

Frequency dependence of gold nanoparticle superassembly by dielectrophoresis

Dielectrophoresis is an effective method for capturing nanoparticles and assembling them into nanostructures. The frequency of the dielectrophoretic alternating current (ac) electric field greatly influences the morphology of resultant nanoparticle assemblies. In this study, frequency regimes associated with specific gold nanoparticle assembly morphologies were identified. Gold nanoparticles suspended in water were captured by microelectrodes at different electric field frequencies onto thin silicon nitride membranes. The resultant assemblies were examined by transmission electron microscopy. For this system, the major frequency-dependent influence on morphology appears to arise not from the Clausius-Mossotti factor of the dielectrophoretic force itself, but instead from ac electroosmotic fluid flow and the influence of the electrical double layer at the electrode-solution interface. Frequency regimes of technological interest include those forming one-dimensional nanoparticle chains, microwires, combinations of microwires and nanoparticle chains suitable for nanogap electrode formation, and dense three-dimensional assemblies with very high surface area.