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391.
392.
Barsanti KC Luo W Isabelle LM Pankow JF Peyton DH 《Magnetic resonance in chemistry : MRC》2007,45(2):167-170
The submicron liquid droplets constituting the particulate matter of mainstream tobacco smoke (PMMTS) are viscous and of a composition that is complex and poorly understood. PMMTS is often approximately 80% w/w 'tar' where 'tar'=total PMMTS- (nicotine+water). Many of the chemical agents in MTS responsible for smoking-related cancers are found at least partially in the PMMTS portion of MTS. The properties of PMMTS vary with brand and with puffing patterns. The chemical forms and total levels of nicotine, the identities/levels of other compositionally dominant compounds, and the identities/levels of carcinogens are of interest. Most studies of the composition of PMMTS have involved extraction then chromatography. Such methods allow the determination of low-level constituents, but alter the samples such that direct information regarding chemical conditions within the PMMTS cannot be obtained. Here, we utilize nuclear magnetic resonance spectroscopy (NMR) to examine native PMMTS in conventional cigarettes, including measurements of the brand-dependent fraction of PMMTS nicotine that is in the free-base form (increasing this fraction in inhaled tobacco smoke affects the rates of the processes governing nicotine deposition in the respiratory tract, and so has implications for smoking behavior and addiction). We also demonstrate the use of NMR for characterizing the composition of PMMTS (including the levels of selected cigarette additives) when the cosolvent DMSO-d6 is added to improve spectral resolution. The native and solvent-assisted results open the door to a range of future studies. 相似文献
393.
Ahrens MJ Kelley RF Dance ZE Wasielewski MR 《Physical chemistry chemical physics : PCCP》2007,9(12):1469-1478
A bichromophoric electron donor-acceptor molecule composed of a zinc tetraphenylporphyrin (ZnTPP) surrounded by four perylene-3,4:9,10-bis(dicarboximide)(PDI) chromophores (ZnTPP-PDI(4)) was synthesized. The properties of this molecule were compared to a reference molecule having ZnTPP covalently bound to a single PDI (ZnTPP-PDI). In toluene, ZnTPP-PDI(4) self-assembles into monodisperse aggregates of five molecules arranged in a columnar stack, (ZnTPP-PDI(4))(5). The monodisperse nature of this assembly contrasts sharply with previously reported ZnTPP-PDI(4) derivatives having 1,7-bis(3,5-di-t-butylphenoxy) groups (ZnTPP-PPDI(4)). The size and structure of this assembly in solution was determined by small angle X-ray scattering (SAXS) using a high flux synchrotron X-ray source. The ZnTPP-PDI reference molecule does not aggregate. Femtosecond transient absorption spectroscopy shows that laser excitation of both ZnTPP-PDI and (ZnTPP-PDI(4))(5) results in quantitative formation of ZnTPP(+*)-PDI(-*) radical ion pairs in a few picoseconds. The transient absorption spectra of (ZnTPP-PDI(4))(5) suggest that the PDI(-*) radicals interact strongly with adjacent PDI molecules within the columnar stack. Charge recombination occurs more slowly within (ZnTPP-PDI(4))(5)(tau= 4.8 ns) than it does in ZnTPP-PDI (tau= 3.0 ns) producing mostly ground state as well as a modest yield of the lowest triplet state of PDI ((3*)PDI). Formation of (3*)PDI occurs by rapid spin-orbit induced intersystem crossing (SO-ISC) directly from the singlet radical ion pair as evidenced by the electron spin polarization pattern exhibited by its time-resolved electron paramagnetic resonance spectrum. 相似文献
394.
Shibata S Zhang Z Korotkov KV Delarosa J Napuli A Kelley AM Mueller N Ross J Zucker FH Buckner FS Merritt EA Verlinde CL Van Voorhis WC Hol WG Fan E 《Analytical and bioanalytical chemistry》2011,401(5):1585-1591
Ultrafiltration provides a generic method to discover ligands for protein drug targets with millimolar to micromolar K(d), the typical range of fragment-based drug discovery. This method was tailored to a 96-well format, and cocktails of fragment-sized molecules, with molecular masses between 150 and 300 Da, were screened against medical structural genomics target proteins. The validity of the method was confirmed through competitive binding assays in the presence of ligands known to bind the target proteins. 相似文献
395.
396.
A comparative study of energy consumption and physical properties of microfibrillated cellulose produced by different processing methods 总被引:1,自引:0,他引:1
Kelley L. Spence Richard A. Venditti Orlando J. Rojas Youssef Habibi Joel J. Pawlak 《Cellulose (London, England)》2011,18(4):1097-1111
Microfibrillated celluloses (MFCs) with diameters predominantly in the range of 10–100 nm liberated from larger plant-based
fibers have garnered much attention for the use in composites, coatings, and films due to large specific surface areas, renewability,
and unique mechanical properties. Energy consumption during production is an important aspect in the determination of the
“green” nature of these MFC-based materials. Bleached and unbleached hardwood pulp samples were processed by homogenization,
microfluidization, and micro-grinding, to determine the effect of processing on microfibril and film properties, relative
to energy consumption. Processing with these different methods affected the specific surface area of the MFCs, and the film
characteristics such as opacity, roughness, density, water interaction properties, and tensile properties. Apparent film densities
were approximately 900 kg/m3 for all samples and the specific surface area of the processed materials ranged from approximately 30 to 70 m2/g for bleached hardwood and 50 to 110 m2/g for unbleached hardwood. The microfluidizer resulted in films with higher tensile indices than both micro-grinding and
homogenization (148 Nm/g vs. 105 Nm/g and 109 Nm/g, respectively for unbleached hardwood). Microfluidization and micro-grinding
resulted in films with higher toughness values than homogenization and required less energy to obtain these properties, offering
promise for producing MFC materials with lower energy input. It was also determined that a refining pretreatment required
for microfluidization or homogenization can be reduced or eliminated when producing MFCs with the micro-grinder. A summary
of the fiber and mechanical energy costs for different fibers and processing conditions with economic potential is presented. 相似文献
397.
Kelley AM 《The Journal of chemical physics》2008,128(22):224702
The enhancement of resonance Raman scattering by coupling to the plasmon resonance of a metal nanoparticle is developed by treating the molecule-metal interaction as transition dipole coupling between the molecular electronic transition and the much stronger optical transition of the nanoparticle. A density matrix treatment accounts for coupling of both transitions to the electromagnetic field, near-resonant energy transfer between the molecule-excited and nanoparticle-excited states, and dephasing processes. This fully quantum mechanical approach reproduces the interference effects observed in extinction spectra of J-aggregated dyes adsorbed to metal nanoparticles and makes testable predictions for surface-enhanced resonance Raman excitation profiles. 相似文献
398.
Jensen RA Kelley RF Lee SJ Wasielewski MR Hupp JT Tiede DM 《Chemical communications (Cambridge, England)》2008,(16):1886-1888
The structure of a cyclic self-assembled tetramer of an asymmetric meso-ethynylpyridyl-functionalized Zn(II)-porphyrin was established by solution-phase X-ray scattering and diffraction; femtosecond transient absorption and anisotropy spectroscopies were used to (a) observe rapid energy transfer (3.8 ps(-1)) between porphyrin subunits and (b) establish that the transfer occurs between adjacent units. 相似文献
399.
Hyper-Raman spectra were obtained for zinc phthalocyanine in a dilute pyridine solution at excitation wavelengths that are two-photon resonant with the one-photon-allowed B band (360-380 nm) as well as with the two-photon absorption near 440 nm reported by Drobizhev et al. ( J. Chem. Phys. 2006, 124, 224701 ). In both regions, the hyper-Raman spectra were very different from the linear resonance Raman spectra at the corresponding excitation frequencies. While the resonance Raman spectra show only g symmetry modes, almost all of the hyper-Raman frequencies can be assigned as fundamentals of E u symmetry that also are observed in the infrared absorption spectrum or E u symmetry combination bands. These results contrast sharply with previous observations of highly noncentrosymmetric push-pull conjugated molecules and are consistent with a structure for phthalocyanine in solution that is centrosymmetric or nearly so. The hyper-Raman spectra show different intensity patterns in the two excitation regions, consistent with different Franck-Condon and/or vibronic coupling matrix elements for the different resonant states. 相似文献
400.
Bringley JF Wunder A Howe AM Wesley RD Qiao TA Liebert NB Kelley B Minter J Antalek B Hewitt JM 《Langmuir : the ACS journal of surfaces and colloids》2006,22(9):4198-4207
A novel precision-assembly methodology is described on the basis of the controlled, simultaneous assembly (CSA) of a core nanoparticle substrate and polyelectrolyte solutions. The method is capable of assembly rates at least as fast as 10(16) core particles s(-1) L(-1) and affords concentrated suspensions of stable colloids with an adsorbed polyelectrolyte. The resulting dispersions are highly homogeneous, have a low viscosity and narrow particle-size distribution, and are stable colloids, even at solid concentrations of at least 33 wt %. The adsorption isotherm and the saturation adsorption for polyethylenimine (PEI) assemblies onto a 15 nm silica colloid have been evaluated with 1H NMR spectroscopy. The saturation adsorption is highly dependent upon the pH at assembly and is given by the equation PEIa (micromol m(-2)) = 1.73pH - 1.89, R2 = 0.986, where micromoles refers to the concentration of the EI monomer. The saturation concentration increases from 6.8 micromol m(-2) at pH 5.0 to 13.7 micromol m(-2) at pH 9.0. The adsorbed polyelectrolyte may be cross-linked and thereby permanently fixed to the colloid surface to prepare nanoparticle-polyelectrolyte colloidal assemblies having enhanced colloid stability, high homogeneity, and a high fraction (>80%) of permanently adsorbed polyelectrolyte. These assemblies are stable at physiological pH and ionic strength and may represent ideal substrates for bioconjugation and, ultimately, the design of nanocarriers for in vivo applications. 相似文献