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991.
Summary A practicable method was developed for the routine determination of formaldehyde in air. Formaldehyde is sampled in small sampling tubes filled with Chromosorb P, coated with 2,4-dinitrophenylhydrazine (= DNPH). The sorbent is extracted with acetonitrile, and the different DNPhydrazones were separated by reversed-phase HPLC. UV-detection at = 345 nm was compared with electrochemical detection. The detection limit was 100 pg for UV- and 50 pg for electrochemical detection with a linear range of more than 3 decades, respectively. For the determination of formaldehyde in air the detection limit is 10 ppb with an average recovery of 99.3% and an estimated relative standard deviation S of 1.5%. This method was compared with the sampling by impingers using the same separation and detection method.
Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday 相似文献
Einige neue Aspekte einer HPLC-Methode zur Spurenbestimmung von Formaldehyd in Luft
Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday 相似文献
992.
Frequency responses associated with adsorption of gas-phase toluene, o-nitrotoluene, valproic acid and the pesticides parathion, malathion and disulfoton on uncoated and protein-coated piezoelectric sensors are reported. Valproic acid antiserum and antibody against parathion were included among the set of protein films studied. Responses, which were reversible in all cases, are attributed to chemisorption or physisorption on electrode and protein surfaces. Under the conditions used, no signals corresponding to selective immunochemical binding were found. Highly sensitive responses of protein-coated sensors to the pesticide species were confirmed, with the lower limit of detection being about 0.01 μg l?1 in nitrogen carrier gas. 相似文献
993.
Chris J. Adams Michael I. Bruce Brian W. Skelton Allan H. White 《Journal of Cluster Science》1994,5(3):419-441
The reactions between Ru5(
5-C2PPh2)(gm-PPh2(CO)13 (1) and cyclopentadienes afforded the hexanuclear clusters Ru6(
6-C)(
3-PPh2)2(CO)10(-C5
R
5) [R
5 = H5 (2), H4Me (3), Me5 (4)] which contain an encapsulated carbide and a face-capping
3-CH group, formed by cleavage of CC and CP bonds of the C2PPh2 moiety in1. In the reaction with cyclopentadiene, the unusual ligand C13H12O, formed by combination of C2, CO and two molecules of C5H6 (or one molecule of dicyclopentadien), was characterized in the complex Ru5(
4-PPh) (
4-C13H12O)(-PPh2(CO)11(-C5H5) (5). In the reaction with pentamethylcyclopentadiene, the vinylidene complex Ru5(
3-CCHPh)(
4-PPh)(
4-PPh) (-PPh2)(CO)9(-C5Me5) (6) was also formed. 相似文献
994.
Ni/SiO2 exhibits higher activity for CO dissociation than coprecipitated Na–Mn–Ni, which is a higher oxygenate synthesis catalyst at 303 K, while Na–Mn–Ni exhibited higher CO dissociation activities at 673 K. 相似文献
995.
Michael H. Abraham Angela F. Danil de Namor Ronald A. Schulz 《Journal of solution chemistry》1977,6(8):491-500
Heats of solution of 13 11 electrolytes in 1-propanol have been determined calorimetrically at various electrolyte concentrations, and extrapolated to zero concentration to give H
s
o
values for these electrolytes. Together with literature data on three additional 11 electrolytes, these measurements yield a self-consistent set of single-ion enthalpies of transfer from water to 1-propanol. Values are tabulated for 10 univalent cations and five univalent anions. It is shown that the H
t
o
(Ph
4
As+)=H
t
o
(Ph
4
B–) assumption yields chemically reasonable single-ion values. Using this assumption, it may be deduced that all the univalent ions studied have about the same enthalpy in 1-propanol as in methanol. 相似文献
996.
Moilanen DE Piletic IR Fayer MD 《The journal of physical chemistry. C, Nanomaterials and interfaces》2007,111(25):8884-8891
The complex environments experienced by water molecules in the hydrophilic channels of Nafion membranes are studied by ultrafast infrared pump-probe spectroscopy. A wavelength dependent study of the vibrational lifetime of the O-D stretch of dilute HOD in H(2)O confined in Nafion membranes provides evidence of two distinct ensembles of water molecules. While only two ensembles are present at each level of membrane hydration studied, the characteristics of the two ensembles change as the water content of the membrane changes. Time dependent anisotropy measurements show that the orientational motions of water molecules in Nafion membranes are significantly slower than in bulk water and that lower hydration levels result in slower orientational relaxation. Initial wavelength dependent results for the anisotropy show no clear variation in the time scale for orientational motion across a broad range of frequencies. The anisotropy decay is analyzed using a model based on restricted orientational diffusion within a hydrogen bond configuration followed by total reorientation through jump diffusion. 相似文献
997.
998.
Hanna C. Wentz Grigorii Skorupskii Ana B. Bonfim Jenna L. Mancuso Christopher H. Hendon Evan H. Oriel Graham T. Sazama Michael G. Campbell 《Chemical science》2020,11(5):1342
Redox-active metal–organic frameworks (MOFs) are promising materials for a number of next-generation technologies, and recent work has shown that redox manipulation can dramatically enhance electrical conductivity in MOFs. However, ligand-based strategies for controlling conductivity remain under-developed, particularly those that make use of reversible redox processes. Here we report the first use of ligand n-doping to engender electrical conductivity in a porous 3D MOF, leading to tunable conductivity values that span over six orders of magnitude. Moreover, this work represents the first example of redox switching leading to reversible conductivity changes in a 3D MOF.Redox-active ligands are used to reversibly tune electrical conductivity in a porous 3D metal–organic framework (MOF). 相似文献
999.
Lei Liu Wes Lee Cassandra R. Youshaw Mingbin Yuan Michael B. Geherty Peter Y. Zavalij Osvaldo Gutierrez 《Chemical science》2020,11(31):8301
A highly chemoselective iron-catalyzed three-component dicarbofunctionalization of unactivated olefins with alkyl halides (iodides and bromides) and sp2-hybridized Grignard reagents is reported. The reaction operates under fast turnover frequency and tolerates a diverse range of sp2-hybridized nucleophiles (electron-rich and electron-deficient (hetero)aryl and alkenyl Grignard reagents), alkyl halides (tertiary alkyl iodides/bromides and perfluorinated bromides), and unactivated olefins bearing diverse functional groups including tethered alkenes, ethers, protected alcohols, aldehydes, and amines to yield the desired 1,2-alkylarylated products with high regiocontrol. Further, we demonstrate that this protocol is amenable for the synthesis of new (hetero)carbocycles including tetrahydrofurans and pyrrolidines via a three-component radical cascade cyclization/arylation that forges three new C–C bonds.A highly selective iron-catalyzed three-component dicarbofunctionalization of unactivated alkenes with alkyl halides and sp2-hybridized Grignard reagents is reported. 相似文献
1000.
A critical comparison of approximation methods and models for equilibrium properties of low-barrier hydrogen bonds 总被引:1,自引:0,他引:1
MacDonald DA Eppard GE Halkides CJ Messina M 《Journal of chemical information and computer sciences》2002,42(6):1390-1397
Recent experimental evidence has led to the conclusion that short, strong hydrogen bonds can stabilize transition states of enzyme catalyzed biochemical reactions. Evidence for such hydrogen bonds is the low value of the isotopic fractionation factor, phi, which is defined as the equilibrium constant for the generic reaction, R-H + DOH <--> R-D + HOH, where H is the hydrogen atom participating in the low-barrier hydrogen bond in a molecule R-H. In this work we assess two approximation methods for computing the isotopic fractionation factors for single and multidimensional systems containing a low-barrier hydrogen bond. These methods are WKB and an approach that corrects the classical partition function via a quantum correction factor. We find that the latter approach is universally accurate and applicable in both single and multidimensional systems containing a low-barrier hydrogen bond. We also assess two different models for the coupling of a molecule's low-barrier hydrogen bond to other degrees of freedom, both internal and external to the molecule, and show that each leads to a lowering of the fractionation factor. 相似文献