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1.
A study has been made of asymmetric hydroformylation of styrene with PtCl 2(PPh 3) 2 + bisphosphine + SnCl 2 (bisphosphine: BDPP = (−)-(2 S,4 S)-2,4-bis(diphenylphosphino)pentane or DIOP = (−)-(4 R,5 R)-2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane) and PtCl 2(bisphosphine) + PPh 3 + SnCl 2 catalysts prepared “in situ”. The presence of an excess of the phosphine ligand slightly lowered the reaction rate, but the enantioselectivity of these systems is significantly higher than those involving PtCl(SnCl 3)(bisphosphine) catalysts. Under mild reaction conditions 88.8% enantiomeric excess was achieved. Replacing SnCl 2 in these catalysts by CuCl 2 or CuCl gave a new homogeneous catalytic system which is active at higher reaction temperature (> 100°C), but has a rather moderate enantioselectivity. 相似文献
2.
Abstract The sorption of pentachlorophenol (PCP) onto the aquatic humic matter (HM) for very wide concentration range (60 ng PCP/L - 1 mg PCP/L) was investigated. The binding affinity increased significantly with the acidity of the solution. The dissolved organic carbon (DOC) normalized sorption coefficients (log K OC) of PCP were 3.39 at pH 3, 3.19 at pH 5.5 and 3.01 at pH 7. The binding of PCP took place via a two step binding mechanism: the rapid first step was followed by a second much slower one indicating that the surface of the HM is very heterogeneous containing binding sites with different binding affinities. It was possible to obtain a “fully saturated” HM-PCP adduct (also all possible micro-voids of the HM were occupied) in a very high PCP concentration. The log K OC value for the whole concentration range was slightly smaller than that obtained under very low PCP concentration level. The Langmuir isotherm was the most suitable for the whole concentration range of PCP, whereas the Freundlich model was the most suitable for the low concentration range of PCP. The dissimilarities between different sorption models were as a whole marginal and thus it is possible without significant loss of information to describe the PCP sorption with a linear model. The results verify that the conventional humic (HA) and fulvic (FA) acid type humic solutes of fresh waters account for the main part of the PCP sorption. 相似文献
3.
Isopinocamphyl-tosylate (2) was treated with indenyllithium to yield 3-(neoisopinocamphyl)-indene (3). Treatment of 3 with methyllithium gave 1-(neoisopinocamphyl)indenyllithium (4) which was then treated with 0.5 molar equivalents of ZrCl 4(thf) 2 to give a 52:48 mixture of one of the “ racemic-like” isomers of bis[1-(neoisopinocamphyl)indenyl]ZrCl 2 (5A) and its “ meso-like” diastereomer 5C. Hydrogenation of the 5A/5C mixture (50 bar H 2, Pt) furnished a mixture of the corresponding tetrahydroindenylzirconium complexes 6A and 6C, from which the “ meso-like” bis[1-(neoisopinocamphyl)-4,5,6,7-tetrahydroindenyl]zirconium dichloride diastereoisomer (6C) was isolated. Treatment of 6C with an excess of methylalumoxane in toluene/propene generated an active -olefin polymerization catalyst. At −30°C partly isotactic polypropylene (
η = 39000) was obtained. The catalyst derived from the chirally-substituted “ meso-like” metallocene complex 6C produced polypropylene predominantly under enantiomorphic site control. 相似文献
4.
Acrylate- and styrene-derived polymers having pendant phenoxyquinones for photochromism were prepared by 2,2′-azoisobutyronitrile (AIBN)-initiated radical polymerization. Synthesis of the monomers were straightforward and the polymers were obtained in high yields in spite of the quinone moieties presented in the monomers, which usually can function as radical scavengers and/or catalysts poison. Photo-induced rearrangement from the “ trans”-quinone forms to the “ ana”-quinone forms readily occurred when the polymer films were irradiated with UV light. 相似文献
5.
The “naked sugar” (+)-(1 R,2 R,4 R)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2- exo-yl acetate ((+)-3) was converted in ten synthetic steps into the new C-nucleoside (1 R)-1-C-(6′-amino-7′H-purin-8′-yl)-1,4-anhydro-3-azido-2,3-dideoxy- D- erythro-pentitol ((+)-2) in 19% overall yield. 相似文献
6.
(1 S,4 S)-7-Oxabicyclo[2.2.1]hept-5-en-2-one ((−)-5, a “naked sugar”) has been converted to (−)-(1 R,4 S,6 S)-6- endo-benzyloxy-2-bromo-7-oxabicyclo[2.2.1]hept-2-ene ((−)-12) in a highly stereoselective fashion. Double hydroxylation of the C=C double bond of (−)-12, followed by acetylation and Baeyer-Villiger oxidation of the resulting -acetoxyketone (−)-14 afforded (−)-5-O-acetyl-2-O-benzyl-3-deoxy-β-D- arabino-hexofuranurono-6,1-lactone ((−)-15). This compound was converted readily into (+)-methyl 3-deoxy--D- arabino-hexofuranoside ((+)-6 and (+)-methyl 3-deoxy-β-L- xylo-hexofuranoside ((+)-7) and partially protected derivatives. (−)-15 was also converted into 4-deoxy-D- lyxo-hexopyranose (34) and several partially protected derivatives such as (+)-methyl 4-deoxy-2,3-O-isopropylidene--D- lyxo-hexopyranoside ((+)-8). 相似文献
7.
An intensive multi-disciplinary research effort is underway at Wayne State University to synthesize and characterize magnetic nanoparticles in a biocompatible matrix for biomedical applications. The particular system being studied consists of 3–10 nm γ-Fe 2O 3 nanoparticles in an alginate matrix, which is being studied for applications in targeted drug delivery, as a magnetic-resonance imaging (MRI) contrast agent, and for hyperthermic treatments of malignant tumors. In the present work we report on our efforts to determine if laser-induced breakdown spectroscopy (LIBS) can offer a more accurate and substantially faster determination of iron content in such nanoparticle-containing materials than competing technologies such as inductively-coupled plasma (ICP). Standardized samples of -Fe 2O 3 nanoparticles (5–25 nm diameter) and silver micropowder (2–3.5 μm diameter) were created with thirteen precisely known concentrations and pressed hydraulically to create solid “pellets” for LIBS analysis. The ratio of the intensity of an Fe(I) emission line at 371.994 nm to that of an Ag(I) line at 328.069 nm was used to create a calibration curve exhibiting an exponential dependence on Fe mass fraction. Using this curve, an “unknown” γ-Fe 2O 3/alginate/silver pellet was tested, leading to a measurement of the mass fraction of Fe in the nanoparticle/alginate matrix of 51 ± 3 wt.%, which is in very good agreement with expectations and previous determinations of its iron concentration. 相似文献
8.
The “naked sugar” (+)-(1 R, 4 R)-7-oxabicyclo[2.2.1]hept-5-en-one((+)-2) has been converted to D-lividosamine ((+)-1: 3-deoxy-D-glucosamine) and derivatives via (+)-2-chloro-2,3-dideoxy-5,6-O-isopropylidene-D- arabino-hexono-1,4-lactone ((+)-33) and (+)-2-azido-2,3-dideoxy-5,6-O-isopropylidene-D- ribo-hexono-1,4-lactone ((+)-34) in a highly stereoselective fashion. Similarly, 2-acetamido-2,3-dideoxy-D- arabino-hexose and derivatives were derived from the “naked sugar” (−)-(1 S,4 S-7-oxabicyclo[2.2.1]-hept-5-en-2-one ((−)-2) via the double hydroxylation of the C=C double bond in (−)-N-benzyl-N-[(1 R,2 S,4 S)-6-bromo-7-oxabicyclo[2.2.1]hept-5-en-2-endo-yl] amine ((−)-40). 相似文献
9.
In recent years the declaration of estimated uncertainty of measurement has become an integral part of analytical results. This study presents the assessment of results generated within the analysis of selected pesticides represented by carbamates, pyrethroides and azoles, residues of which may be found in treated apples. Multiresidue method used for analysis of spiked samples (residues at levels 0.040–0.163 mg/kg) consisted of (i) ethyl acetate extraction, (ii) GPC clean-up and (iii) identification/quantification of residues by GC. Procedures utilizing either conventional (electron-capture, nitrogen–phosphorus) or mass-selective detectors (quadrupole and ion trap analyzer) were evaluated. The results generated through alternative strategies of uncertainty estimation (“bottom-up”, “top-down”) were compared. Using the “bottom-up” approach uncertainty of extraction which comprises two components—(i) repeatability of extraction and (ii) uncertainty of extraction recovery was shown to represent the main source of combined standard uncertainty (values of uncertainty of extraction for tested pesticides ranged from 4.6% to 21.6%). On the other hand, uncertainties associated with the GC calibration (uncertainties of weighing and diluting standards, uncertainties of purity of standards) were not so important (most of them did not exceed 2%). Combined standard uncertainties associated with the described analytical method ranged for individual compounds from 9.3% to 24.3%. Similar values of combined standard uncertainties were obtained using the alternative “top-down” approach. 相似文献
10.
The mobility of inorganic phosphate (P) attached to solid humic acid (HA) and fulvic acid (FA) via a metal “anchor” was investigated by 31P NMR spectroscopy. The peak width of the 31P resonance was monitored as an indicator of the degree of attachment of the element to the humic matrix. The concept was demonstrated by contrasting peak widths of thoroughly dry M–HA–P complexes with those that had been allowed to absorb different amounts of moisture. It was shown that the presence of moisture, which enhances the mobility of P, results in a significant reduction of chemical shift peak width. The work was extended to comparisons between dry systems with and without metal anchors; systems with anchors consisting of different metals; systems comprising different humates and fulvates; and systems with different size fractions of a humate. It was shown that both the type of humate/fulvate, and the metal anchor used lead to different degrees of mobility within the humic matrix. It was also found that the effect of metal addition on 31P peak width is greater with fulvates and smaller HA fractions than with the larger HA components. 相似文献
11.
The diffuse bands near 6100 Å in the laser-induced fluorescence spectrum of Cs 2 are analyzed through quantum-mechanical spectral simulations. These bands are interpreted as bound-free emission to the vibrational continuum of the ground state from an excited state of ion-pair character. The lower region of this state, which we have labeled E′, is described approximately by the spectroscopic constants, Te = 19400 cm −1, Re = 9 Å, and ω e = 13 cm −1. Experiments with a single-mode Ar + laser as excitation source clearly reveal fine structure in the E′ → X spectrum, which was not evident for multimode laser excitation. This fine structure confirms our analysis and supports our suggestion that extensive averaging over initial (υ′, J′) levels is responsible for the absence of fine structure in the spectra excited by a multimode laser. Various averaging mechanisms are investigated in the spectral calculations. The paper includes a brief review of other work on “structured continua” in diatomic spectra, and a semiclassical treatment of such structure, with emphasis on the distinction between “reflection” structure and “interference” structure. 相似文献
12.
In order to gain understanding about how “HA-like substances” from organic amendments may change some properties in the soil solution, the knowledge of chemical and physicochemical characteristics (charge development, acid–base behavior and heterogeneity) should be known. The aim of this research were (i) to study the elemental and functional composition, (ii) to determine charge behavior, acid–base properties (apparent dissociation constant and buffer capacity) and (iii) to evaluate heterogeneity of humic acids (HA) isolated from municipal solid waste compost (MWC) and from the corresponding MWC-amended soil, in comparison to those of the unamended soil HA using potentiometric titration and differential scanning potentiometry (DSP). Potentiometric titration and the first derivative of −Q versus pH (negative charge development versus pH) curves could be used to determine proton-affinity distribution and the chemical heterogeneity of the HA as well as the average pKapp and buffer capacity in a wide range of pH. Differential scanning potentiometry allows determination of the pKapp values in a narrower range of pH than potentiometric titrations and is another simple methodology to study acid–base behavior of HA. DSP allows us to determine seven different pKapp values for HA-S and HA-E and four different pKapp for HA-C. Each one of these values corresponds to known acidic groups that can be present in the macromolecule of HA. 相似文献
13.
The structural study of some γ-butyrolactones substituted (i) in position 2 (position ): C 4H 4O 2Br 2 (II) and C 4H 5O 2R [R = Oφ (III); R = OCOφ (IV); R = OH (V); R = Br (VI); R = Cl (VII)] or (ii) in position 3 or 4 (β or β′): C 4H 5O 2Cl (VIII and IX) has been carried out by using different techniques of physical chemistry. Crystallographic data analysis demonstrates that in the solid state, 2,2-dibromo-γ-butyrolactone, unlike the 2,2-diphenyl-γ-butyrolactone, adopts an “envelope” structure which is comparable to those of compounds (III) and (IV). Spectroscopic data relative to the methylene bending mode δ(CH 2) are interpreted for the dissolved state in terms of rigid (III, IV, V, IX) or exchanging (VI, VII, VIII) “envelope” forms. For and β halogenated derivatives (VI, VII, VIII), quantitative analysis of infrared spectra shows a pseudo-axial predominance in apolar solvents, as found by application of the PCILO method. Interpretation of NMR spectra recorded at 250 MHz (III, IV, V, VI) confirms the data obtained by vibrational spectroscopy. 相似文献
14.
The substitution structure ( rs) of ethyleneimine (aziridine) has been found by analysis of microwave gas spectra of the parent molecule and of the necessary number (5) of mono-isotopically substituted species, all of which were chemically enriched. Two coordinates (<0.1 Å) had to be derived using the conditions Σ mici = Σ mibici = 0. Data from microwave spectra of two double-isotopically substituted species [1-D]-, [1− 15N]-ethyleneimine, and [2,2'-D 2]-ethyleneimine were applied as a further check. The agreement was satisfactory. In the resulting rs structure the C-C distance is shorter than the C-N distance, in accordance with the larger nuclear charge of nitrogen compared to carbon, but qualitatively disagreeing with the results of earlier investigations. Also, the plane defined by H(2), C(2), H(2') is not perpendicular to the N(1), C(2), C(3) plane as assumed earlier. The former plane forms and angle of 87° with the latter which, however, almost exactly bisects the HCH angle. The CH 2 groups may, therefore, be described as slightly “twisted”. 相似文献
15.
Polarised Fourier transform infrared (FT-IR) external-reflection spectroscopy has been used to measure molecular orientation at the surface of uniaxially drawn poly(ethylene terephthalate) (PET) films as a function of draw ratio. The spectra, which were obtained using an FT-IR microscope operating in the reflectance mode, were of high signal-to-noise ( S/ N) ratio, and contained only the specular component of the reflected radiation. The dichroic ratio of the 1019 cm −1 ring stretching band was used to measure the PET orientation function, P200. Prior to quantifying band intensities, the reflectance spectra were either transformed using the Kramers-Kronig algorithm, or simply differentiated; it was found that the dichroic ratios obtained using either pretreatment were similar. It was shown that the P200 values obtained using the FT-IR method compared well with those obtained using surface refractive index measurements, provided that the intensity of the 1019 cm −1 band was normalised relative to a non-dichroic band in the spectrum prior to computing dichroic ratios. The use of a reflecting microscope to perform the analysis of surface orientation not only simplifies sample alignment compared with “macro” reflectance accessories, but also allows awkward-shaped or small samples to be examined with relative ease. Unfortunately, a significant current limitation is that samples must be sufficiently “optically thick” to prevent double-pass (“transflectance”) radiation reaching the detector and yielding non-specular features in the reflectance spectrum. For polyaromatics, this probably means thicknesses in excess of 50 μm to obtain good spectra in the fingerprint region. Polarised attenuated total reflectance microscopy may present an alternate approach for examining thinner films. 相似文献
16.
Phase equilibria in the LaFeO 3–“LaNiO 3” were studied at 1100 °C in air. The samples were synthesized by standard ceramic and/or solution route via nitrate or citrate precursors. According to the results of XRD it was found that the homogeneity ranges of LaFe 1−xNi xO 3−δ solid solution lay within 0.0 ≤ x ≤ 0.4 (sp.gr. Pbnm) and 0.6 ≤ x ≤ 0.8 (sp.gr. ). The structural parameters (bond lengths, atom coordinates) for the single-phase samples were refined using Rietveld analysis. The unit cell parameters versus LaFe 1−xNi xO 3−δ composition are presented. 相似文献
17.
Mass spectra of humic acids (HA) from different sampling sites (Antarctica, Brazil, Czech Republic, Mexico and USA) and origin (plant, soil, peat, and coal derived) were obtained by laser desorption/ionization time of flight mass spectrometry (LDI-TOF MS). Optimisation of the experimental conditions are given as the optimal value of the laser energy at 20–30% higher than the threshold. Under these conditions, reproducible mass spectra of HA samples were obtained. In the mass spectra the majority of the peaks are observed in the m/ z region 100–1000 Da. Mass spectra fingerprints of HA were analyzed and, in spite of the differences in their origin, a number of common features and profiles (patterns of peaks) were observed in most of the samples. Very similar structural groups (patterns) of the peaks are present in the m/ z range 717–918 Da for HA samples of quite different origins, countries or continents. The tandem LDI-TOF MS and multivariate statistical tools allowed us to extract and elucidate underlying information contained in the mass spectra of the HA samples under study. Applying principal components and cluster analysis, it was, e.g. demonstrated that most of the Antarctica HA samples show distinguishable differences when compared with humic acids from other continents and of different origin. 相似文献
18.
The complex Fe(η 6-C 5H 5CMe 3) 2 crystallizes in the centrosymmetric triclinic space group P
( Ci1; No. 2) with unit cell dimensions of a 8.770(1) Å, b 8.878(1) Å, c 11.991(1) Å, 107.56(1)°, β 90.85(1)°, γ 90.13(1)°, V 890.0(2) Å 3 and Z = 2. A full sphere of data was collected on a four-circle diffractometer. The structure was solved and refined to R 7.93% for all 3155 independent reflections and R 4.98% for those 2002 data with | F0 | > 6σ. | F0 |. The molecules lie on crystallographic inversion centers at 0, 0, 0 and 1/2, 0, 1/2; the crystallographic asymmetric unit therefore consists of two independent half molecules. The molecule centered at 0, 0, 0 (molecule “A”) is ordered and well-defined; that centered on 1/2, 0, 1/2 (molecule “B”)is probably disordered, as indicated by larger “thermal parameters” and a greater range of apparent interatomic distances. Discussion em phasizes the geometry of molecule A, which has precise Ci symmetry with Fe(1A)-B(1A) 2.297(4) Å and Fe(1A)-C(ring) distances ranging from 2.057(6) Å to 2.138(4) Å. 相似文献
19.
Interaction of human serum albumin with poly(styrene)- b-poly(ethylene oxide) (PS- b-PEO) monolayer at air/solution interface was studied by measuring surface pressure. The density of PEO chains in the monolayer was controlled using Langmuir trough barriers. The thickness of PS- b-PEO monolayer prior to and after albumin adsorption was computed from in situ surface plasmon resonance (SPR) measurements. Depending on the initial PEO surface density the surface pressure kinetics of albumin insertion displayed two different regimes: below the PEO “pancake-brush” transition albumin binding was initially very rapid and itself induced the “pancake-brush” transition in the monolayer, and above the “pancake-brush” transition where some albumin penetration into the free PS- b-PEO monolayer still occurred into the PEO “brush”. In the case of SPR-immobilized monolayer, more than 0.1 PEO chain/nm 2 was required to inhibit albumin or ferritin adsorption. A half-reduction of albumin adsorption required approx. three-fold higher PEO surface density than the half-reduction of ferritin adsorption. 相似文献
20.
An extensive study of the radiation resistance of microbial species constituting the bioburden of a number of different medical devices obtained from Japanese medical device manufacturers has been carried out. A standard protocol for determining radiation resistance was used and validated at the fourteen centres involved in the study. Individual microbial isolates from the bioburden obtained from seven different devices manufactured in these centres were studied. A total of 3742 unselected isolates were obtained, of which 197 failed to survive long enough for subsequent radiation resistance studies. The remainder were subjected to an initial screen test to identify those organisms that were sensitive to the lethal effects of radiation with a D 10 of < 1.5kGy. The 465 isolates that survived the screen doses were then tested for survival in an incremental series of radiation doses using methods similar to those of Whitby (1979) and Yan and Tallentire(1995). The isolates from “dry” devices were more resistant than those obtained from the one water filled (“wet”) device studied. The overall distribution of radiation resistance among the isolates was considered to be similar to that forming the “Standard Distribution of Resistance” (SDR) included in the ISO International Standard 11137 “Sterilization of Health Care Products — Requirements for validation and routine control — Radiation sterilization”. 相似文献
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