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Overtone spectrum of o, m and p-nitrobenzaldehydes and p-chlorobenzaldehyde has been studied in 2000–12000 cm−1 region. Vibrational frequencies and anharmonicity constants for aryl as well as alkyl CH stretch vibrations have been determined.
We have also determined the internuclear distances for the aryl CH bond in the different molecules. The small variation observed
in these distances is an indication of the substitution effect.
It is observed that in the case of p-disubstituted benzens, the shift in aryl CH bond is proportional to sum of the Hammet σ of the substituents. However in the
case of o-disubstituted benzenes it is only 80% of the para-substituted shift. 相似文献
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Hollenhorst MA Bumpus SB Matthews ML Bollinger JM Kelleher NL Walsh CT 《Journal of the American Chemical Society》2010,132(44):15773-15781
The gene cluster from Pantoea agglomerans responsible for biosynthesis of the dapdiamide antibiotics encodes an adenylation-thiolation didomain protein, DdaD, and an Fe(II)/α-ketoglutarate-dependent dioxygenase homologue, DdaC. Here we show that DdaD, a nonribosomal peptide synthetase module, activates and sequesters N(β)-fumaramoyl-l-2,3-diaminopropionate as a covalently tethered thioester for subsequent oxidative modification of the fumaramoyl group. DdaC catalyzes Fe(II)- and α-ketoglutarate-dependent epoxidation of the covalently bound N(β)-fumaramoyl-l-2,3-diaminopropionyl-S-DdaD species to generate N(β)-epoxysuccinamoyl-DAP (DAP = 2,3-diaminopropionate) in thioester linkage to DdaD. After hydrolytic release, N(β)-epoxysuccinamoyl-DAP can be ligated to l-valine by the ATP-dependent ligase DdaF to form the natural antibiotic N(β)-epoxysuccinamoyl-DAP-Val. 相似文献
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Two experimental values (?19.3 ± 0.3 and ?17.8 ± 0.1 kcal/mol) for the gas phase heat of formation (δfH) (298k) of nitromethane have been reported. Although these values differ by only 1.5 kcal/mol, substantially greater differences in theoretical and experimental results occur when these differing values are used to calculate thermodynamic properties. This is especially evident when these two values for the δfH of nitromethane are used to calculate thermodynamic properties of polynitro compounds. For example, when density functional theory (DFT) is coupled with the use of isodesmic reactions, the ΔfH of octanitrocubane is calculated to be 160.6 or 172.6 kcal/mol, depending on which value is used. It should also be appreciated that several computational theories depend upon having access to reliable experimental data for testing and development. We have examined this discrepancy using several computational models and several levels of theory. Our results coupled with a comprehensive review of the literature support the lower (?19.3 ± 0.3 kcal/mol) experimental value. This is problematic because the higher value (?17.8 ± 0.1 kcal/mol) has been used in the development and/or testing of several semiempirical quantum mechanical models as well as ab initio Gaussian theory (G2 and G3). Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
5.
Timothy W. Bumpus Prof. Dr. Jeremy M. Baskin 《Angewandte Chemie (International ed. in English)》2016,55(42):13155-13158
Phosphatidic acid (PA) is a potent lipid secondary messenger, the synthesis of which is tightly regulated in both space and time. Established tools for detecting PA involve ex vivo analysis and do not provide information on the subcellular locations where this lipid is synthesized. Here, a chemoenzymatic strategy for imaging sites of cellular PA synthesis by phospholipase D (PLD) enzymes is reported. PLDs were found to be able to catalyze phospholipid head‐group exchange with alkynols to generate alkyne‐labeled PA analogues within cells. Subsequent fluorophore tagging through Cu‐catalyzed azide–alkyne cycloaddition enabled both visualization by fluorescence microscopy and quantification by HPLC. Our studies revealed several intracellular sites of PLD‐mediated PA synthesis. We envision applications of this approach to dissect PA‐dependent signaling pathways, image PLD activity in disease, and remodel intracellular membranes with new functionality. 相似文献
6.
The loading module of mycosubtilin: an adenylation domain with fatty acid selectivity 总被引:1,自引:0,他引:1
Hansen DB Bumpus SB Aron ZD Kelleher NL Walsh CT 《Journal of the American Chemical Society》2007,129(20):6366-6367
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With the advent of medium and large gamma detector arrays, it is now possible to look at nuclear structure at high rotational
forces. The role of pairing correlations and their eventual breakdown, along with the shell effects have showed us the interesting
physics for nuclei at high spins — superdeformation, shape co-existence, yrast traps, alignments and their dramatic effects
on nuclear structure and so on. Nuclear structure studies have recently become even more exciting, due to efforts and possibilities
to reach nuclei far off from the stability valley. Coupling of gamma ray arrays with ‘filters’, like neutron wall, charged
particle detector array, gamma ray total energy and multiplicity castles, conversion electron spectrometers etc gives a great
handle to study nuclei produced online with ‘low’ cross-sections. Recently we studied, nuclei in mass region 80 using an array
of 8 germanium detectors in conjunction with the recoil mass analyser, HIRA at the Nuclear Science Centre and, most unexpectedly
came across the phenomenon of identical bands, with two quasi-particle difference. The discovery of magnetic rotation is another
highlight. Our study of light In nucleus, 107In brought us face to face with the ‘dipole’ bands. I plan to discuss some of
these aspects. There is also an immensely important development — that of the ‘radioactive ion beams’. The availability of
RIB, will probably very dramatically influence our ‘conventional’ concept of nuclear structure. The exotic shapes of these
exotic nuclei and some of their expected properties will also be touched upon. 相似文献
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Rare earth element substituted bismuth ferrites (BiFeO3) are of enormous importance as magnetoelectric materials. The polycrystalline samples of Bi
x
La1−x
FeO3 (x=0, 0.2, 0.4, 0.6, 0.8) were prepared by solid-state reaction using standard ceramic method. The single-phase formation of
these compounds was confirmed by X-ray diffraction (XRD) studies. The samples with x=0, 0.2, 0.4, 0.6 are found to be orthorhombic while the sample with x=0.8 is triclinic. The dielectric constant (ε′) and dissipation factor (tan δ) were measured in the frequency range 100 Hz
to 1 MHz at room temperature and as a function of temperature at certain fixed frequencies (1 kHz, 10 kHz, 100 kHz, 1 MHz).
All the samples showed dielectric dispersion. The dielectric constant with temperature shows a broad peak; the peak temperature
shifts with frequency which reflects the relaxor-type behavior. The peak above 600 K in the measured temperature range corresponds
to antiferromagnetic ordering temperature (Néel temperature). The broadness of the peak changes with composition. The ac conductivity
as well as ε′ are found to be maximum for the sample x=0.2 at room temperature. 相似文献
10.
Vagstad AL Bumpus SB Belecki K Kelleher NL Townsend CA 《Journal of the American Chemical Society》2012,134(15):6865-6877
Nonreducing iterative polyketide synthases (NR-PKSs) are responsible for assembling the core of fungal aromatic natural products with diverse biological properties. Despite recent advances in the field, many mechanistic details of polyketide assembly by these megasynthases remain unknown. To expand our understanding of substrate loading, polyketide elongation, cyclization, and product release, active site occupancy and product output were explored by Fourier transform mass spectrometry using the norsolorinic acid anthrone-producing polyketide synthase, PksA, from the aflatoxin biosynthetic pathway in Aspergillus parasiticus. Here we report the simultaneous observation of covalent intermediates from all catalytic domains of PksA from in vitro reconstitution reactions. The data provide snapshots of iterative catalysis and reveal an underappreciated editing function for the C-terminal thioesterase domain beyond its recently established synthetic role in Claisen/Dieckmann cyclization and product release. The specificity of thioesterase catalyzed hydrolysis was explored using biosynthetically relevant protein-bound and small molecule acyl substrates and demonstrated activity against hexanoyl and acetyl, but not malonyl. Processivity of polyketide extension was supported by the inability of a nonhydrolyzable malonyl analog to trap products of intermediate chain lengths and by the detection of only fully extended species observed covalently bound to, and as the predominant products released by, PksA. High occupancy of the malonyl transacylase domain and fast relative rate of malonyl transfer compared to starter unit transfer indicate that rapid loading of extension units onto the carrier domain facilitates efficient chain extension in a manner kinetically favorable to ultimate product formation. 相似文献