The cyclodimerisation of 3-methyl-2-butenenitrile

3-Methyl-2-butenenitrile (1) cyclodimerised on treatment with lithium diisopropylamide in dimethoxyethane at temperatures between ?78°C and 0°C to 3-amino-4-cyano-1,5,5-trimethyl-1,3-cyclohexadiene (2) the structure of which was established by acid hydrolysis to the known 4-cyano-1,5,5-trimethyl-1-cyclohexene-3-one (3).     

Conical parametric scattering of a single extraordinary beam in BaTiO3 crystal

In this paper, the parametric scattering of a single extraordinary polarized beam of laser in BaTiO₃ photorefractive crystal has been investigated experimentally and theoretically. The resulting pattern consists of beam fanning, isotropic ring, and anisotropic one. Among all parts of scattering pattern, isotropic ring has not been studied as much as beam fanning and anisotropic ring, and there still are some differences in reports about it. Therefore, the study has mainly focused on this part. In this experimental configuration, isotropic ring is just visible in positive angles although the other parts of parametric scattering pattern can be visible from behind and in front of the crystal. In addition to steady state pattern in forward and backward directions, its transient behavior with the rotation of crystal has been studied. The results of experiments have been analyzed carefully, and their theoretical explanations have been presented based on the standard theory of parametric scattering in photorefractive crystals. It has been shown that this configuration corresponds to the so called parametric B-process scattering.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.     

Oxazolo analogs of the actinomycin D chromophore

Condensation of a tricyclic phenoxazin-2-amino-3-one (a model for the actinomycin D ring system) with acetaldehyde or benzaldehyde or with pyruvic acid as an acetaldehyde precursor gave tetracyclic 5H-oxazolo[4,5-b]phenoxazines. The pyruvic acid reaction proceeds efficiently in one step. The latter compounds were oxidized in a novel reaction by 2,3-dichloro-5,6-dicyano-benzoquinone exclusively at position 8 in the benzenoid ring. Uv, ir, nmr, and mass spectrometric data are reported.     

“Reverse chromophore” of actinomycin d. Synthesis of 2-substituted 7-amino-8H-8-oxo-oxazolo[4,5-b] phenoxazine ring system

The synthesis and physico-chemical properties of a new 7-amino-8H-8-oxo-oxazolo[4,5-b]-phenoxazine ring system (8a and 8b) are reported. These tetracyclic heteroaromatic rings posses an extra oxazolo ring fused to the phenoxazinone chromophore observed in actinomycin D (1b). These tetracyclic compounds (8a-8b) possess a structure in which the orientation of the A and B rings in 1b are “reversed”. Since DNA binding and the resulting specificity of the antitumor antibiotic 1b is believed to depend on the spatial orientation of P(α) and P(β) relative to the functions on the B ring of 1b , these new compounds represent a novel approach for investigating AMD-DNA interactions.     

怀孕期头发中一些元素含量的变化趋势

用同步辐射激发X射线荧光分析,对11个产妇怀孕期间头发内一些元素含量的变化趋势进行了测量,在各自对比的基础上,得到了一些结果。     

Reaction of 4,5-diaminopyrimidine and ethyl acetoacetate: Synthesis and chemistry of isomeric dihydropyrimido[4,5-b][1,4] diazepinones

Depending upon reaction conditions, 4,5-diaminopyrimidine and acetoacetic ester gave a variety of condensation products, including the two isomeric dihydropyrimido[4,5-b][1,4]-diazepinones. Under conditions leading to bicyclic products, the formation of 1,5-dihydro-4-methyl-2H-pyrimido[4,5-b][1,4]diazepin-2-one ( 2 ) was strongly favored. The isomeric 3,5-dihydro-2-methyl-4H-4-one compound ( 4 ) was best obtained by cyclization of ethyl 3-(4-amino-5-pyrimidylamino)crotonate ( 3 ) under base catalysis. Thermal rearrangement of 2 and 4 proceeded, in each instance, with loss of the isopropenyl moiety and gave 8-purinone. Compound 4 underwent ring contraction under the influence of alkoxide to yield a product which was shown to be the 7-isopropenyl-8-purinone ( 6 ).     

The effect of voice amplification on occupational vocal dose in elementary school teachers

Two elementary school teachers, one with and one without a history of vocal complaints, wore a vocal dosimeter all day at school for a 3-week period. In the second week, each teacher wore a portable voice amplifier. Each teacher showed a reduction in vocal intensity during the week of amplification, with a larger effect for the teacher with vocal difficulties. This teacher also showed a decrease in hourly vocal fold distance dose as measured by the dosimeter despite incurring longer phonation times. Fundamental frequency and vocal fold cycle dose did not appear to be affected by the use of amplification during the teaching day. Both teachers showed evidence of a possible moderate effect of adjusting vocal intensity in the week after amplification, possibly as a means to recalibrate their perceived vocal loudness. This study demonstrates the usefulness of both vocal dosimetry and amplification in monitoring and modifying vocal dose in an occupational setting and reinforces previous data suggesting the effectiveness of amplification in reducing the vocal load in schoolteachers. Implications of the data for future research regarding prevention and treatment of occupational voice disorders are discussed.     

In silico targeting PAD4 for the treatment of rheumatoid arthritis

Structural Chemistry - Rheumatoid arthritis (RA) is an autoimmune disorder that causes chronic inflammation with periodic bursts of activity in multiple synovial joints which lead to irreversible...     

Nuclear orbiting and anomalies in nuclear reactions

In this paper, we report our measurements of back-angle oxygen and carbon particle yields from ¹⁶O+⁸⁹Y, ¹²C+⁹³Nb reactions forming the same compound nucleus ¹⁰⁵Ag at the same excitation energy and spin distribution. We find anomalously large oxygen yield and entrance channel dependence at high excitation energies from ¹⁶O+⁸⁹Y reaction implying formation of a dinuclear orbiting complex. Possible connection between nuclear orbiting and fast fission is also discussed.