The electric dipole moment of the hydrogen-bonded heterodimer HCN⋯HF. An investigation of the conditions leading to inadequacy of the second- and fourth-order perturbation theories of the Stark effect for linear molecules

We have detected large deviations of the M_J = 0, J = 2 ← 1 Stark effect transition in the linear molecule HCN?HF from predictions of second-, and even fourth-, order perturbation theory. In order to account satisfactorily for the observed effect it has been necessary to set up and diagonalize the appropriate energy matrix. Smaller deviations in the case of M_J = 1, J = 2 ← 1 have likewise been treated. The values of the electric dipole moment for HCN?HF calculated from these transitions, which show large and small deviations from second-order theory, and from one (M_J = 3, J = 4 ← 3) which shows effectively zero deviation, are now consistent and are as follows:

     

2.

Vibrational spectra and vibrational states of simple gas-phase hydrogen-bonded dimers     

D.J. Millen 《Journal of Molecular Structure》1983

The article aims to outline the growth of evidence and ideas about infrared band broadening for simple, gaseous, moderately strong, hydrogen bonded dimers B…HA, to draw attention to areas in need of further development and to collect together experimental information available at the present time about vibrational states associated with such dimers. The band associated with the modified HA stretching mode, ν_s, is observed for several dimers not only to be broad, but to have sub-band structure, which is satisfactorily interpreted as arising from combination bands of ν_s with the low frequency stretch-mode ν_σ, giving a progression ν_s ± nν_σ as a result of strong anharmonic coupling. For weaker dimers with lower values of ν_σ the sub-band structure is less evident, and may appear only as shoulders, while for still weaker dimers, the sub-bands may be merged into a featureless broad band. A major factor contributing to the breadth of the individual sub-bands in the band structure is the presence of hot-bands, especially a long series based on successive excited states of the low-frequency bending mode ν_β. A link is indicated with the interpretation of band-broadening for moderately strong hydrogen-bonded complexes in the liquid state. The anharmonic coupling of ν_s and ν_σ is again a central feature but there is a new factor, namely the coupling of ν_σ through a fluctuating potential with the surroundings, which has the result that the ν_s mode rapidly loses phase coherence resulting in a broad structureless band.     

3.

Electron impact mass spectra of synthetically modified milbemycins     

M. T. Jones  W. G. Millen  M. L. Thomson 《Journal of mass spectrometry : JMS》1993,28(5):635-642

The potent endectocide 23-(O-methyloximino)-F28249α and related compounds were identified and characterized by mass spectrometry. The fragmentation pathway of 23-(O-methyloximino)-F28249α was identified by its high-resolution mass spectrum and the electron impact unit mass spectra of its homologs. This fragmentation pathway is presented and discussed.     

4.

yDNA versus xDNA pyrimidine nucleobases: computational evidence for dependence of duplex stability on spacer location     

Lait LA  Rutledge LR  Millen AL  Wetmore SD 《The journal of physical chemistry. B》2008,112(39):12526-12536

The structural and binding properties of the natural and x- and y-pyrimidines were compared using computational methods. Our calculations show that although the x-pyrimidines favor different orientations about the glycosidic bond compared to the natural pyrimidines, which could have implications for the formation and resulting stability of xDNA duplexes and jeopardize the selectivity of expanded nucleobases, y-pyrimidines have rotational profiles more similar to the natural bases. Increasing the pyrimidine size using a benzene spacer leads to relatively minor changes in the hydrogen-bond strength of isolated Watson-Crick base pairs. However, differences in the anomeric carbon distances in pairs composed of x- or y-pyrimidines suggest yDNA may yield a more optimal expanded structure. By stacking two monomers via their centers of mass, we find that the expanded nucleobases stack much stronger than the natural bases. Additionally, although replacing xT by yT changes the stacking energy by less than 5 kJ mol (-1), replacing xC by yC significantly strengthens complexes with the natural nucleobases (by up to 30%). Calculations on larger duplex models composed of four nucleobases reveal that x- and y-pyrimidines can increase duplex stability of natural helices by strengthening both the intra and interstrand stacking interactions. Furthermore, when the total stability (sum of all hydrogen-bonding and (intrastrand and interstrand) stacking interactions) of the larger models is considered, y-pyrimidines lead to more stable complexes than x-pyrimidines for all but three duplex sequences. Thus, through analysis of a variety of properties, our calculations suggest that the location of the benzene spacer affects the properties of expanded nucleobases and the stability of expanded duplexes, and therefore should be carefully considered when designing future expanded analogues.     

5.

On-Line Measurement of Mass Flow of Pneumatically Conveyed Solids     

David A. Abernethy  Nicholas G. Cutmore  Thressa G. Evans  Michael J. Millen  Brian D. Sowerby 《Particle & Particle Systems Characterization》1998,15(1):42-46

CSIRO has developed an ultrasonic attenuation and transit time technique and a microwave transmission technique for on-line determination of the mass flow of pneumatically conveyed solids. In a comparative plant trial on a single burner line at Bayswater power station, the ultrasonic technique determined the coal density and velocity with rms errors of 3.9 and 5.9% relative respectively; the microwave technique successfully determined the coal density with an rms error of 6.2% relative, but was unable to accurately determine solids flow velocity at the low coal densities typical of the trial. In a plant trial at a direct smelter, the microwave technique successfully determined the mass flow of pneumatically conveyed iron ore fines feeding the smelter with an rms error of 10.2% relative.     

6.

Internal energy content of n-butylbenzene, bromobenzene, iodobenzene and aniline molecular ions generated by two-photon ionization at 266 nm. A photodissociation study     

OK Yoon  WG Hwang  JC Choe  MS Kim 《Rapid communications in mass spectrometry : RCM》1999,13(14):1515-1521

A technique to investigate photodissociation kinetics on a nanosecond time scale has been devised for molecular ions generated by multiphoton ionization (MPI) using mass-analyzed ion kinetic energy spectrometry. The branching ratio or rate constant has been determined for the photodissociation of the n-butylbenzene, bromobenzene, iodobenzene, and aniline molecular ions generated by MPI at 266 nm. The ion internal energies have been estimated by comparing the measured kinetic data with the previous energy dependence data. The analysis has shown that only those molecular ions generated by two-photon ionization contribute to the photodissociation signals. Around half of the available energy has been found to remain as molecular ion internal energy in the two-photon ionization process. Copyright 1999 John Wiley & Sons, Ltd.     

7.

Comparative infrared study of hydrogen-bonded heterodimers formed by HCl,DCl, HF and DF with (CH₃)₂O,CH₃OH and (CH₃)₃COH in the gas phase. Assignment of vibrational band structure in (CH₃)₂O… HCl     

D.J. Millen  O. Schrems 《Chemical physics letters》1983,101(3):320-325

Observation of v_s bands in the infrared spectra of some O…H-Cl and O…H-F dimers and their deutero derivatives completes the investigation of a series of twelve related dimers. Comparison is made with related spectra, and arguments are advanced in favour of the earlier assignment of the band structure in the spectrum of (CH₃)₂O… H-Cl.     

8.

Economic justification of modern computer-based factory automation equipment: A status report     

G. J. Michael  R. A. Millen 《Annals of Operations Research》1985,3(2):23-34

This paper provides a status report on the economic justification of modern computer-based factory automation equipment. Such equipment, although offering improved productivity and flexibility, is nevertheless oftentimes difficult to justify using traditional discounted cash flow evaluation methodologies. In this paper, we first establish and explain four different categories into which most of the literature on this subject generally falls. We then present the results of interviews with executives in manufacturing companies that have experienced varying degrees of success in justifying automation. During these interviews, we sought to determine how the automation was justified as well as the difficulties encountered. Finally, we consolidate the information obtained from our examination of the literature and our interviews, and we synthesize a set of options available to todays manager attempting to justify the introduction of automation systems. We present these options in terms of immediate, near-term and long-term managerial alternatives.     

9.

The angle deformation force field for the hydrogen-bonded heterodimer CH₃CN⋯HF determined with the aid of the centrifugal distortion constant D_JK     

A.C. Legon  D.J. Millen  S.C. Rogers 《Journal of Molecular Structure》1980

The relationships between the valence force field and the centrifugal distortion constants are established for a molecule of the general type XY₃WZ?AB and are used in the case of CH₃CN?HF to determine the angle deformation force field by employing D_JK in combination with the wavenumbers of the appropriate vibrational modes.     

10.

Computational and experimental evidence for the structural preference of phenolic C-8 purine adducts     

Millen AL  McLaughlin CK  Sun KM  Manderville RA  Wetmore SD 《The journal of physical chemistry. A》2008,112(16):3742-3753

The structural and spectral properties of (ortho and para) C8-aryl-purine adducts formed from carbon attachment by phenolic toxins were investigated through DFT calculations and UV-vis absorbance and emission studies. The global minima of both the deoxyadenosine (dA) and deoxyguanosine (dG) adducts adopted a syn conformation about the glycosidic bond due to the presence of an O5'-H...N3 hydrogen bond, where the anti minima are 20-30 kJ mol-1 higher in energy. While the nucleobase adducts are planar, the presence of the deoxyribose sugar induces a twist about the carbon-carbon bond connecting the phenol and nucleobase rings. ortho-Phenolic adducts are less twisted than the corresponding para adducts due to stabilization provided by an intramolecular O-H...N7 bond. Solvation calculations, in combination with UV-vis studies, demonstrate that the structural preference is solvent dependent, where solvents with hydrogen-bonding abilities disrupt the intramolecular O-H...N7 hydrogen bond such that a greater degree of twist is observed, and less polar solvents stabilize the planar structure. Indeed, the ratio of twisted to planar conformers is estimated to be as large as 50:50 in some aprotic solvents. Thus, the combined experimental and computational approach has provided a greater understanding of the structure of the ortho- and para-dA and dG C-bonded phenoxyl adducts as the first step to understanding the biological consequences of this form of DNA damage.     

1 [2] [3] 下一页 » 末  页»

$\text{J + 1 ← J}$	$\text{M}{}_{\mathrm{J}}$		μ/D
2 ← 1	0		5.627
	1		5.601
4 ← 3	3		5.608
		Mean	5.612

Vibrational spectra and vibrational states of simple gas-phase hydrogen-bonded dimers

The article aims to outline the growth of evidence and ideas about infrared band broadening for simple, gaseous, moderately strong, hydrogen bonded dimers B…HA, to draw attention to areas in need of further development and to collect together experimental information available at the present time about vibrational states associated with such dimers. The band associated with the modified HA stretching mode, ν_s, is observed for several dimers not only to be broad, but to have sub-band structure, which is satisfactorily interpreted as arising from combination bands of ν_s with the low frequency stretch-mode ν_σ, giving a progression ν_s ± nν_σ as a result of strong anharmonic coupling. For weaker dimers with lower values of ν_σ the sub-band structure is less evident, and may appear only as shoulders, while for still weaker dimers, the sub-bands may be merged into a featureless broad band. A major factor contributing to the breadth of the individual sub-bands in the band structure is the presence of hot-bands, especially a long series based on successive excited states of the low-frequency bending mode ν_β. A link is indicated with the interpretation of band-broadening for moderately strong hydrogen-bonded complexes in the liquid state. The anharmonic coupling of ν_s and ν_σ is again a central feature but there is a new factor, namely the coupling of ν_σ through a fluctuating potential with the surroundings, which has the result that the ν_s mode rapidly loses phase coherence resulting in a broad structureless band.     

Electron impact mass spectra of synthetically modified milbemycins

The potent endectocide 23-(O-methyloximino)-F28249α and related compounds were identified and characterized by mass spectrometry. The fragmentation pathway of 23-(O-methyloximino)-F28249α was identified by its high-resolution mass spectrum and the electron impact unit mass spectra of its homologs. This fragmentation pathway is presented and discussed.     

yDNA versus xDNA pyrimidine nucleobases: computational evidence for dependence of duplex stability on spacer location

The structural and binding properties of the natural and x- and y-pyrimidines were compared using computational methods. Our calculations show that although the x-pyrimidines favor different orientations about the glycosidic bond compared to the natural pyrimidines, which could have implications for the formation and resulting stability of xDNA duplexes and jeopardize the selectivity of expanded nucleobases, y-pyrimidines have rotational profiles more similar to the natural bases. Increasing the pyrimidine size using a benzene spacer leads to relatively minor changes in the hydrogen-bond strength of isolated Watson-Crick base pairs. However, differences in the anomeric carbon distances in pairs composed of x- or y-pyrimidines suggest yDNA may yield a more optimal expanded structure. By stacking two monomers via their centers of mass, we find that the expanded nucleobases stack much stronger than the natural bases. Additionally, although replacing xT by yT changes the stacking energy by less than 5 kJ mol (-1), replacing xC by yC significantly strengthens complexes with the natural nucleobases (by up to 30%). Calculations on larger duplex models composed of four nucleobases reveal that x- and y-pyrimidines can increase duplex stability of natural helices by strengthening both the intra and interstrand stacking interactions. Furthermore, when the total stability (sum of all hydrogen-bonding and (intrastrand and interstrand) stacking interactions) of the larger models is considered, y-pyrimidines lead to more stable complexes than x-pyrimidines for all but three duplex sequences. Thus, through analysis of a variety of properties, our calculations suggest that the location of the benzene spacer affects the properties of expanded nucleobases and the stability of expanded duplexes, and therefore should be carefully considered when designing future expanded analogues.     

On-Line Measurement of Mass Flow of Pneumatically Conveyed Solids

CSIRO has developed an ultrasonic attenuation and transit time technique and a microwave transmission technique for on-line determination of the mass flow of pneumatically conveyed solids. In a comparative plant trial on a single burner line at Bayswater power station, the ultrasonic technique determined the coal density and velocity with rms errors of 3.9 and 5.9% relative respectively; the microwave technique successfully determined the coal density with an rms error of 6.2% relative, but was unable to accurately determine solids flow velocity at the low coal densities typical of the trial. In a plant trial at a direct smelter, the microwave technique successfully determined the mass flow of pneumatically conveyed iron ore fines feeding the smelter with an rms error of 10.2% relative.     

Internal energy content of n-butylbenzene, bromobenzene, iodobenzene and aniline molecular ions generated by two-photon ionization at 266 nm. A photodissociation study

A technique to investigate photodissociation kinetics on a nanosecond time scale has been devised for molecular ions generated by multiphoton ionization (MPI) using mass-analyzed ion kinetic energy spectrometry. The branching ratio or rate constant has been determined for the photodissociation of the n-butylbenzene, bromobenzene, iodobenzene, and aniline molecular ions generated by MPI at 266 nm. The ion internal energies have been estimated by comparing the measured kinetic data with the previous energy dependence data. The analysis has shown that only those molecular ions generated by two-photon ionization contribute to the photodissociation signals. Around half of the available energy has been found to remain as molecular ion internal energy in the two-photon ionization process. Copyright 1999 John Wiley & Sons, Ltd.     

Comparative infrared study of hydrogen-bonded heterodimers formed by HCl,DCl, HF and DF with (CH3)2O,CH3OH and (CH3)3COH in the gas phase. Assignment of vibrational band structure in (CH3)2O… HCl

Observation of v_s bands in the infrared spectra of some O…H-Cl and O…H-F dimers and their deutero derivatives completes the investigation of a series of twelve related dimers. Comparison is made with related spectra, and arguments are advanced in favour of the earlier assignment of the band structure in the spectrum of (CH₃)₂O… H-Cl.     

Economic justification of modern computer-based factory automation equipment: A status report

This paper provides a status report on the economic justification of modern computer-based factory automation equipment. Such equipment, although offering improved productivity and flexibility, is nevertheless oftentimes difficult to justify using traditional discounted cash flow evaluation methodologies. In this paper, we first establish and explain four different categories into which most of the literature on this subject generally falls. We then present the results of interviews with executives in manufacturing companies that have experienced varying degrees of success in justifying automation. During these interviews, we sought to determine how the automation was justified as well as the difficulties encountered. Finally, we consolidate the information obtained from our examination of the literature and our interviews, and we synthesize a set of options available to todays manager attempting to justify the introduction of automation systems. We present these options in terms of immediate, near-term and long-term managerial alternatives.     

The angle deformation force field for the hydrogen-bonded heterodimer CH3CN⋯HF determined with the aid of the centrifugal distortion constant DJK

The relationships between the valence force field and the centrifugal distortion constants are established for a molecule of the general type XY₃WZ?AB and are used in the case of CH₃CN?HF to determine the angle deformation force field by employing D_JK in combination with the wavenumbers of the appropriate vibrational modes.     

Computational and experimental evidence for the structural preference of phenolic C-8 purine adducts

The structural and spectral properties of (ortho and para) C8-aryl-purine adducts formed from carbon attachment by phenolic toxins were investigated through DFT calculations and UV-vis absorbance and emission studies. The global minima of both the deoxyadenosine (dA) and deoxyguanosine (dG) adducts adopted a syn conformation about the glycosidic bond due to the presence of an O5'-H...N3 hydrogen bond, where the anti minima are 20-30 kJ mol-1 higher in energy. While the nucleobase adducts are planar, the presence of the deoxyribose sugar induces a twist about the carbon-carbon bond connecting the phenol and nucleobase rings. ortho-Phenolic adducts are less twisted than the corresponding para adducts due to stabilization provided by an intramolecular O-H...N7 bond. Solvation calculations, in combination with UV-vis studies, demonstrate that the structural preference is solvent dependent, where solvents with hydrogen-bonding abilities disrupt the intramolecular O-H...N7 hydrogen bond such that a greater degree of twist is observed, and less polar solvents stabilize the planar structure. Indeed, the ratio of twisted to planar conformers is estimated to be as large as 50:50 in some aprotic solvents. Thus, the combined experimental and computational approach has provided a greater understanding of the structure of the ortho- and para-dA and dG C-bonded phenoxyl adducts as the first step to understanding the biological consequences of this form of DNA damage.