Single vibronic level fluorescence spectra of sulfur dioxide

Single vibronic level fluorescence spectra of sulfur dioxide have been recorded throughout most of the region corresponding to the $\text{A}\text{?}\text{-}\text{X}\text{?}$ absorption. These spectra show progressions in the symmetric stretching mode of at least five members. Twelve origins between 30 972 and 31 776 cm^?1 show remarkably similar Franck-Condon (FC) patterns for this progression. Seven origins between 31 840 and 32 257 cm^?1 show another distinct FC pattern. This behavior is repeated for three more regions of excitation, each with a different distinct FC pattern and each containing numerous origins spread throughout a region of about 700 cm^?1. The progressions in the symmetric bending mode are essentially absent in the lowest energy excitation spectra and then slowly increase in length as the excitation energy increases. There is limited activity in both even and odd quanta of the antisymmetric stretching mode. These results are interpreted in terms of the levels of a zero-order ¹B₁ electronic state (with zero-order origin at around 31 240 cm^?1) that are very strongly vibronically coupled to many more ¹A₂ levels (with lower energy zero-order origin). The bulk of the emission is what would be expected from the zero-order ¹B₁ levels spread among the ¹A₂ levels.     

A LEED-AES study of the initial stages of oxidation of Fe (001)

LEED and AES have been used to study the structural changes and kinetics of the initial interaction between Fe(001) and oxygen at room temperature. The AES oxygen signal was quantified by using a two-dimensional oxide layer as a calibration point. This reproducible oxide layer was prepared by the high temperature reaction of H₂O at 10^?6 torr with Fe(001). The initial oxygen sticking coefficient was observed to be close to unity, which suggests that the chemisorption is non-activated and involves a mobile adsorption step. The rate of chemisorption decreased as (1-Θ) and exhibited a minimum at Θ = 0.5. LEED data indicate that the minimum value of the sticking coefficient corresponded to the completion of a c (2 × 2) surface structure. Upon additional exposure to oxygen, an increase in the sticking coefficient was observed in conjunction with the disappearance of the c (2 × 2) and a gradual fade out of all diffraction features. After mild heating, epitaxial FeO (001) and FeO (111) structures were observed. The simultaneous appearance of a shifted M_2,3M_4,5M_4,5 iron Auger transition with the increase in the sticking coefficient and the disappearance of the c (2 × 2) indicated that oxide nucleated on the surface after the complete formation of the c (2 × 2) structure. The relatively high sticking coefficient during the initial oxidation indicates that formation of a mobile adsorbed oxygen state precedes the formation of oxide.     

Comparison of the tractive performance of a tractor driving wheel during its first and second passes in the same track

The tractive performance of a conventional 13.6–38 tractor driving wheel tyre was measured in 19 different fields using the NIAE Single Wheel Tester. In each field the performance was measured on the undisturbed ground and again in the rut formed by a previous run with the same tyre. The second run simulated the operation of the rear wheels on a four-wheel drive tractor.The performance during the second pass was generally better than during the first pass. On average, the coefficient of traction increased by 7%, rolling resistance reduced by 11% and maximum tractive efficiency increased by 5%. The improvement increased as ground conditions deteriorated but was never large enough to fully explain the differences in performance between two and four-wheel drive tractors previously measured. It is suggested, therefore, that these differences may be primarily due to the greater ease with which power, weight, implement size and working speed can be matched with four-wheel drive tractors.     

The physics of lightning

Despite being one of the most familiar and widely recognized natural phenomena, lightning remains relatively poorly understood. Even the most basic questions of how lightning is initiated inside thunderclouds and how it then propagates for many tens of kilometers have only begun to be addressed. In the past, progress was hampered by the unpredictable and transient nature of lightning and the difficulties in making direct measurements inside thunderstorms, but advances in instrumentation, remote sensing methods, and rocket-triggered lightning experiments are now providing new insights into the physics of lightning. Furthermore, the recent discoveries of intense bursts of X-rays and gamma-rays associated with thunderstorms and lightning illustrate that new and interesting physics is still being discovered in our atmosphere. The study of lightning and related phenomena involves the synthesis of many branches of physics, from atmospheric physics to plasma physics to quantum electrodynamics, and provides a plethora of challenging unsolved problems. In this review, we provide an introduction to the physics of lightning with the goal of providing interested researchers a useful resource for starting work in this fascinating field.     

Spectral Asymptotics for Higher-Order Ordinary Differential Equations

This paper gives one-term componentwise asymptotics for theM and spectral matrices of a self-adjoint realisation of aneven-order ordinary differential expression. The underlyinginterval is assumed to have at least one regular endpoint, andthe boundary conditions are supposed to be separated. Furthermore,the weight function and the reciprocal of the highest-ordercoefficient are supposed to be of regular variation at the regularendpoint, in the sense of Bingham, Goldie and Teugels. 1991Mathematics Subject Classification: 34B24, 34E05.     

Proteomics-Based Discovery of First-in-Class Chemical Probes for Programmed Cell Death Protein 2 (PDCD2)

Chemical probes are essential tools for understanding biological systems and for credentialing potential biomedical targets. Programmed cell death 2 (PDCD2) is a member of the B-cell lymphoma 2 (Bcl-2) family of proteins, which are critical regulators of apoptosis. Here we report the discovery and characterization of 10 e , a first-in-class small molecule degrader of PDCD2. We discovered this PDCD2 degrader by serendipity using a chemical proteomics approach, in contrast to the conventional approach for making bivalent degraders starting from a known binding ligand targeting the protein of interest. Using 10 e as a pharmacological probe, we demonstrate that PDCD2 functions as a critical regulator of cell growth by modulating the progression of the cell cycle in T lymphoblasts. Our work provides a useful pharmacological probe for investigating PDCD2 function and highlights the use of chemical proteomics to discover selective small molecule degraders of unanticipated targets.     

Efforts toward expansion of the genetic alphabet: structure and replication of unnatural base pairs

Expansion of the genetic alphabet has been a long-time goal of chemical biology. A third DNA base pair that is stable and replicable would have a great number of practical applications and would also lay the foundation for a semisynthetic organism. We have reported that DNA base pairs formed between deoxyribonucleotides with large aromatic, predominantly hydrophobic nucleobase analogues, such as propynylisocarbostyril (dPICS), are stable and efficiently synthesized by DNA polymerases. However, once incorporated into the primer, these analogues inhibit continued primer elongation. More recently, we have found that DNA base pairs formed between nucleobase analogues that have minimal aromatic surface area in addition to little or no hydrogen-bonding potential, such as 3-fluorobenzene (d3FB), are synthesized and extended by DNA polymerases with greatly increased efficiency. Here we show that the rate of synthesis and extension of the self-pair formed between two d3FB analogues is sufficient for in vitro DNA replication. To better understand the origins of efficient replication, we examined the structure of DNA duplexes containing either the d3FB or dPICS self-pairs. We find that the large aromatic rings of dPICS pair in an intercalative manner within duplex DNA, while the d3FB nucleobases interact in an edge-on manner, much closer in structure to natural base pairs. We also synthesized duplexes containing the 5-methyl-substituted derivatives of d3FB (d5Me3FB) paired opposite d3FB or the unsubstituted analogue (dBEN). In all, the data suggest that the structure, electrostatics, and dynamics can all contribute to the extension of unnatural primer termini. The results also help explain the replication properties of many previously examined unnatural base pairs and should help design unnatural base pairs that are better replicated.