Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene) n , n = 1,2

The S0 ↔ S1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene)2 (P·(4ClE)2) are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets. The S0 → S1 vibrationless transitions of P·4ClE and P·(4ClE)2 are shifted by δν = −451 and −858 cm–1 relative to perylene, translating to excited-state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The red shift is ∼30% larger than that of perylene·trans-1,2-dichloroethene; therefore, the increase in chlorination increases the excited-state stabilization and CT character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1au) vibration (42 cm–1 in S0 and 55 cm–1 in S1), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (Tz) and internal rotation (Rc) vibrations are weak; therefore, the P·4ClE intermolecular potential energy surface (IPES) changes little during the S0 ↔ S1 transition. The minimum-energy structures and inter- and intramolecular vibrational frequencies of P·4ClE and P·(4ClE)2 are calculated with the dispersion-corrected density functional theory (DFT) methods B97-D3, ωB97X-D, M06, and M06-2X and the spin-consistent-scaled (SCS) variant of the approximate second-order coupled-cluster method, SCS-CC2. All methods predict the global minima to be π-stacked centered coplanar structures with the long axis of tetrachloroethene rotated by τ ≈ 60° relative to the perylene long axis. The calculated binding energies are in the range of −D0 = 28–35 kJ/mol. A second minimum is predicted with τ ≈ 25°, with ∼1 kJ/mol smaller binding energy. Although both monomers are achiral, both the P·4ClE and P·(4ClE)2 complexes are chiral. The best agreement for adiabatic excitation energies and vibrational frequencies is observed for the ωB97X-D and M06-2X DFT methods.

Arctic Siberia: Modern pollen dataset and pollen spectra changes over the last 7,000 years from a lacustrine sediment core (southern Taymyr region)

Palaeoecological investigations in the larch forest-tundra ecotone in northern Siberia have the potential to reveal Holocene environmental variations, which likely have consequences for global climate change because of the strong high-latitude feedback mechanisms. A sediment core, collected from a small lake (radius ~100 m), was used to reconstruct the development of the lake and its catchment as well as vegetation and summer temperatures over the last 7100 calibrated years. A multi-proxy approach was taken including pollen and sedimentological analyses. Our data indicate a gradual replacement of open larch forests by tundra with scattered single trees as found today in the vicinity of the lake. An overall trend of cooling summer temperature from a ~2 °C warmer-than-present mid-Holocene summer temperatures until the establishment of modern conditions around 3000 years ago is reconstructed based on a regional pollen-climate transfer function. The inference of regional vegetation changes was compared to local changes in the lake's catchment. An initial small water depression occurred from 7100 to 6500 cal years BP. Afterwards, a small lake formed and deepened, probably due to thermokarst processes. Although the general trends of local and regional environmental change match, the lake catchment changes show higher variability. Furthermore, changes in the lake catchment slightly precede those in the regional vegetation. Both proxies highlight that marked environmental changes occurred in the Siberian forest-tundra ecotone over the course of the Holocene.

Signature p53 mutation at DNA cross-linking sites in 8-methoxypsoralen and ultraviolet A (PUVA)-induced murine skin cancers.

A combination of psoralen and ultraviolet A radiation (PUVA) is widely used in the treatment of psoriasis. However, PUVA treatment increases the risk of developing skin cancer in psoriasis patients and induces skin cancer in mice. Since the DNA damage induced by PUVA is quite different from that induced by UV, we investigated whether PUVA-induced mouse skin cancers display carcinogen-specific mutations in the p53 tumor suppressor gene. The results indicated that 10 of 13 (77%) PUVA-induced skin tumors contained missense mutations predominantly at exons 6 and 7. In contrast, tumor-adjacent, PUVA-exposed skin from tumor-bearing animals did not exhibit p53 mutation in exons 4-8. Interestingly, about 40% of all mutations in PUVA-induced skin tumors occurred at 5'-TA sites, and an equal number of mutations occurred at one base flanking 5'TA or 5'-TAT sites. Since PUVA induces DNA cross-links exclusively at these sites and since UV "signature" mutations were rarely detected in PUVA-induced skin cancers, we can conclude that PUVA acts as a carcinogen by inducing unique PUVA signature mutations in p53. This finding may have implications for identifying the etiology of skin cancer in psoriasis patients who have undergone PUVA therapy.

Close correspondence between the action spectra for the blue light responses of the guard cell and coleoptile chloroplasts, and the spectra for blue light-dependent stomatal opening and coleoptile phototropism.

Fluorescence spectroscopy was used to characterize blue light responses from chloroplasts of adaxial guard cells from Pima cotton (Gossypium barbadense) and coleoptile tips from corn (Zea mays). The chloroplast response to blue light was quantified by measurements of the blue light-induced enhancement of a red light-stimulated quenching of chlorophyll a fluorescence. In adaxial (upper) guard cells, low fluence rates of blue light applied under saturating fluence rates of red light enhanced the red light-stimulated fluorescence quenching by up to 50%. In contrast, added blue light did not alter the red light-stimulated quenching from abaxial (lower) guard cells. This response pattern paralleled the blue light sensitivity of stomatal opening in the two leaf surfaces. An action spectrum for the blue light-induced enhancement of the red light-stimulated quenching showed a major peak at 450 nm and two minor peaks at 420 and 470 nm. This spectrum matched closely an action spectrum for blue light-stimulated stomatal opening. Coleoptile chloroplasts also showed an enhancement by blue light of red light-stimulated quenching. The action spectrum of this response, showing a major peak at 450 nm, a minor peak at 470 nm, and a shoulder at 430 nm, closely matched an action spectrum for blue light-stimulated coleoptile phototropism. Both action spectra match the absorption spectrum of zeaxanthin, a chloroplastic carotenoid recently implicated in blue light photoreception of both guard cells and coleoptiles. The remarkable similarity between the action spectra for the blue light responses of guard cells and coleoptile chloroplasts and the spectra for blue light-stimulated stomatal opening and phototropism, coupled to the recently reported evidence on a role of zeaxanthin in blue light photoreception, indicates that the guard cell and coleoptile chloroplasts specialize in sensory transduction.

Linear operators and their spectra with applications to quantum mechanics.

From lectures given at the New York university Institute for mathematica and mechanics, by R. Cournat and others.

Doppler radar observations of weather and aircraft spectra.

"Internal research."

Analysis of probability distributions and power spectra of time histories of maneuvering flight.

"Bureau of Naval Weapons Contract Noa(s) 60-6114-c."

Researches on the chemical origin of various lines in solar and stellar spectra : being the results of investigations made at the Solar physics observatory, South Kensington, after discussion /

At head of title: Solar physics committee.

The rearrangements of naphthyinitrenes: UV/Vis and IR spectra of azirines, cyclic ketenimines, and cyclic nitrile ylides

Ar matrix photolysis of 1- and 2-naphthyl azides 3 and 4 at 313 nm initially affords the singlet naphthyl nitrenes, (1)1 and (1)2. Relaxation to the corresponding lower energy, persistent triplet nitrenes (3)1 and (3)2 competes with cyclization to the azirines 15 and 18, which can also be formed photochemically from the triplet nitrenes. On prolonged irradiation, the azirines can be converted to the seven-membered cyclic ketenimines 10 and 13, respectively, as described earlier by Dunkin and Thomson. However, instead of the o-quinoid ketenimines 16 and 19, which are the expected primary ring-opening products of azirines 15 and 18, respectively, we observed their novel bond-shift isomers 17 and 20, which may be formally regarded as cyclic nitrile ylides. The existence of such ylidic heterocumulenes has been predicted previously, but this work provides the first experimental observation of such species. The factors which are responsible for the special stability of the ylidic species 17 and 20 are discussed.

Near-infrared and star-forming properties of local luminous infrared galaxies

We use Hubble Space Telescope (HST) NICMOS continuum and Paα observations to study the near-infrared and star formation properties of a representative sample of 30 local (d ~ 35-75 Mpc) luminous infrared galaxies (LIRGs, infrared [8-1000 μm] luminosities of log L_IR = 11-11.9 L_☉). The data provide spatial resolutions of 25-50 pc and cover the central ~3.3-7.1 kpc regions of these galaxies. About half of the LIRGs show compact (~1-2 kpc) Paα emission with a high surface brightness in the form of nuclear emission, rings, and minispirals. The rest of the sample show Paα emission along the disk and the spiral arms extending over scales of 3-7 kpc and larger. About half of the sample contains H II regions with Hα luminosities significantly higher than those observed in normal galaxies. There is a linear empirical relationship between the mid-IR 24 μm and hydrogen recombination (extinction-corrected Paα) luminosity for these LIRGs, and the H II regions in the central part of M51. This relation holds over more than four decades in luminosity, suggesting that the mid-IR emission is a good tracer of the star formation rate (SFR). Analogous to the widely used relation between the SFR and total IR luminosity of R. Kennicutt, we derive an empirical calibration of the SFR in terms of the monochromatic 24 μm luminosity that can be used for luminous, dusty galaxies.