SF Rate Research Articles

Quantum Beats in Crystalline Tetracene Delayed Fluorescence Due to Triplet Pair Coherences Produced by Direct Singlet Fission

A detailed analysis of the oscillations seen in the delayed fluorescence of crystalline tetracene is presented in order to study the mechanism of singlet fission. Three quantum beat frequencies of 1.06 ± 0.05, 1.82 ± 0.05, and 2.92 ± 0.06 GHz are resolved, which are damped on a time scale of 20 ns. The effects of sample morphology, excitation wavelength, and temperature are examined. A density matrix model for singlet fission is developed that quantitatively describes the frequencies, amplitudes, and damping of the oscillations. The model assumes a direct coupling of the initially excited singlet exciton to the triplet pair manifold. There is no electronic coherence between the singlet and triplet pair states, but the rapid singlet decay time of ∼200 ps in solution-grown single crystals provides the impulsive population transfer necessary to create a coherent superposition of three zero-field triplet pair states |xx>, |yy>, and |zz> with overall singlet character. This superposition of the three states gives rise to the three quantum beat frequencies seen in the experiment. Damping of the quantum beats results from both population exchange between triplet and singlet manifolds and pure dephasing between the triplet pair states. By lowering the temperature and slowing the SF rate, the visibility of the oscillations decreases. There is no evidence of magnetic dipole-dipole coupling between the product triplets. Our model provides good overall agreement with the data, supporting the conclusion that singlet fission in tetracene proceeds through the "direct" mechanism without strong electronic coupling between the singlet and triplet pair states.

Integral field spectroscopy based Hαsizes of local luminous and ultraluminous infrared galaxies

Aims. We study the analogy between local U/LIRGs and high-z massive SFGs by comparing basic H{\alpha} structural characteristics, such as size, and luminosity (and SFR) surface density, in an homogeneous way (i.e. same tracer and size definition, similar physical scales). Methods. We use Integral Field Spectroscopy based H{\alpha} emission maps for a representative sample of 54 local U/LIRGs (66 galaxies). From this initial sample we select 26 objects with H{\alpha} luminosities (L(H{\alpha})) similar to those of massive (i.e. M\ast \sim 10^10 M\odot or larger) SFGs at z \sim 2, and observed on similar physical scales. Results. The sizes of the H{\alpha} emitting region in the sample of local U/LIRGs span a large range, with r1/2(H{\alpha}) from 0.2 to 7 kpc. However, about 2/3 of local U/LIRGs with Lir > 10^11.4 L\odot have compact H{\alpha} emission (i.e. r1/2 < 2 kpc). The comparison sample of local U/LIRGs also shows a higher fraction (59%) of objects with compact H{\alpha} emission than the high-z sample (25%). This gives further support to the idea that for this luminosity range the size of the star forming region is a distinctive factor between local and distant galaxies of similar SF rates. However, when using H{\alpha} as a tracer for both local and high-z samples, the differences are smaller than the ones recently reported using a variety of other tracers. Despite of the higher fraction of galaxies with compact H{\alpha} emission, a sizable group (\sim 1/3) of local U/LIRGs are large (i.e. r1/2 > 2 kpc). These are systems showing pre-coalescence merger activity and they are indistinguishable from the massive high-z SFGs galaxies in terms of their H{\alpha} sizes, and luminosity and SFR surface densities.

Detailed Chemical Abundances of Globular Clusters in Local Group Dwarf Galaxies

We present detailed chemical abundances of Fe, Ca and Ba for 17 globular clusters (GCs) in 5 Local Group dwarf galaxies: NGC 205, NGC 6822, WLM, the SMC and LMC. These abundances are part of a larger sample of over 20 individual elements measured in GCs in these galaxies using a new analysis method for high resolution, integrated light spectra. Our analysis also provides age and stellar population constraints. The existence of GCs in dwarf galaxies with a range of ages implies that there were episodes of rapid star formation throughout the history of these galaxies; the abundance ratios of these clusters suggest that the duration of these burst varied considerably from galaxy to galaxy. We find evolution of Fe, Ca, and Ba with age in the LMC, SMC, and NGC 6822 that is consistent with extended, lower-efficiency SF between bursts, with an increasing contribution of low-metallicity AGB ejecta at late times. Our sample of GCs in NGC 205 and WLM are predominantly old and metal-poor with high [Ca/Fe] ratios, implying that the early history of these galaxies was marked by consistently high SF rates.

LOW-MASS GALAXY FORMATION IN COSMOLOGICAL ADAPTIVE MESH REFINEMENT SIMULATIONS: THE EFFECTS OF VARYING THE SUB-GRID PHYSICS PARAMETERS

We present numerical simulations aimed at exploring the effects of varying the sub-grid physics parameters on the evolution and the properties of the galaxy formed in a low-mass dark matter halo (~7 times 10^10 Msun/h at redshift z=0). The simulations are run within a cosmological setting with a nominal resolution of 218 pc comoving and are stopped at z = 0.43. In all of our simulations, an extended old/intermediate-age stellar halo and a more compact younger stellar disk are formed. We found that a non negligible fraction of the halo stars are formed in situ in a spheroidal distribution. Changes in the sub-grid physics parameters affect significantly and in a complex way the evolution and properties of the galaxy: (i) Lower threshold densities nsf produce larger stellar effective radii Re, less peaked circular velocity curves V_c(R), and greater amounts of low-density and hot gas in the disk mid-plane; (ii) When stellar feedback is modeled by temporarily switching off radiative cooling in the star forming regions, Re increases (by a factor of ~ 2 in our particular model), the circular velocity curve becomes flatter, and a complex multi-phase gaseous disk structure develops; (iii) A more efficient local conversion of gas mass to stars, measured by a stellar particle mass distribution biased toward larger values, increases the strength of the feedback energy injection -driving outflows and inducing burstier SF histories; iv) If feedback is too strong, gas loss by galactic outflows -which are easier to produce in low-mass galaxies- interrupts SF, whose history becomes episodic. The simulations exhibit two important shortcomings: the baryon fractions are higher, and the specific SF rates are much smaller, than observationally inferred values for redshifts ~ 0.4-1.

SPITZEROBSERVATIONS OF PASSIVE AND STAR-FORMING EARLY-TYPE GALAXIES: AN INFRARED COLOR–COLOR SEQUENCE

We describe the infrared properties of a large sample of early type galaxies, comparing data from the Spitzer archive with Ks-band emission from 2MASS. While most representations of this data result in correlations with large scatter, we find a remarkably tight relation among colors formed by ratios of luminosities in Spitzer-MIPS (24, 70 and 160 um) bands and the Ks-band. Remarkably, this correlation among E and S0 galaxies follows that of nearby normal galaxies of all morphological types. In particular, the tight infrared color-color correlation for S0 galaxies alone follows that of the entire Hubble sequence of normal galaxies, roughly in order of galaxy type from ellipticals to spirals to irregulars. The specific star formation rate of S0 galaxies estimated from the 24um luminosity increases with decreasing Ks-band luminosity (or stellar mass) from essentially zero, as with most massive ellipticals, to rates typical of irregular galaxies. Moreover, the luminosities of the many infrared-luminous S0 galaxies can significantly exceed those of the most luminous (presumably post-merger) E galaxies. Star formation rates in the most infrared-luminous S0 galaxies approach 1-10 solar masses per year. Consistently with this picture we find that while most early-type galaxies populate an infrared red sequence, about 24% of the objects (mostly S0s) are in an infrared blue cloud together with late type galaxies. For those early-type galaxies also observed at radio frequencies we find that the far-infrared luminosities correlate with the mass of neutral and molecular hydrogen, but the scatter is large. This scatter suggests that the star formation may be intermittent or that similar S0 galaxies with cold gaseous disks of nearly equal mass can have varying radial column density distributions that alter the local and global SF rates.

The young stellar population at the center of NGC 205

Context. NGC 205 is a peculiar dwarf elliptical galaxy hosting in its center a population of young blue stars. Their origin is still matter of debate, the central fresh star formation activity possibly being related to dynamical interactions between NGC 205 and M31. Aims. The star formation history in the central 30\arcsec ($\sim$120 pc) around the NGC 205 central nucleus is investigated in order to obtain clues to the origin of the young stellar population. Methods. Deep HST/ACS CCD photometry is compared with theoretical isochrones and luminosity functions to characterize the stellar content of the region under study and compute the recent SF rate. Results. Our photometry reveals a previously undetected blue plume of young stars clearly distinguishable down to I$\simeq$26. Our analysis suggests that 1.9$\times10^5$ M$_\odot$ were produced between approximately 62 Myr and 335 Myr ago in the NGC 205 inner regions, with a latest minor episode occurring $\sim$25 Myr ago. This implies a star formation rate of $\sim7\times10^{-4}$ M$_\odot$/yr over this period. Conclusions. The excellent fit of the observed luminosity function of young main sequence stars obtained with a model having a constant star formation rate argues against a tidally triggered star formation activity over the last $\sim$300 Myr. Rather, a constant SF may be consistent with NGC 205 being on its first interaction with M 31.

Radiographic prognostic criteria for extracorporeal shock-wave lithotripsy: A study of 485 patients

Objectives. We studied 485 patients treated by extracorporeal shock-wave lithotripsy (ESWL) using anultrasound electrohydraulic apparatus in an effort to define radiographic criteria for better patient selection for ESWL. Methods. Results were assessed according to plain x-ray nephrotomography and ultrasound. The criteriafor measuring success (stone free [SF]) excluded all residual fragments. After per-criteria analysis of the results, a multivariate analysis as well as an analysis of stone composition by infrared spectroscopy were performed. Results. The SF rate was 57.5% (279 of 485). Calculi that were smooth, denser than bone, located in thelower calyx, and larger than 15 mm had less satisfactory results despite a greater number of impulses. A correlation was established between the radiographic appearance of the calculus, its composition, and ESWL results. Rough, less dense calcium oxalate dihydrate yielded satisfactory results (65%), whereas smooth, dense calcium oxalate monohydrate led to less conclusive results (41%). Multivariate analysis demonstrated the predominant influence of radiographic calculus profile on the results: rough, less dense calculi yielded a 79.4% SF rate, whereas smooth, dense calculi yielded a 33.6% SF rate. Conclusions. We propose that patients with dense, smooth calculi located in the lower calyx and larger than15 mm be treated by other techniques, such as percutaneous nephrolithotomy. This would not only increase the ESWL effectiveness rate, but would also reduce the cost of treating kidney stones.

Postprandial lipoproteins and progression of coronary atherosclerosis

The relations between triglyceride-rich lipoproteins, alimentary lipaemia and coronary heart disease (CHD) have remained obscure and much debated. We studied the basal and postprandial plasma levels of chylomicron remnants and very low density lipoproteins (VLDL) of varying particle size in 32 male postinfarction patients (mean (S.D.) age 48.8 (3.2) years) and in 10 age-matched control men. The selective quantification of postprandial intestinal and hepatic lipoproteins was accomplished by determining apolipoproteins B-48 and B-100 in lipoprotein subfractions of Svedberg flotation (Sf) rates > 12 before and 3, 6 and 12 h after an oral fat load. Since all patients had undergone two coronary angiographies with an intervening time interval of around 5 years, lipoprotein fractions were examined in relation to the global severity as well as the rate of progression of coronary lesions. The postprandial plasma levels of small chylomicron remnants (Sf 20–60 apolipoprotein B-48) were found to relate distinctly to the rate of progression of coronary lesions between the angiographies ( r = 0.51, P = 0.01). Adjustment for the possible confounding effect of the HDL cholesterol and dense LDL apolipoprotein B concentrations did not substantially alter the strength of this association. Neither the increment of plasma triglyceride during the postprandial period nor the concentrations of other lipoprotein fractions closely reflected the amount of small chylomicron remnants in the circulation or correlated with progression of coronary lesions. Our data suggest that small chylomicron remnants are implicated in the progression of coronary artery disease.

Nonuniform radiolabeling of VLDL apolipoprotein B: implications for the analysis of studies of the kinetics of the metabolism of lipoproteins containing apolipoprotein B.

Radiolabeling of whole lipoproteins or individual apolipoproteins has been an essential tool for the determination of the kinetics of apolipoprotein metabolism in vivo. Mathematical analysis of specific radioactivity (SA) or total radioactivity data has demonstrated the existence of significant complexity in the plasma decay curves of several apolipoproteins. Results obtained during development of methods to study the metabolism of apolipoprotein B (apoB) in very low density lipoprotein (VLDL) subclasses isolated according to flotation (Sf) rates from whole radiolabeled (d less than 1.006 g/ml) VLDL suggested nonuniform radiolabeling of apoB in the three Sf subclasses being studied. We therefore determined apoB SA in VLDL Sf subclasses in ten hypertriglyceridemic and five normal subjects. After radioiodination of apoB in whole VLDL, different apoB SA were found in Sf 400-100, Sf 100-60, and Sf 60-20. The pattern of labeling was quite variable among subjects. On average, apoB SA in the VLDL tracer was greatest in Sf 400-100, and least in Sf 60-20. Nonuniform labeling could also be demonstrated in five studies in which samples were obtained 3 min after intravenous injection of the tracer into subjects with a wide range of plasma triglycerides. Nonuniform labeling of apoB in whole VLDL was also demonstrated in two of the subjects by isolating subclasses of their VLDL that did not bind to an anti-apolipoprotein E immunoaffinity column. These results indicate that the usual assumption of homogeneous labeling of apoB may be erroneous. We have derived a simple mathematical formula to study the consequences of this assumption in estimating kinetic parameters. It is shown that an erroneous assumption of homogeneous tracer labeling may significantly underestimate or overestimate the true production rate, even in a simple two-pool model. Identification of labeling characteristics and incorporation of this information into the mathematical analysis of the plasma radioactivity data can improve the accuracy of the analysis as well as the sensitivity of compartmental models generated by such data.

Limited Tryptic Digestion of Human Serum Low‐Density Lipoprotein: Islation and Characterisation of the‐Deficient Particle and of Its Apoprotien

Limited tryptic digestion of human serum low-density (LD) lipoprotein (rho 1.024-1.045 g/ml) under defined conditions permitted isolation by gel filtration chromatography of a stable, protein-deficient lipoprotein; the liberated protein was separated as a mixture of peptides of low molecular weight (less than 5000). Comparison of the chemical, physical and immunological characteristics of the trypsin-treated LD-lipoprotein with those of the native preparation revealed several differences, including (a) a diminished protein content (loss of some 20-25% of the total protein of LD-lipoprotein) and increased proportions of the various lipid components, except for triglyceride (probably resulting from a loss of bound free fatty acids with the liberated peptides); (b) a greater heterogeneity in particle size and slightly larger mean diameter; (c) a lower hydrated density and greater peak sf rate than the native LD-lipoprotein (d) an increased net negative charge; and (e) a partial immunological identity between LD-lipoprotein and the corresponding trypsin-treated fraction. While the amino acid compositions of the protein moieties of LD-lipoprotein and of trypsin-treated LD-lipoprotein were essentially identical, trypsin-treated apo-LD-lipoprotein was distinct in its complete solubility in urea-containing buffers at high concentrations, and also in its partial solubility in buffers lacking denaturing agents. Comparison of the apoproteins of the native and trypsin-treated LD-lipoproteins by electrophoretic techniques based on molecular weight revealed a transformation of the high-molecular weight material (greater than 250 000) characteristic of apo-LD lipoprotein into several polypeptide species (10 major forms) ranging in size from 161 500 to about 10 000. The largest of these (band b1: 161 500) could be completely dissociated into smaller components (b2: 93 500 and b3: 77 000) upon extensive heat treatment at 90 degrees C. Electrophoresis of the soluble fraction of apo-LD-lipoprotein and of that from its trypsin-treated counterpart in polyacrylamide gels containing urea at basic pH showed the disappearance of the small amounts (less than 5%) of C apoproteins of apo-LD-lipoprotein upon tryptic treatment. These results, which were highly reproducible in LD-lipoprotein preparations from different individuals, suggest that trypsin-treated LD-lipoprotein may provide a model for investigation of the organisation and structural role of the prinicipal apoprotein (apolipoprotein-B) in the LD-lipoprotein molecule.

Dyslipoproteinemia (a remnant lipoprotein disease) in uremic patients on hemodialysis

Plasma lipoproteins of uremie patients on hemodialysis were studied by chemical, electrophoretic, ultracentrifugal and electron microscopic techniques. Low-density lipoproteins ( d 1.006–1.063) isolated from the plasma of five patients who were on hemodialysis therapy for 1 to 54 months showed two or three midband lipoproteins (bands between pre-β and (β-lipoproteins) when studied by polyacrylamide gel electrophoresis. Correspondingly, two or three peaks were observed in the analytical ultracentrifugal patterns of the isolated low-density lipoproteins of these patients. Low-density lipoproteins of a plasma which showed three midband lipoprotein components on polyacrylamide gel electrophoresis and three peaks by analytical ultracentrifugal analysis were isolated and each midband lipoprotein subfraction was characterized. As demonstrated with the isolated lipoprotein subfractions, low-density lipoproteins of the patient consisted of Sf 13, Sf 10, and Sf 7 + Sf 6 low-density lipoproteins. The lipoproteins with the higher Sf rate (Sf 13) contained more triglyceride and less cholesteryl ester and showed a larger lipoprotein particle size than the other low-density lipoprotein subfractions, which properties are characteristics of the intermediate-density, remnant lipoproteins. These findings indicate that the previously-reported “broad-midband lipoprotein pattern” on polyacrylamide gel electrophoresis which was detected in 58% of hemodialysis patients is a result of the accumulation of the remnant or intermediatedensity lipoproteins.

Studies on a Dyslipoproteinemia in Hemodialysis Patients

Grossly abnormal serum lipoprotein (Lp) profile which appeared as a broad-midband pattern (BMP) in PAG electrophoresis was detected in 67% of uremic patients maintained by prolonged hemodialysis therapy (hemodialysis patients). It was revealed that BMP was ascribed to the presence of a discrete series of Lps which were intermediate between beta-migrating LDL and pre-beta-migrating VLDL regarding buoyant density, Sf rate, chemical composition, and behavior in electrophoresis. The results in the present study indicate that the accumulation of these Lps, which may include the previously-known Lp species such as the intermediate-density Lp or the remnant particles, is taking place in hemodialysis patients.

Interaction of rat plasma very low density lipoprotein with lipoprotein lipase-rich (postheparin) plasma.

Incubation of 125I-labeled very low density lipoprotein (VLDL) with lipoprotein lipase-rich (postheparin) plasma obtained from intact or supradiaphragmatic rats resulted in the transfer of more than 80% of apoprotein C from VLDL to high density lipoprotein (HDL), whereas apoprotein B was associated with lipoprotein of density less than 1.019 g/ml (intermediate lipoprotein). The transfer of 125I-labeled apoprotein C from VLDL to HDL increased with time and decreased in proportion to the amount of VLDL in the incubation system. A relationship was established between the content of triglycerides and apoprotein C in VLDL, whereas the amount of apoprotein C in VLDL was independent of that of other apoproteins, especially apoprotein B. The injection of heparin to rats preinjected with 125I-labeled VLDL caused apoprotein interconversions similar to those observed in vitro. The intermediate lipoprotein was relatively rich in apoprotein B, apoprotein VS-2, cholesterol, and phospholipids and poor in triglycerides and apoprotein C. The mean diameter of intermediate lipoprotein was 269 A (compared with 427 A, the mean Sf rate was 30.5 (compared with 115), and the mean weight was 7.0 X 10(6) daltons (compared with 23.1 X 10(6)). From these data it was possible to calculate the mass of lipids and apoproteins in single lipoprotein particles. The content of apoprotein B in both particles was virtually identical, 0.7 X 10(6) daltons. The relative amount of all other constituents in intermediate lipoprotein was lower than in VLDL: triglycerides, 22%; free cholesterol, 37%; esterified cholesterol, 68%; phospholipids, 41%; apoprotein C, 7%, and VS-2 apoprotein, 60%. The data indicate that (a) one and only one intermediate lipoprotein is formed from each VLDL particle, and (b) during the formation of the intermediate lipoprotein all lipid and apoprotein components other than apoprotein B leave the density range of VLDL to a varying degree. Whether these same changes occur during the clearance of VLDL in vivo is yet to be established.

Friedel-Crafts Alkylation of Aromatic Compounds with Phosphorus Esters

The alkylations of aromatic compounds with trialkyl phosphites (1), dialkyl phosphites (2), and trialkyl phosphates (3) in the presence of aluminum chloride were studied involving several raction variables, such as time, ratio of reactants, nature of catalyst and solvent, and combinations thereof. Extensive disproportionation and isomerization were observed in the reaction with monosubstituted alkylbenzenes under heterogeneous reaction conditions obtained by the use of an excess of aromatic substrates. A combination of aluminum chloride—nitromethane complex and dichloromethane as solvent was used to eliminate these undesirable effects and to give homogeneous and practically non-isomerizing conditions. The scope of the reaction was studied with a number of aromatic substrates, and their relative reactivities were compared to that of benzene in competitive isopropylations with triisopropyl phosphite. The relative rates and isomer distributions showed low substrate and low positional selectivities and poor agreement with Brown’s selectivity relationship. The substrate selectivity was somewhat higher and the positional selectivities were somewhat lower than those obtained in competitive isopropylation reactions with other isopropylating agents. The selectivity factor, Sf, and partial rate factors were calculated. An electrophilic alkylation mechanism is proposed on the basis of (1) the relative rates of isopropylation, (2) the isomer distribution of dialkylated aromatics, and (3) the necessity of a strong Lewis acid in these reactions.

Flotation rates, molecular weights and hydrated densities of the low-density lipoproteins.

AbstractA method involving three computer programs is described for characterizing the major component of the Sf 0–12 low‐density lipoprotein class by its Sf rate, hydrated density and molecular weight. All necessary information is obtained from a standard low and high‐density lipoprotein ultracentrifugal analysis. Moving‐boundary flotation rates are measured in 1.061 g/ml sodium chloride and 1.200 g/ml sodium bromide solutions and are corrected to flotation at zero concentration. Hydrated densities are calculated from η Fo versus ρ plots and minimum hydrated molecular weights calculated using Stokes' frictional factor, assuming spherical molecules. Preliminary application of this procedure indicates higher Sfo rates, higher molecular weights, and lower hydrated densities in females than in males. Molecular weights and standard deviations of the principal Sf 0–12 component for non‐fasting normal adult females and males were 2.36±0.16 and 2.12±0.20 millions, respectively.