Complexation of Syndiotactic Polystyrene with 12‐Crown‐4

Solid‐state complexation of syndiotactic polystyrene (sPS) with a crown ether compound, 1,4,7,10‐tetraoxa‐cyclododecane (12‐crown‐4), took place when a film of sPS/chloroform clathrate was subjected to a guest exchange procedure assisted with a plasticizing agent. The new guest 12‐crown‐4 molecules were incorporated into the crystalline region of the sPS film, without causing a large conformational change of host sPS helices. X‐ray diffraction and thermogravimetric investigations showed that sPS/12‐crown‐4 complex had a clathrate complex structure which contained four 12‐crown‐4 molecules per unit cell. IR and Raman data suggested that 12‐crown‐4 took a C_i‐type conformation in the sPS complex phase.

     

An Analysis of UVA Emissions from Sunlamps and the Potential Importance for Melanoma

Abstract— Exposure to solar UV radiation is a risk factor for cutaneous malignant melanoma (CMM). Epidemiologic studies have also considered the use of sunlamps as a possible contributor to CMM. We measured and analyzed the emission spectra of six different currently marketed sunlamps and a historical sunlamp, the UVB-emitting FS lamp, and compared the results to solar exposure. For a typical tanner (20 sessions @ 2 minimal erythema doses (MED)/session), the annual UVA doses from commonly used fluorescent sunlamps were 0.3-1.2 times that received from the sun. For a frequent tanner (100 sessions @ 4 MED/session), the annual UVA doses from fluorescent sunlamps were 1.2-4.7 times that received from the sun and 12 times for recently available, high-pressure sunlamps. To determine biologically effective doses, action spectra for squamous cell carcinoma (SCC) in humans and for melanoma in the Xiphophorus fish (XFM) were applied to the sunlamps' emission spectra. The results for the effective doses using the SCC action spectrum tracked the UVB doses, while the results using the XFM action spectrum tracked the UVA doses. When combined with UV exposure received from the sun, typical sunlamp use results in an approximate doubling of annual effective dose, if the XFM action spectrum is applied. Frequent use, however, can increase the annual effective XFM dose by as much as 6 times what would be received from the sun alone for fluorescent sunlamps and as much as 12 times for newer, high-pressure sunlamps.     

Supramolecular hybrid of metal nanoparticles and semiconducting single-walled carbon nanotubes wrapped by a fluorene-carbazole copolymer

The first approach for the preparation of metal nanoparticle/semiconducting single-walled carbon nanotube (SWNT) hybrids with specified chirality is described. For this purpose, a copolymer of a fluorene derivative with two long-chain alkyl substituents and a carbazole derivative carrying a thiol group was used. The copolymer was found to selectively dissolve (7,6)- and (8,7)SWNTs, as determined by UV/Vis/NIR absorption and Raman spectroscopy and 2D photoluminescence mapping. Gold and silver nanoparticles with diameters of about 3.8 and about 3.2 nm, respectively, were readily attached along the SWNTs by means of coordination bonds between the nanoparticles and the thiol moieties on the copolymer, as revealed by atomic force and electron microscopy studies. The study provides a novel way to design and fabricate metal nanoparticle/semiconducting SWNT hybrids with specific nanotube chirality.     

Artificial intelligence designed drug synthesis: One-pot preparation of trans β-lactams and application to cholesterol absorption inhibitor SCH 47949 synthesis

An artificial intelligence designed SCH 47949 synthesis is achieved in a stereoselective manner. The key step contains a stereoselective one-pot construction of the trans β-lactam framework via thermal electrocyclization. N-arylation of the β-lactam ring system and a series of functional group transformations synthesized SCH 47949 in a reasonable chemical yield.     

Spectral Gap and Transience for Ruelle Operators on Countable Markov Shifts

We find a necessary and sufficient condition for the Ruelle operator of a weakly Hölder continuous potential on a topologically mixing countable Markov shift to act with spectral gap on some rich Banach space. We show that the set of potentials satisfying this condition is open and dense for a variety of topologies. We then analyze the complement of this set (in a finer topology) and show that among the three known obstructions to spectral gap (weak positive recurrence, null recurrence, transience), transience is open and dense, and null recurrence and weak positive recurrence have empty interior.     

Sources of DPOAEs revealed by suppression experiments,inverse fast Fourier transforms,and SFOAEs in impaired ears

DPOAE sources are modeled by intermodulation distortion generated near the f2 place and a reflection of this distortion near the DP place. In a previous paper, inverse fast Fourier transforms (IFFTs) of DPOAE filter functions in normal ears were consistent with this model [Konrad-Martin et al., J. Acoust. Soc. Am. 109, 2862-2879 (2001)]. In the present article, similar measurements were made in ears with specific hearing-loss configurations. It was hypothesized that hearing loss at f2 or DP frequencies would influence the relative contributions to the DPOAE from the corresponding basilar membrane places, and would affect the relative magnitudes of SFOAEs at frequencies equal to f2 and fDP. DPOAEs were measured with f2 = 4 kHz, f1 varied, and a suppressor near fDP. L2 was 25-55 dB SPL (L1 = L2 + 10 dB). SFOAEs were measured at f2 and at 2.7 kHz (the average fDP produced by the f1 sweep) for stimulus levels of 20-60 dB SPL. SFOAE results supported predictions of the pattern of amplitude differences between SFOAEs at 4 and 2.7 kHz for sloping losses, but did not support predictions for the rising- and flat-loss categories. Unsuppressed IFFTs for rising losses typically had one peak. IFFTs for flat or sloping losses typically have two or more peaks; later peaks were more prominent in ears with sloping losses compared to normal ears. Specific predictions were unambiguously supported by the results for only four of ten cases, and were generally supported in two additional cases. Therefore, the relative contributions of the two DPOAE sources often were abnormal in impaired ears, but not always in the predicted manner.     

An automated fluorescence protein sequencer using 7-methylthio-4-(2,1,3-benzoxadiazolyl) isothiocyanate (MTBD-NCS) as an Edman reagent

An automated fluorescence protein sequencer using 7-methylthio-5-(2,1,3-benzoxadiazolyl) isithiocyanate (MTBD-NCS), a fluorescent Edman reagent, is developed by the modification of a commercial protein sequencer. The generated MTBD-thiohydantoin amino acids fluoresced strongly, whereas the by-products such as MTBD-thiocarbamoyl amino acids and MTBD-carbamoly amino acids did not fluoresce. A few interfering peaks were observed in the chromatogram and amino acid sequence was easily determined. The coupling and cyclization/cleavage reaction conditions and extraction conditions of generated MTBD-thiazolinone amino acids were optimized using an autonalyzer. Finally, the sequence of a synthetic peptide (25 pmol), leucine-enkephalin-Thr-amide, was determined and up to six residues were successively analyzed.     

Detection and characterization of 20-oxosteroids in rat brains using LC-electron capture APCI-MS after derivatization with 2-nitro-4-trifluoromethylphenylhydrazine

The detection and characterization of 20-oxosteroids in rat brains by liquid chromatography (LC)-electron capture atmospheric pressure chemical ionization (ECAPCI)-mass spectrometry (MS) is described. In the present method, oxosteroids were derivatized with a highly electron-affinitive reagent, 2-nitro-4-trifluoromethylphenylhydrazine, to convert them to the corresponding hydrazones. The derivatized steroids showed over 20-fold higher sensitivity in ECAPCI-MS than intact steroids measured in positive-APCI-MS. A brain sample was homogenized, purified with two disposable cartridges, derivatized and subjected to LC-ECAPCI-MS. Pregnenolone, progesterone, 5alpha-dihydroprogesterone, allopregnanolone and epiallopregnanolone were clearly detected with a 50 mg sample of the brain tissue.     

Visualization of how light changes affect ion movement in rice plants using a real-time radioisotope imaging system

Journal of Radioanalytical and Nuclear Chemistry - We developed a real-time radioisotope imaging system (RRIS) technique that can nondestructively visualize the element absorption and transport...