Absorption,fluorescence and stimulated fluorescence by polaritons in thin anthracene crystals. A re-interpretation of spectroscopic properties of anthracene

The transmission, absorption (excitation spectra) and fluorescence spectra of thin (? 47 nm) free mounted anthracene flakes have been measured. True absorption in b polarization in the region of the lowest exciton state occurs as a result of scattering by phonons. It has a minimum near the transverse exciton frequency and a maximum near the longitudinal exciton frequency, in agreement with expected polariton behaviour. Thickness dependent polariton states have finite absorption and fluorescence transition probabilities (due to crystal inhomogeneities) and are observed below the transverse exciton frequency. These polariton states represent the energy reservoir for excitation energy in the bulk of the crystal. A surface-induced exciton state is the origin of the sharp line fluorescence from pure crystals and accounts for the high efficiency of stimulated fluorescence at low temperatures. Stimulated fluorescence can also be observed from the polariton modes when excitation occurs in these modes. Resonance interactions between polariton modes and impurity levels represent an important pathway for fluorescence quenching in crystalline anthracene.     

Glucuronide conjugates of Soraprazan (BY359), a new potassium-competitive acid blocker (P-CAB) for the treatment of acid-related diseases

Glucuronide conjugates of Soraprazan (BY359), a potent novel anti-secretory drug (currently in Phase II clinical trials), were not directly accessible synthetically. This was due to the relative instability of Soraprazan under the harsh Lewis acid conditions employed in popular glucuronidation methodologies and a lack of reactivity under alternative, Koenigs-Knorr, coupling conditions. We have now devised a successful synthesis using the novel N-acetylated Soraprazan to access the required glucuronide metabolites on gram scale. Coupling of this novel aglycone with methyl 1-O-trichloroacetimidoyl-2,3,5-tri-O-isobutyryl-α-d-glucopyran-uronate in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) gave the protected glucuronide intermediates. A one-pot two-step deprotection involving hydrolysis of the ester functionalities and removal of the N-acetyl group with alkaline hydrazine delivered the title compounds in satisfactory yield.     

Bond interchange reactions in functionalized triglyceride oil/poly(ethylene terephthalate) compositions

Naturally functionalized triglyceride oils are renewable resources which contain reactive chemical groups, hydroxyl in the case of castor oil, and epoxide in the case of vernonia oil. In this article, the reaction of these groups, and the ester linkages between the glycerol and acid residue portions of the oil molecule with poly(ethylene terephthalate) (PET) is investigated through a variety of means. Multiple reactions are possible in the triglyceride–PET system, some of which form a copolymer that increases miscibility, and if allowed to continue, forms a completely random copolymer mixture. Among the numerous reactions possible, PET–ester exchange with the hydroxyl or epoxide functionality of the triglyceride oils is found to be the most significant, and the effects of these and other reactions are observed and structural implications discussed. © 1993 John Wiley & Sons, Inc.     

Reactions and X-ray crystal structure of (3-cyano-2,4-pentanedionato-N)pentaamminecobalt(III) perchlorate chloride dihydrate

The pentaamminecobalt(III) complex with the 3-cyano-2,4-pentanedionate anion coordinated through the nitrile nitrogen has been characterized by X-ray crystallography. The crystals of [(NH₃)₅CoNCacac](Cl)(ClO₄)·2H₂O are triclinic, space group P , a = 10.245(2) Å, b = 14.071(4) Å, c = 6.971(2) Å, = 90.03(3)°, β = 109.86(2)°, γ = 108.91(2)°, V= 887.1 ų, Z = 2, D_c = 1.64 g cm⁻³, F(000) = 456, Mo-K radiation, λ = 0.71069 Å, μ(Mo-K) = 12.7 cm⁻¹. The structure was determined by the heavy-atom method, and refined by block-diagonal least-squares calculations, R = 0.0537, R_w = 0.0607, for 2499 observed reflections. Principal dimensions are: Co---N(NH₃) trans to NCacac⁻ 1.940(5), other Co---N(NH₃) 1.967(2), Co---N(NCacac⁻) 1.911(5) Å. The pendant acac moiety is best described in terms of a delocalized bond network with, for example, C---C distances in the range 1.44–1.52(1) Å. Several reactions involving this free acac group are also described including the preparation and characterization of the dimeric species pentaamminecobalt(III) - μ - (3 - cyano - 2,4 - pentanedionato) - bis(propylenediamine) cobalt(III) perchlorate.     

Characterization of phosphopeptides from protein digests using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and nanoelectrospray quadrupole time-of-flight mass spectrometry

A two-step mass spectrometric method for characterization of phosphopeptides from peptide mixtures is presented. In the first step, phosphopeptide candidates were identified by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) based on their higher relative intensities in negative ion MALDI spectra than in positive ion MALDI spectra. The detection limit for this step was found to be 18 femtomoles or lower in the case of unfractionated in-solution digests of a model phosphoprotein, beta-casein. In the second step, nanoelectrospray tandem mass (nES-MS/MS) spectra of doubly or triply charged precursor ions of these candidate phosphopeptides were obtained using a quadrupole time-of-flight (Q-TOF) mass spectrometer. This step provided information about the phosphorylated residues, and ruled out nonphosphorylated candidates, for these peptides. After [(32)P] labeling and reverse-phase high-performance liquid chromatography (RP-HPLC) to simplify the mixtures and to monitor the efficiency of phosphopeptide identification, we used this method to identify multiple autophosphorylation sites on the PKR-like endoplasmic reticulum kinase (PERK), a recently discovered mammalian stress-response protein.     

PHOTO-CIDNP DETECTION OF PYRIMIDINE DIMER RADICAL CATIONS IN ANTHRAQUINONESULFONATE- SENSITIZED SPLITTING

Anthraquinone-2-sulfonate (AQS) photosensitizes pyrimidine dimer splitting. Electron abstraction from the dimer is thought to induce dimer splitting, but direct evidence for the existence and intermediacy of dimer radical cations has been lacking. By employing photochemically induced dynamic nuclear polarization, we have found emission signals in the NMR spectra of dimers upon photolysis of dimers in the presence of anthraquinone-2-sulfonate. The two dimers employed were cis, syn-thymine dimer in which the N(1)-positions were linked by a three-carbon bridge and the N(3), N(3')-dimethyl derivative of that compound. The anthraquinone-2-sulfonate sensitized photochemically induced dynamic nuclear polarization spectrum of the methylated derivative exhibited an emission signal from the dimer-C(6) hydrogens. This result implied the existence of a dimer radical cation (mD+.) formed by electron abstraction by excited anthraquinone-2-sulfonate and nuclear spin sorting within a solvent caged radical ion pair [mD+. AQS-.]. Product pyrimidine photochemically induced dynamic nuclear polarization signals were also seen [enhanced absorption by C(6)-hydrogens and emission by C(5)-methyl groups]. Nuclear spin polarization in the product resulted from spin sorting in one or more of its precursors, including mD+. The results support the conclusion that dimer radical cations not only exist but are intermediates in the photosensitized splitting of pyrimidine dimers by anthraquinonesulfonate.     

The structure of projection-valued states: A generalization of Wigner's theorem

A projection-valued state is defined to be a completely orthoadditive map from the projections on one Hilbert space into the projections on another Hilbert space, which preserves the unit. Any such mapping is shown to have the formP U ₁(P 1₁)U ₁ ^–1 U ₂(P 1₂)U ₂ ^–1 , whereU ₁ is unitary andU ₂ is antiunitary, generalizing Wigner's theorem on symmetry transformations. A physical interpretation is given and the relation to quantum logic is discussed.The contents of this paper are a portion of the author's dissertation at the University of Massachusetts at Amherst.     

Diphosphine-phosphenium coordination complexes representing monocations with pendant donors and ligand tethered dications

Homoatomic P-P coordinate bonding is exploited to prepare the first examples of triphosphorus monocations and tetraphosphorus dications using dimethylphosphenium or diphenylphosphenium Lewis acceptors with diphosphinomethane, diphosphinoethane, diphosphinohexane, or diphosphinobenzene ligands. Solid-state structures and spectroscopic characterization data for complexes involving bis(diphenylphosphino)methane ligands show coordination of only one donor site of the diphosphine ligand in the monocations, and chelate complexation is not observed. Tetraphosphorus dications are observed with longer diphosphines, in which the ligand tethers two phosphenium acceptors. The structural preferences between monocations with pendant phosphines and tethered dications are dependent on intramolecular steric interactions and the flexibility of the tether.     

An intraindividual study of the characteristics of erythema induced by bath and oral methoxsalen photochemotherapy and narrowband ultraviolet B

We compared the characteristics of psoralen and ultraviolet A (PUVA) erythema in skin photosensitized by bath or oral methoxsalen in 20 subjects. Erythema was assessed visually and with a reflectance instrument at 24 h intervals for 7 days. In addition, narrowband ultraviolet B (TL-01 UVB) erythema was examined in 19 of these subjects at 4, 8, 12, 24, 48 and 72 h and in another nine subjects at 12, 15, 18, 21 and 24 h. Both bath and oral PUVA exhibited broad erythemal peaks beyond 72 h. For topical PUVA the lowest minimal phototoxic dose (MPD) occurred at 120 and 144 h (P = 0.01 and 0.03 compared with 72 h). Oral PUVA erythema peaked earlier at 96 h: the MPD was significantly lower at 96, 120 and 144 h compared with 72 h (P = 0.001, 0.01 and 0.02, respectively). At 120 h, bath PUVA had a significantly steeper slope compared with oral PUVA. The TL-01 UVB minimal erythema dose was significantly lower at 12 h compared with 24 h (P = 0.019). The majority of subjects were at maximal erythema at 12 h (22 of 28) and 15 h (eight of nine). Our results suggest that peak erythema for bath PUVA, oral PUVA and TL-01 UVB occurs at 120, 96 and 12-15 h, respectively.