MassBank: a public repository for sharing mass spectral data for life sciences

MassBank is the first public repository of mass spectra of small chemical compounds for life sciences (<3000 Da). The database contains 605 electron‐ionization mass spectrometry(EI‐MS), 137 fast atom bombardment MS and 9276 electrospray ionization (ESI)‐MSⁿ data of 2337 authentic compounds of metabolites, 11 545 EI‐MS and 834 other‐MS data of 10 286 volatile natural and synthetic compounds, and 3045 ESI‐MS² data of 679 synthetic drugs contributed by 16 research groups (January 2010). ESI‐MS² data were analyzed under nonstandardized, independent experimental conditions. MassBank is a distributed database. Each research group provides data from its own MassBank data servers distributed on the Internet. MassBank users can access either all of the MassBank data or a subset of the data by specifying one or more experimental conditions. In a spectral search to retrieve mass spectra similar to a query mass spectrum, the similarity score is calculated by a weighted cosine correlation in which weighting exponents on peak intensity and the mass‐to‐charge ratio are optimized to the ESI‐MS² data. MassBank also provides a merged spectrum for each compound prepared by merging the analyzed ESI‐MS² data on an identical compound under different collision‐induced dissociation conditions. Data merging has significantly improved the precision of the identification of a chemical compound by 21–23% at a similarity score of 0.6. Thus, MassBank is useful for the identification of chemical compounds and the publication of experimental data. Copyright © 2010 John Wiley & Sons, Ltd.     

Crystal-like periodic mesoporous organosilica bearing pyridine units within the framework

Periodic mesoporous organosilica with densely packed pyridine units within the framework and crystal-like molecular-scale periodicity was synthesized. The framework pyridines were chemically active and fully accessible for protonation and Cu(2+) adsorption.     

Determination of catecholamines and indoleamines in human urine based on intramolecular excimer-forming derivatization and fluorescence detection.

A liquid chromatographic (LC) determination of catecholamines and indoleamines is described. This is based on intramolecular excimer-forming fluorescence derivatization with 4-(1-pyrene)butanoyl chloride, followed by reversed-phase LC. The analytes, containing an amino moiety and phenolic hydroxyl moieties in a molecule, were converted to the corresponding polypyrene-labeled derivatives by one-step derivatization. They afforded intramolecular excimer fluorescence, which can clearly be discriminated from the normal fluorescence emitted from reagent blanks. The detection limits (S/N = 3) for catecholamines and indoleamines were femto-mole levels per 20-microL injection. Furthermore, this method was applied to a urine assay.     

Laser-driven metal exchange and preparation of metal phthalocyanine

Two types of laser-driven dry processes for the preparation of metal phthalocyanine are reported. In the first one, laser-driven metal exchange, the excimer laser beam was focused on a copper target, and ablated copper atoms were injected onto a thin film of dilithium phthalocyanine (Li₂Pc). The central metal atoms of Li₂Pc were partially exchanged by copper atoms, and the blue thin film of copper phthalocyanine (CuPc) was obtained after removal of the residual Li₂Pc by the hydrochloric acid treatment. In the second one, direct synthesis using the component organic molecule, CuPc was prepared by the implantation of laser-ablated copper atoms onto a thin film of 1,3-diiminoisoindoline (D I I I).     

One-electron oxidized nickel(II)-(disalicylidene)diamine complex: temperature-dependent tautomerism between Ni(III)-phenolate and Ni(II)-phenoxyl radical states

The one-electron oxidized species of a Ni(II)-phenolate complex has been shown to be in the Ni(II)-phenoxyl radical state at room temperature and the Ni(III)-phenolate state at < -120 degrees C, indicating that the oxidation state is temperature dependent.     

Local environments and dynamics of hydrogen atoms in protonated forms of ion-exchangeable layered perovskites estimated by solid-state H NMR

The local environments and dynamics of hydrogen atoms in five samples of protonated forms of ion-exchangeable layered perovskites, Dion-Jacobson-type H[LaNb₂O₇] and H[LaTa₂O₇], Ruddlesden-Popper-type H₂[SrTa₂O₇] and H₂[La₂Ti₃O₁₀], and H_1.8[(Sr_0.8Bi_0.2)Ta₂O₇] derived from an Aurivillius phase, Bi₂Sr₂Ta₂O₉, have been investigated by solid-state ¹H nuclear magnetic resonance spectroscopy (NMR). Solid-state ¹H NMR with a magic-angle spinning technique conducted at room temperature reveals that the mean electron densities around the ¹H nuclei in these protonated forms are relatively low, and that they decrease in the following order: H_1.8[(Sr_0.8Bi_0.2)Ta₂O₇]>H[LaNb₂O₇]>H₂[SrTa₂O₇]>H[LaTa₂O₇]>H₂[La₂Ti₃O₁₀]. The temperature-dependent solid-state ¹H broad-line NMR spectra measured at 140-400 K reveal a decrease in the signal width for all of these five samples upon heating due to motional narrowing. The NMR spectra of H[LaNb₂O₇] and H[LaTa₂O₇] are different from the other three protonated forms due to the weaker dipole-dipole interactions at low temperatures and lower mobility of the hydrogen atoms at high temperatures.     

Preparation of Weinreb amides using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM)

Weinreb amides were successfully prepared from the corresponding carboxylic acids using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) in the solvents, methanol, isopropyl alcohol, and acetonitrile, which can solubilize DMT-MM. A variety of carboxylic acids were converted to the corresponding Weinreb amides in excellent yields by simply mixing with DMT-MM and N,O-dimethylhydroxylamine hydrochloride.     

Low-temperature polymerization of lactams by using as catalyst the salt derived from NaAlEt4 and monomer and with several compounds as initiator

Low-temperature polymerization of α-pyrrolidone, α-piperidone, and ?-caprolactam was examined by using the salts derived from NaAlEt₄ and monomer, sodium lactamates, or the salt derived from AlEt₃ and monomer as catalyst and with N-acetyl lactams, ethyl acetate, or lactones as initiator. Sodium lactamate catalyst gave unsatisfactory results in the cases of ethyl acetate or lactones initiators, and gave the following order for the relative efficiency of initiators: N-acetyl lactam > ?-caprolactone ≥ ethyl acetate > β-propiolactone. The polymerization results obtained by the salt from NaAlEt₄ catalyst–ethyl acetate initiator system were nearly the same as those with N-acetyl lactam. The increases in the degree of polymerization and in the yield of polymer were observed in case of the salt from NaAlEt₄ catalyst-lactone initiator system, particularly in the cases of α-piperidone and ?-caprolactam. Also an incorporation of initiator into polymer chain was observed.     

Total synthesis of (+--oudemansin

($\text{+}\text{-}$)-Oudemansin has been synthesized starting from $\text{trans}$-cinnamaldehyde by a route involving the stereoselective Zn(BH₄)₂ reduction of β-keto ester.