Mixed Cationic‐nonionic Surfactants and pH Adjustment Route to Synthesize High‐quality MCM‐48

Using the mixture of cetyltrimethylammonium bromide (CTAB) and p‐Octyl polyethylene glycol phenyl ether (OP‐10) as templates, siliceous MCM‐48 materials can be synthesized with low molar ratio of CTAB to silica (0.139:1) and low concentration of mixed surfactants (ca.5%) and within a wide range of OP‐10/CTAB ratio (0.08?0.25). The materials were characterized by X‐ray powder diffraction, N₂ adsorption/desorption isotherm, TEM, TG‐DSC and ²⁹Si MAS NMR. Measurements indicated that the use of mixed surfactants allowed better condensation and higher ordering of the cubic mesostructure; at the same time, some properties of these materials were sensitive to the OP‐10/CTAB ratio. It was also found that the reduced pH of the gel which had been crystallized for a certain time gave a highly reproducible synthesis with a high silica yield (about 95%). Furthermore, the reaction mechanism of the synthesis is discussed in detail.     

Nonalkaloid Constituents from Stemona japonica

Five new nonalkaloid constituents, a neolignan, japonin A ( 1 ), a macrocyclic lactone, japonin B ( 2 ), a (phenylethyl)benzoquinone, japonin C ( 3 ), a phenanthraquinone, japonin D ( 4 ), as well as a dihydrostilbene, stilbostemin M ( 5 ), were isolated from the roots of Stemona japonica, together with eight known compounds. Their structures were established by spectroscopic analyses.     

Bis[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(perchlorato‐κO)copper(II) bis­[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(methanol‐κO)copper(II) bis­(perchlorate) methanol disolvate

The title compound, [Cu(ClO₄)₂(C₄H₉N₃O₂)₂][Cu(C₄H₉N₃O₂)₂(CH₄O)₂](ClO₄)₂·2CH₃OH, comprises two independent Cu^II species lying on different inversion sites. In the Cu complexes, a distorted octa­hedral geometry arises (from basic square‐planar N₄ coordination) from the weak coordination of two perchlorate ions (as Cu—O) in one species and two methanol mol­ecules in the other (also as Cu—O). Inter­actions between the O atoms of the perchlorate anions or methanol groups and the imide or amine NH groups afford an extensive inter­molecular hydrogen‐bonding network.     

Two salts of 5‐sulfosalicylic acid and 3‐aminopyridine

5‐Sulfosalicylic acid (5‐SSA) and 3‐aminopyridine (3‐APy) crystallize in the same solvent system, resulting in two kinds of 1:1 proton‐transfer organic adduct, namely 3‐aminopyridinium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate, C₅H₇N₂⁺·C₇H₅O₆S⁻·H₂O or 3‐APy·5‐SSA·H₂O, (I), and the anhydrous adduct, C₅H₇N₂⁺·C₇H₅O₆S⁻ or 3‐APy·5‐SSA, (II). Both compounds have extensively hydrogen‐bonded three‐dimensional layered polymer structures, with interlayer homo‐ and heterogeneous π–π interactions in (I) and (II), respectively.     

Interaction of l-malic acid with alkaline metals and open chain polyammonium cations in aqueous solution

This work reports a potentiometric, calorimetric and spectropolarimetric ultraviolet circular dichroism (UV/CD) study of the interaction of l-malic acid with alkaline metals or (poly)ammonium (methylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, spermine, tetraethylenepentamine and pentaethylenehexamine) cations. Stability data (logK, DeltaG(0)) were obtained potentiometrically for the l-malic acid with (poly)ammonium cations systems; calorimetric measurements (25 degrees C) made it possible to obtain DeltaH(0) and TDeltaS(0) values for the complexes formed in the systems under examination. logK values calculated (for the reaction: H(i)A(i+)+H(j)L((j-z))=ALH(r)((i+j-z)), with r=i+j) range between 0.8 and 4.6, i.e., the interactions are from weak to fairly strong while maximum stability for each system is given by the species with the highest z(anion)xz(cation) (z=charge) value. Enthalpy changes associated with reactions H(n)A(n+)+L(2-)=ALH(n)((n-2)) and H(n)A(n+)+HL(-)=ALH(n+1)((n-1)) are always positive and increase progressively with n. The same is valid for T DeltaS(0) values, which indicate that these species are entropically stabilized, as expected for electrostatic interactions. It was verified that the UV/CD signal depends on both ionic medium and ionic strength value; for comparison, we used the l-malic acid signal recorded in tetramethylammonium chloride as baseline background salt (as in potentiometry). UV/CD spectra were recorded for solutions containing both cationic and anionic species. When the cation was a protonated polyamine, CD spectra calculations were performed for most stable ion pairs: the results show remarkable differences in Deltaepsilon (dm(3) mol(-1) cm(-1)) values at 205 nm (which is the l-malate UV/CD lambda(max)) between the chiral ligand and its complex with a polyamine.     

Total synthesis of the microtubule-stabilizing agent (-)-laulimalide

[structure: see text] The total synthesis of the potent microtubule-stabilizing anticancer agent (-)-laulimalide has been achieved in 27 steps and 2.9% overall yield. Notable features are the use of Jacobsen HDA chemistry for the enantioselective construction of the side chain dihydropyran, a diastereoselective aldol coupling using chiral boron enolate methodology, a Mitsunobu macrolactonization, and a Sharpless AE to introduce the epoxide onto des-epoxy-laulimalide.     

SUPPRESSION OF CONTACT HYPERSENSITIVITY BY UV RADIATION AND ITS RELATIONSHIP TO UV-INDUCED SUPPRESSION OF TUMOR IMMUNITY

Abstract— In this study, we examine some of the photobiologic and immunologic characteristics of the suppression of contact hypersensitivity (CHS) by UV radiation. BALB/c mice were irradiated on the shaved dorsal skin with FS40 sunlamps and sensitized 5 days later by applying a contact sensitizer lo the shaved abdomen. The suppression of CHS resulting from exposure to a given total dose of UV radiation was unaffected by changes in dose fractionation over a 5-day period and by changes in dose-rate over a 10-fold range. Elimination of wavelengths below 315 nm with a mylar filter abrogated the suppressive effect of the sunlamps, even when the same total energy was administered. Irradiation of unshaved mice required 14 times more energy to produce 50% suppression than was required for shaved mice, suggesting that the exposed skin is the primary target of this effect. Contact sensitization of UV-irradiated, but not unirradiated, mice induced the appearance of antigen-specific suppressor T lymphocytes in their spleen. The photobiologic and immunologic similarities between the suppression of CHS by UV radiation and the UV-mediated suppression of tumor rejection that we described previously suggest that these two immunosuppressive effects of UV exposure share certain steps in their pathways.     

Mass spectral structure elucidation of substituted 4-oxazolidones,the photocycloexpansion products of 2,4-azetidindiones

Abstract-2-Methoxy-4-oxazolidone structures are assigned to the photocycloexpansion products of the substituted 2,4-azetidindiones on the basis of mass spectral evidence. A discussion is given of the mass spectra of 2-methoxy-4-oxazolidones and of their hydrolysis products, the 2-hydroxy-4-oxazolidones and the ring opened substituted 2-hydroxy-N-formyl acetamides. Ring and chain forms, when both isolated, yield completely different mass spectra, indicating that no rapid tautomeric equilibrium is established in the gas phase.