A proposal for the mechanism-of-action of diazoparaquinone natural products

Treatment of the representative diazoparaquinone prekinamycin dimethyl ether with Bu3SnH/AIBN in aromatic solvents furnishes moderate-to-good yields of formal aryl adducts wherein a molecule of solvent is attached to the carbon (C(11)) previously bearing the diazo function. Substituent studies provide evidence in support of a radical aromatic substitution mechanism, in which radical addition to the diazoparaquinone function generates an intermediate C(11) vinylic radical.     

SEASONAL TRENDS IN ERYTHEMAL and CARCINOGENIC ULTRAVIOLET RADIATION AT MID-SOUTHERN LATITUDES1989–1991

A network of solar carcinogenic/erythemal ultraviolet radiometers has been established in New Zealand. Daily integrated irradiances of this biologically harmful ultraviolet radiation for 1989, 1990 and 1991 are reported from radiometers located at Wellington (41°S) and Christchurch (43.5°S) and for 1990 and 1991 from the Auckland (37°S) radiometer. Although the monitoring program has not been running sufficiently long to discern any long-term changes in levels of solar ultraviolet radiation, shorter term trends are apparent, which are attributed to a seasonal cycle in levels of ozone at midlatitudes and changes in atmospheric aerosols.     

Furanodictine A and B: amino sugar analogues produced by cellular slime mold Dictyostelium discoideum showing neuronal differentiation activity

We investigated the constituents of Dictyostelium discoideum to clarify the diversity of secondary metabolites of Dictyostelium cellular slime molds and to explore biologically active substances that could be useful in the development of novel drugs. From a methanol extract of the multicellular fruit body of D. discoideum, we isolated two novel amino sugar analogues, furanodictine A (1) and B (2). They are the first 3,6-anhydrosugars to be isolated from natural sources. Their relative structures were elucidated by spectral means, and the absolute configurations were confirmed by asymmetric syntheses of 1 and 2. These furanodictines potently induce neuronal differentiation of rat pheochromocytoma (PC-12) cells.     

NMR studies of phosphinenickel(0) complexes of ethyl methacrylate Ni(PR3)2(CH2=C(CH3)COOC2H5)

¹³C NMR data are given for a series of phosphinenickel(0) complexes of ethyl methacrylate (ema), Ni(PR₃)₂(CH₂=C(CH₃)COOC₂H₅) (PR₃ = PPh₃ (Ia), PEtPh₂ (Ib), PEt₂Ph (Ic), PMe₂Ph (Id), PEt₃ (Ie)). The olefinic carbon signals of ema shift upfield by 71.5–86.5 ppm on coordination, the magnitude of the upfield shift increasing with increase in the bacisity of the phosphine ligand. The effect of the basicity of PR₃ is discussed on the basis of the back-bonding from Ni to ema. Variable temperature¹H NMR studies reveal that the ema of Id, the complex having the least sterically demanding phosphine ligands, exchanges with free ema in toluene on the NMR time scale. The dependence of the rate of exchange on the concentration of ema shows that the exchange proceeds through anS_N2 mechanism. The activation parameters are: ΔH₂₇₃^≠ 2.75 kcal/mol, ΔG₂₇₃^≠ 12.7 kcal/mol, ΔS₂₇₃^≠ ?37 e.u. The³¹P NMR spectra of the complexes show two doublets when the exchange is frozen out, indicating the inequivalence of the two phosphine ligands in the ema-coordinated complex. The difference in the³¹P chemical shifts of the two coordinated tertiary phosphines increases with increase in the basicity of the PR₃ ligand.     

The endomorphism spectrum of an ordered set

Theendomorphism spectrum of an ordered setP, spec(P)={|f(P)|:f End(P)} andspectrum number, sp(P)=max(spec(P)\{|P|}) are introduced. It is shown that |P|>(1/2)n(n – 1) ^{n – 1} implies spec(P) = {1, 2, ...,n} and that if a projective plane of ordern exists, then there is an ordered setP of size 2n ²+2n+2 with spec(P)={1, 2, ..., 2n+2, 2n+4}. Lettingh(n)=max{|P|: sp(P)n}, it follows thatc ₁ n ²h(n)c ₂ n ⁿ⁺¹ for somec ₁ andc ₂. The lower bound disproves the conjecture thath(n)2n. It is shown that if |P| – 1 spec(P) thenP has a retract of size |P| – 1 but that for all there is a bipartite ordered set with spec(P) = {|P| – 2, |P| – 4, ...} which has no proper retract of size|P| – . The case of reflexive graphs is also treated.Partially supported by a grant from the NSERC.Partially supported by a grant from the NSERC.     

LOWLAD: a locally weightedL 1 smoothing spline algorithm with cross validated choice of smoothing parameters

The computation ofL ₁ smoothing splines on large data sets is often desirable, but computationally infeasible. A locally weighted, LAD smoothing spline based smoother is suggested, and preliminary results will be discussed. Specifically, one can seek smoothing splines in the spacesW _m (D), with [0, 1] ⁿ D. We assume data of the formy _i =f(t _i )+ _i ,i=1,..., N with {t _i } _i=1 ^N D, the _i are errors withE( _i )=0, andf is assumed to be inW _m . An LAD smoothing spline is the solution,s , of the following optimization problem

Galloyl-Derived Orthoquinones as Reactive Partners in Nucleophilic Additions and Diels-Alder Dimerizations: A Novel Route to the Dehydrodigalloyl Linker Unit of Agrimoniin-Type Ellagitannins

Orthochloranil-mediated oxidation of galloyl monoethers furnishes the derived orthoquinones in excellent yield. These reactive electrophiles participate in a variety of nucleophilic addition reactions with heteroatomic and carbanionic partners. In addition, Lewis acid-mediated dimerization of the orthoquinones provides an efficient route to dehydrodigalloyl-type diaryl ether units characteristic of several ellagitannin natural products. The implications for ellagitannin biosynthesis and gallotannin-protein covalent attachment are discussed.     

AnL 1 smoothing spline algorithm with cross validation

We propose an algorithm for the computation ofL ₁ (LAD) smoothing splines in the spacesW _M (D), with . We assume one is given data of the formy _i =(f(t _i ) + _i , i=1,...,N with {itt_i} _i=1 ^{N D} , the _i are errors withE( _i )=0, andf is assumed to be inW _M . The LAD smoothing spline, for fixed smoothing parameter0, is defined as the solution,s , of the optimization problem (1/N) _i=1 ^N ¦y _i –g(t _i ¦+J _M (g), whereJ _M (g) is the seminorm consisting of the sum of the squaredL ₂ norms of theMth partial derivatives ofg. Such an LAD smoothing spline,s , would be expected to give robust smoothed estimates off in situations where the _i are from a distribution with heavy tails. The solution to such a problem is a thin plate spline of known form. An algorithm for computings is given which is based on considering a sequence of quadratic programming problems whose structure is guided by the optimality conditions for the above convex minimization problem, and which are solved readily, if a good initial point is available. The data driven selection of the smoothing parameter is achieved by minimizing aCV() score of the form .The combined LAD-CV smoothing spline algorithm is a continuation scheme in 0 taken on the above SQPs parametrized in, with the optimal smoothing parameter taken to be that value of at which theCV() score first begins to increase. The feasibility of constructing the LAD-CV smoothing spline is illustrated by an application to a problem in environment data interpretation.