Total Synthesis of the Anti‐inflammatory and Pro‐resolving Lipid Mediator MaR1n−3 DPA Utilizing an sp3–sp3 Negishi Cross‐Coupling Reaction

The first total synthesis of the lipid mediator MaR1_{n?3 DPA} ( 5 ) has been achieved in 12 % overall yield over 11 steps. The stereoselective preparation of 5 was based on a Pd‐catalyzed sp³–sp³ Negishi cross‐coupling reaction and a stereocontrolled Evans–Nagao acetate aldol reaction. LC‐MS/MS results with synthetic material matched the biologically produced 5 . This novel lipid mediator displayed potent pro‐resolving properties stimulating macrophage efferocytosis of apoptotic neutrophils.     

Tunability of the M(II)M(III)/M(II)(2) and M(III)(2)/M(II)M(III) (M=Mn, Co) couples in bis-μ-O,O'-carboxylato-μ-OR bridged complexes

A comparison of the electrochemical properties of a series of dinuclear complexes [M(2)(L)(RCO(2))(2)](+) with M = Mn or Co, L = 2,6-bis(N,N-bis-(2-pyridylmethyl)-sulfonamido)-4-methylphenolato (bpsmp(-)) or 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato (bpbp(-)) and R = H, CH(3), CF(3) or 3,4-dimethoxybenzoate demonstrates: (i) The electron-withdrawing sulfonyl groups in the backbone of bpsmp(-) stabilize the [M(2)(bpsmp)(RCO(2))(2)](+) complexes in their M(II)(2) oxidation state compared to their [M(2)(bpbp)(RCO(2))(2)](+) analogues. Manganese complexes are stabilised by approximately 550 mV and cobalt complexes by 650 mV. (ii) The auxiliary bridging carboxylato ligands further attenuate the metal-based redox chemistry. Substitution of two acetato for two trifluoroacetato ligands shifts redox couples by 300-400 mV. Within the working potential window, reversible or quasi-reversible M(II)M(III)? M(II)(2) processes range from 0.31 to 1.41 V for the [Co(2)(L)(RCO(2))(2)](+/2+) complexes and from 0.54 to 1.41 V for the [Mn(2)(L)(RCO(2))(2)](+/2+) complexes versus Ag/AgCl for E(M(II)M(III)/M(II)(2)). The extreme limits are defined by the complexes [M(2)(bpbp)(CH(3)CO(2))(2)](+) and [M(2)(bpsmp)(CF(3)CO(2))(2)](+) for both metal ions. Thus, tuning the ligand field in these dinuclear complexes makes possible a range of around 0.9 V and 1.49 V for the one-electron E(M(II)M(III)/M(II)(2)) couple of the Mn and Co complexes, respectively. The second one-electron process, M(II)M(III)? M(III)(2) was also observed in some cases. The lowest potential recorded for the E°(M(III)(2)/M(II)M(III)) couple was 0.63 V for [Co(2)(bpbp)(CH(3)CO(2))(2)](2+) and the highest measurable potential was 2.23 V versus Ag/AgCl for [Co(2)(bpsmp)(CF(3)CO(2))(2)](2+).     

Factorizing multivariate time series operators

Motivated by problems occurring in the empirical identification and modelling of a n-dimensional ARMA time series X(t) we study the possibility of obtaining a factorization (I + a₁B + … + a_pB^p) X(t) = [Π_i=1^p (I ? α_iB)] X(t), where B is the backward shift operator. Using a result in [3] we conclude that as in the univariate case such a factorization always exists, but unlike the univariate case in general the factorization is not unique for given a₁, a₂,…, a_p. In fact the number of possibilities is limited upwards by $\text{(np)!}\text{(n!)}{}^{\mathrm{p}}$, there being cases, however, where this maximum is not reached. Implications for the existence and possible use of transformations which removes nonstationarity (or almost nonstationarity) of X(t) are mentioned.     

Carbon-13 nuclear magnetic resonance assignments and biosynthesis of ochratoxin A

The carbon-13 chemical shifts have been assigned to all the carbons in the isocoumarin portion of ochartoxin A. Incorporation of carbon-13 enriched acetate was used to confirm the biosynthesis of ochratoxin A.     

Resolving Inflammation: Synthesis,Configurational Assignment,and Biological Evaluations of RvD1n−3 DPA

New drugs that can resolve inflammation without immunosuppressive effects are at the medicinal chemistry frontier. Pro-resolving endogenously formed small molecules, that is, the resolvins, are excellent candidates displaying such bioactions. The first total synthesis of the specialized pro-resolving mediator RvD1_{n−3 DPA} has been achieved using the underutilized sp³–sp³ Negishi cross coupling reaction and an alkyne hydrosilylation–protodesilylation protocol. Biological evaluations revealed that this novel mediator displays low nanomolar pro-resolving properties and potently activates the human DRV1/GPR32 receptor. As such, this endogenous natural product is a lead compound for the development of novel immunoresolvents.     

Computational study of the dissolution of cellulose into single chains: the role of the solvent and agitation

Cellulose - We investigate the dissolution mechanism of cellulose using molecular dynamics simulations in both water and a mixture solvent consisting of water with Na $$^+$$ , OH $$^-$$...     

A note on symbolic and ordinary powers of homogeneous ideals

In this note we are interested in the graded modulesM _k=I^(k)/I^k and , whereI is a saturated ideal in the homogeneous coordinate ringS=K[x₀,…,x_n] of ℙⁿ,I ^(k) is the symbolic power and is the saturation of the ordinary power. Very little is known about these modules, and we provide a bound on their diameters, we compute the Hilbert functions and we study some characteristic submodules in the special case ofn+1 general points in ℙⁿ.

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Sunto In questa nota siamo interessati ai moduli graduatiM _k=I(k)/I^k e , doveI è un ideale saturato nell'anello delle coordinate omogeneeS:=K[x₀,…,x_n] di ℙⁿ,I ^(k) è la potenza simbolica e è la saturazione della potenza ordinaria. Poco è noto su questi moduli e qui viene fornito un limite superiore ai loro diametri. Ne calcoliamo inoltre le funzioni di Hilbert e studiamo alcuni sottomoduli caratteristici nel caso speciale din+1 punti in posizione generale, in ℙⁿ.

     

Double structures on rational space curves

There are very many non‐reduced schemes. In this paper, we consider two examples to back this statement: we give lists of double scheme structures on a twisted cubic, and we construct rank two bundles on projective 3‐space with prescribed Chern classes, from double structures on smooth rational curves. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Monomial multiple structures

In this paper we study Cohen–Macaulay monomial multiple structures (non-reduced schemes) on a linear subspace of codimension two in projective space. We show that these structures determine smooth points in their respective Hilbert schemes, with (smooth) neighbourhoods of two such points intersecting if their Hilbert functions are equal. We generalize a construction for multiple structures on points in the plane to this setting, giving a kind of product of monomial multiple structures. For points, this construction can be found in Nakajima’s book (Lectures on Hilbert schemes of points on surfaces, Univ Lecture Ser AMS, vol 18, 1999). The tools we use for studying multiple structures are developed in Vatne (Math Nachr 281(3):434–441, 2008; Comm Algebra 37(11):3861–3873, 2009) (see also Vatne in Towards a classification of multiple structures, PhD thesis, University of Bergen, 2001).     

Integral relations for the heat and mass transfer resistivities of the liquid–vapor interface

We derived integral relations for the heat and mass transfer resistivities of the liquid–vapor interface in a one-component system. These relations were obtained assuming the validity of the standard expression for the local entropy production rate as the product of the measurable heat flux times the gradient of the inverse temperature through the surface. The integral relations will be useful to interpret results from nonequilibrium molecular dynamics simulations. We verified in this paper that earlier results obtained using the nonequilibrium van der Waals square gradient model are reproduced. For this case, we calculated the Kapitza length along the coexistence curve.