An unexpected P-cluster like intermediate en route to the nitrogenase FeMo-co

The nitrogenase MoFe protein contains two different FeS centers, the P-cluster and the iron–molybdenum cofactor (FeMo-co). The former is a [Fe₈S₇] center responsible for conveying electrons to the latter, a [MoFe₇S₉C-(R)-homocitrate] species, where N₂ reduction takes place. NifB is arguably the key enzyme in FeMo-co assembly as it catalyzes the fusion of two [Fe₄S₄] clusters and the insertion of carbide and sulfide ions to build NifB-co, a [Fe₈S₉C] precursor to FeMo-co. Recently, two crystal structures of NifB proteins were reported, one containing two out of three [Fe₄S₄] clusters coordinated by the protein which is likely to correspond to an early stage of the reaction mechanism. The other one was fully complemented with the three [Fe₄S₄] clusters (RS, K1 and K2), but was obtained at lower resolution and a satisfactory model was not obtained. Here we report improved processing of this crystallographic data. At odds with what was previously reported, this structure contains a unique [Fe₈S₈] cluster, likely to be a NifB-co precursor resulting from the fusion of K1- and K2-clusters. Strikingly, this new [Fe₈S₈] cluster has both a structure and coordination sphere geometry reminiscent of the fully reduced P-cluster (P^N-state) with an additional μ²-bridging sulfide ion pointing toward the RS cluster. Comparison of available NifB structures further unveils the plasticity of this protein and suggests how ligand reorganization would accommodate cluster loading and fusion in the time-course of NifB-co synthesis.

The K-cluster of NifB as a key intermediate in the synthesis of the nitrogenase active site supports [Fe₄S₄] cluster fusion occurs before carbide and sulfide insertion and displays ligand spatial arrangement reminiscent to that of the P-cluster.     

High pressure [4+2] and [2+2+2] reactions between cycloheptatriene and methyl propiolate

Under high pressure conditions, cycloheptatriene reacts with methyl propiolate to afford mono-, bis- and trisadducts all retaining, the norcaradiene structure. The four new compounds are formed via [4+21] and [2+2+2] cycloadditions. The latter are examples for the high pressure extension of the scope of homo-Diels-Alder reactions.     

Reactions CO/H2 en phase liquide. Synthese de precurseurs de l'ethanol par homologation du methanol.: I. Influences de la temperature et de la pression

The CO/H₂ homologation of methanol to acetaldehyde and subsequently to its dimethyl acetal in the presence of cobalt acetate promoted by iodine was examined under various conditions. Temperature and pressure were found as critical parameters. High pressures (140 MPa) and low temperatures (160–170°C) give optimal yields and selectivity to acetaldehyde. According to pressure, temperature, contact time, gas ratio and ligand/catalyst ratio, the reaction is oriented towards acetaldehyde, its dimethyl acetal or methyl acetate.     

High pressure catalyzed addition of lactams to siloxydienes

Abstract

Lactams add to Danishefsky's diene 1 yielding N-alkenyl substituted lactams 3-5. The reaction occurs only under pressure (100-300MPa) and, preferentially, in the presence of a mild Lewis acid catalyst such as bismuth chloride or ytterbium triflate. The reactions are fully regioselective and afford linear trans multifunctional 1:1 adducts.     

Lithium perchlorate-diethyl ether as a medium in organic addition reactions. An ersatz to high pressure methodology?

Abstract

The effect of lithium perchlorate-diethyl ether solutions (LPDE) is compared to the pressure effect in several addition reactions. The results cannot be accounted for either internal pressure, or electrostriction, but point to a Lewis-acid catalytic effect, in agreement with recent propositions. It is also concluded that the high pressure methodology is generally superior to the use of LPDE to improve yields.     

High pressure (4+2) cyclodimerisation of 2,3-dimethyl 1,3-butadiene possible competition between concerted and stepwise mechanisms

The study of the pressure dependence of the rate constant in the (4+2) cyclodimerisation of 2,3-dimethyl 1,3-butadiene reveals a possible competition between concerted and stepwise mechanisms.     

0.35 μm CMOS T/R Switch for 2.4 GHz Short Range Wireless Applications

This paper describes the design and implementation of a transmit/receive switch for 2.4 GHz ISM band applications. The T/R switch is implemented in a 0.35 m bulk CMOS process and it occupies 150 m · 170 m of die area. A parasitic MOSFET model including bulk resistance is used to optimize the physical dimensions of the transistors with regard to insertion loss and isolation. The measured insertion loss is 1.3 dB without port matching. Simulations using measured s-parameters indicate that an insertion loss of 0.8 dB can be obtained with a conjugate match. The measured isolation is 42 dB and the maximum transmit power is 16 dBm.     

A comprehensive note on: An inventory model under two levels of trade credit and limited storage space derived without derivatives

In 2006, Huang proposed an inventory model with two warehouses when the supplier offers the retailer a permissible delay of M periods, and the retailer also provides its customers a permissible delay of N periods. He then solved it without derivatives. In this note, we extend his model to complement the shortcomings of his model. In contrast to the complicated and tedious quadratic–algebraic method suggested by Huang, we propose a simple arithmetic–geometric method to solve the inventory problem. Finally, we run computer programs for several numerical examples to illustrate the proposed model and obtain some managerial implications.     

UTRA/FDD RF Transceiver Requirements

Unified RF requirements are derived for an UMTS Terrestrial RadioAccess/Frequency Division Duplex (UTRA/FDD) compliant mobile transceiver. Aset of transceiver requirements are proposed with consideration to systemissues including duplex aspects. From these design-compatible requirements areproposed for each functional block in the transceiver.