Reactivity of acyclic (pentadienyl)iron(1+) cations: Synthetic studies directed toward the frondosins

A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2′,5′-dimethoxyphenyl)pentadienyl]Fe(CO)3+ cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)3. Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)3 along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl2, affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane

A Study of the Reset Cycle of a Half-Wave Self-Saturable Magnetic Amplifier

It was the purpose of this study (1) to investigate the reset cycle of a half-wave self-saturable magnetic amplifier by graphical analysis of the irregular voltage functions appearing across the gate winding during reset; and (2) to determine if possible from this analysis a more satisfactory design method than those now available. Conditions of constant current reset were employed and the core material used had a nearly rectangular hysteresis loop. Resistive loads only are considered

Reactivity of Acyclic (pentadienyl)iron(1+) Cations with Phosphonate Stabilized Nucleophiles: Application to the Synthesis of Oxygenated Metabolites of Carvone

The addition of phosphonate stabilized carbon nucleophiles to acyclic (pentadienyl)iron(1+) cations proceeds predominantly at an internal carbon to afford (pentenediyl)iron complexes. Those complexes bearing an electron withdrawing group at the σ-bound carbon (i.e., 13/14) are stable and isolable, while complexes which do not contain an electron withdrawing group at the σ-bound carbon undergo CO insertion, reductive elimination and conjugation of the double bond to afford cyclohexenone products (21/22). Deprotonation of the phosphonate 13/14 or 21 and reaction with paraformaldehyde affords the olefinated products. This methodology was utilized to prepare oxygenated carvone metabolites (±)-25 and (±)-26

Magnetic helicity in magnetohydrodynamic turbulence with a mean magnetic field

A computational investigation of magnetic helicity of the fluctuatingmagnetic fieldHm in ideal and freely decaying three‐dimensional (3‐D) magnetohydrodynamics (MHD) in the presence of a uniform mean magnetic field is performed. It is shown that for ideal 3‐D MHDHm, which is a rugged invariant in the absence of a mean magnetic field [Frisch et al., J. Fluid Mech. 77, 796 (1975)], decays from its initial value and proceeds to oscillate about zero. The decay of Hm is shown to result from the presence of a new ‘‘generalized’’ helicity invariant, which includes contributions from the uniform magnetic field. The loss of invariance of Hm will diminish the effects of inverse transfer of Hm on freely decaying turbulence. This is demonstrated in a discussion of the selective decay relaxation process

Minimally Invasive Ablative Therapies for Definitive Treatment of Localized Prostate Cancer in the Primary Setting

Traditionally, the patient with a new diagnosis of localized prostate cancer faces either radical therapy, in the form of surgery or radiation, or active surveillance. A growing subset of these men may not be willing to accept the psychological burden of active surveillance nor the side effects of extirpative or radiation therapy. Local ablative therapies including cryotherapy, high-intensity focused ultrasound, and vascular-targeted photodynamic therapy have emerged as a means for minimally invasive definitive treatment. These treatments are well tolerated with decreased morbidity in association with improvements in technology; however, long-term oncologic efficacy remains to be determined

Adiponectin Deficiency Impairs Maternal Metabolic Adaptation to Pregnancy in Mice.

Hypoadiponectinemia has been widely observed in patients with gestational diabetes mellitus (GDM). To investigate the causal role of hypoadiponectinemia in GDM, adiponectin gene knockout (Adipoq-/- ) and wild-type (WT) mice were crossed to produce pregnant mouse models with or without adiponectin deficiency. Adenoviral vector-mediated in vivo transduction was used to reconstitute adiponectin during late pregnancy. Results showed that Adipoq-/- dams developed glucose intolerance and hyperlipidemia in late pregnancy. Increased fetal body weight was detected in Adipoq-/- dams. Adiponectin reconstitution abolished these metabolic defects in Adipoq-/- dams. Hepatic glucose and triglyceride production rates of Adipoq-/- dams were significantly higher than those of WT dams. Robustly enhanced lipolysis was found in gonadal fat of Adipoq-/- dams. Interestingly, similar levels of insulin-induced glucose disposal and insulin signaling in metabolically active tissues in Adipoq-/- and WT dams indicated that maternal adiponectin deficiency does not reduce insulin sensitivity. However, remarkably decreased serum insulin concentrations were observed in Adipoq-/- dams. Furthermore, β-cell mass, but not glucose-stimulated insulin release, in Adipoq-/- dams was significantly reduced compared with WT dams. Together, these results demonstrate that adiponectin plays an important role in controlling maternal metabolic adaptation to pregnancy