Electrophilic As-functionalisation of σ-arsolido complexes.

The σ-arsolido complex [Mo(AsCMe)(CO)(η-CH)] is alkylated at arsenic by MeOTf to afford the pentamethylarsole complex [Mo(MeAsCMe)(CO)(η-CH)](OTf) while iodomethane affords a mixture of [MeAsCMe]I, [MoMe(CO)(η-CH)], [MoI(CO)(η-CH)] and the arsole complexes - and -[MoI(MeAsCMe)(CO)(η-CH)] and -[Mo{C(O)Me}(MeAsCMe)(CO)(η-CH)], The arsole ligand in [Mo(MeAsCMe)(CO)(η-CH)](OTf) is readily liberated by NaI in acetone to afford free MeAsCMe and [MoI(CO)(η-CH)]. In a similar manner, the reaction of [Mo(AsCPh)(CO)(η-CH)] with MeI affords MeAsCPh and [MoI(CO)(η-CH)], while [Mo{AsC(SiMe)-2-Me-3,4}(CO)(η-CH)] with MeOTf affords [Mo{MeAsC(SiMe)-2-Me-3,4}(CO)(η-CH)](OTf). The reaction of [Mo(AsCMe)(CO)(η-CH)] with activated alkynes (RCCR: R = CF, COMe) does not proceed [4 + 2] -addition but rather electrophilic attack at arsenic followed by metallacyclisation with incorporation of a carbonyl ligand in the spirocyclic complexes [Mo{As(CMe)CRCRCO}(CO)(η-CH)].

σ-Arsolido complexes.

The σ-stannyl complexes [M(SnBu)(CO)(η-CH)] ( = 3, M = Mo, W; = 2, M = Fe) serve as mild reagents for the installation of σ-arsolyl ligands in transmetallation reactions with As-chloro-arsoles ClAsCR (R = Me, Ph) to afford [M(σ-AsCR)(CO)(η-CH)]. The reaction of [Cr(SnBu)(CO)(η-CH)] with ClAsCPh most likely proceeds in a similar manner but is immediately followed by rapid formation of (AsCPh) and [Cr(CO)(η-CH)]. The reaction of [Mo(SnBu)(CO)(η-CH)] with ClAsC(SiMe)-2,5-Me-3,4 is accompanied by monodesilylation to afford [Mo{σ-AsC(SiMe)-2-Me-3,4}(CO)(η-CH)].

Poly(imidazolyliden-yl)borato Complexes of Tungsten: Mapping Steric vs. Electronic Features of Coordinating Ligands.

A convenient synthesis of [HB(HImMe)](PF) (ImMe = -methylimidazolyl) is decribed. This salt serves in situ as a precursor to the tris(imidazolylidenyl)borate Li[HB(ImMe)] pro-ligand upon deprotonation with BuLi. Reaction with [W(≡CCHMe-4)(CO)(pic)(Br)] (pic = 4-picoline) affords the carbyne complex [W(≡CCHMe-4)(CO){HB(ImMe)}].

Free and coordinated biarsolyls.

A trace side product from the reaction of [Mo(AsCMe)(CO)(η-CH)] with [Mn(THF)(CO)(η-CHMe)] was identified as the biarsolyl complex [Mn{μ-(AsCMe)}(CO)(CHMe)] on the basis of a strategic synthesis from [Mn(THF)(CO)(η-CHMe)] and the pre-formed and structurally characterised biarsolyl (AsCMe). Crystallographic and computational data for this first example of a biarsolyl complex and free biarsolyls are discussed in the context of those for free biarsolyls.

Bridging arsolido complexes.

The σ-arsolyl complex [Mo(AsCMe)(CO)(η-CH)] serves as a metallo-ligand for the strategic construction of μ-arsolido bridged heterobimetallic complexes [MoCr(μ-AsCMe)(CO)(η-CH)], [MoMn(μ-AsCMe)(CO)(η-CH)(η-CHMe)], [MoAu(μ-AsCMe)(CF)(CO)(η-CH)] and [MoFe(μ-AsCMe)(CO)(η-CH)]PF reactions with [Cr(THF)(CO)], [Au(CF)(THT)], [Mn(THF)(CO)(η-CHMe)] and [Fe(THF)(CO)(η-CH)]PF, respectively. The reaction of [Mo(AsCMe)(CO)(η-CH)] with [Co(μ-CH)(CO)] affords the tetrametallic species [MoCo(AsCMe)(μ-CH)(CO)(η-CH)]. Crystallographic and computational data for all products are discussed.

Evaluation of the orally bioavailable 4-phenylbutyrate-tethered trichostatin A analogue AR42 in models of spinal muscular atrophy.

Proximal spinal muscular atrophy (SMA) is a leading genetic cause for infant death in the world and results from the selective loss of motor neurons in the spinal cord. SMA is a consequence of low levels of SMN protein and small molecules that can increase SMN expression are of considerable interest as potential therapeutics. Previous studies have shown that both 4-phenylbutyrate (4PBA) and trichostatin A (TSA) increase SMN expression in dermal fibroblasts derived from SMA patients.

A transcriptional constraint mechanism limits the homeostatic response to activity deprivation in mammalian neocortex.

Healthy neuronal networks rely on homeostatic plasticity to maintain stable firing rates despite changing synaptic drive. These mechanisms, however, can themselves be destabilizing if activated inappropriately or excessively. For example, prolonged activity deprivation can lead to rebound hyperactivity and seizures.

Osteomyelitis associated with infection in a young cat.

Case Summary: A 1-year-old male intact domestic shorthair cat was evaluated for acute onset non-weightbearing left forelimb lameness and generalized peripheral lymphadenopathy. CT identified a monostotic aggressive bone lesion with an incomplete fracture of the left radial metaphysis. Bone aspirates yielded osteoblasts with minimal nuclear atypia.

Arsolyl-supported intermetallic dative bonding.

The first examples of late transition metal η-arsolyls (L = CO, P(OMe); R = Ph, Me, Et, SiMe; R' = Ph, H, Me, Et, Me) serve as ditopic donors to extraneous metal centres (M = Pt, Au, Hg) through both conventional As → M and polar-covalent (dative) Co → M interactions.

Heterocyclic arsinocarbynes via tandem transmetallation.

Gold(i)-catalysed tandem transmetallation (Sn→Au→As) of the stannylcarbyne [W(≡CSnBu)(CO)(Tp*)] (Tp* = hydrotris-(dimethylpyrazolyl)borate) with haloarsines gives direct access to a range of novel arsinocarbyne complexes, LM≡CAsR, including unusual heterocyclic phenarsazininyl and arsolyl examples.

Lacking Advanced Degrees are not a Barrier to Entry into Academic Surgery Leadership.

Background: Undergraduate and graduate medical education offerings continue to create opportunities for medical students to pursue MD+ degree education. These educational endeavors provide formal education in fields related to surgery, which gives trainees and surgeons diverse perspectives on surgical care. This study sought to assess current prevalence of additional advanced degrees among leaders in academic surgery to assess the relationship between dual degree attainment and holding various leadership positions within surgical departments.

Thyroid storm in a dog secondary to thyroid carcinoma.

Objective: To describe the clinical presentation, clinical course, and management of a dog with thyroid storm (TS) secondary to a functional thyroid carcinoma.

Case Summary: A 12-year-old neutered female Golden Retriever was evaluated for severe weight loss, hyperthermia, and tachycardia. The dog had a ventral neck mass and markedly increased thyroxine concentration.

Effects of clonidine on progressive ratio schedule performance in Fmr1 knockout mice.

Rationale: Fragile X syndrome (FXS), the most prevalent genetic form of intellectual disability, is characterized by intellectual impairment, impaired sociability, aggression, self-injury, hyperactivity, and attention deficits. A consequence of the hyperactivity and attention deficits is that individuals with FXS are frequently diagnosed with attention deficit hyperactivity disorder (ADHD) and treated with medications approved for ADHD (e.g.

Investigation of the effects of storage with preservatives at room temperature or refrigeration without preservatives on urinalysis results for samples from healthy dogs.

Objective: To compare urinalysis results for canine urine samples stored in preservative-containing tubes at room temperature (20°C to 25°C [68°F to 77°F]) or refrigerated at 4°C (39.2°F) in plain glass tubes with results for the same samples immediately after collection.

Samples: Urine samples from 20 healthy dogs.

Analysis of retention of gadolinium by brain, bone, and blood following linear gadolinium-based contrast agent administration in rats with experimental sepsis.

Purpose: It is important to identify populations that may be vulnerable to the brain deposition of gadolinium (Gd) from MRI contrast agents. At intervals from 24 hours to 6 weeks following injection of a linear Gd contrast agent, the brain, blood and bone content of Gd were compared between control rats and those with experimental endotoxin-induced sepsis that results in neuroinflammation and blood-brain barrier disruption.

Methods: Male rats were injected intraperitoneally with 10 mg/kg lipopolysaccharide.

Lipopolysaccharide exposure in a rat sepsis model results in hippocampal amyloid-β plaque and phosphorylated tau deposition and corresponding behavioral deficits.

Sepsis is a severe systemic inflammatory response to infection associated with acute and chronic neurocognitive consequences, including an increased risk of later-life dementia. In a lipopolysaccharide-induced rat sepsis model, we have demonstrated neuroinflammation, cortical amyloid-beta plaque deposition, and increased whole brain levels of phosphorylated tau. Hippocampal abnormalities, particularly those of the dentate gyrus, are seen in Alzheimer's disease and age-related memory loss.

Lipopolysaccharide endotoxemia induces amyloid-β and p-tau formation in the rat brain.

Amyloid beta (Aβ) plaques are not specific to Alzheimer's disease and occur with aging and neurodegenerative disorders. Soluble brain Aβ may be neuroprotective and increases in response to neuroinflammation. Sepsis is associated with neurocognitive compromise.

The effects of C5-substituted 2,4-diaminoquinazolines on selected transcript expression in spinal muscular atrophy cells.

C5-substituted 2,4-diaminoquinazolines (2,4-DAQs) ameliorate disease severity in SMA mice. It is uncertain, however, that these compounds increase SMN protein levels in vivo even though they were identified as activators of the SMN2 promoter. These compounds also regulate the expression of other transcripts in neuroblastoma cells.

Treatment of meloxicam overdose in a dog via therapeutic plasma exchange.

Objective: To describe the treatment of a meloxicam overdose in a dog with therapeutic plasma exchange (TPE).

Case Summary: A 6-month-old female Bulldog, presented for routine laparoscopic ovariectomy. Postoperatively the dog received an accidental overdose of meloxicam (1 mg/kg IV [intravenously]).

Treatment of ibuprofen intoxication in a dog via therapeutic plasma exchange.

Objective: To describe the treatment of ibuprofen intoxication with therapeutic plasma exchange in a dog (TPE).

Summary: A 13-year-old male neutered mixed breed dog presented after ingesting approximately 200 mg/kg of ibuprofen. Treatment consisted of supportive medical therapy with IV fluids, gastrointestinal protectants, antiemetics and prostaglandin analogs, and TPE.