Ocular and cervical vestibular-evoked myogenic potentials (VEMPs) evaluate the function of otolithic pathways in central as well as peripheral vestibular disorders. This study aimed to determine the associations and dissociations of otolithic dysfunction in lateral medullary infarction (LMI), the most well-known disorder of central vestibulopathy. At the Dizziness Clinic of a referral-based University Hospital, 45 patients with isolated LMI (28 men, mean age = 55.6 ± 12.5) had evaluation of the ocular tilt reaction (OTR), tilt of the subjective visual vertical (SVV), and ocular and cervical VEMPs from Janurary 2011 to August 2015 during the acute phase, 1-11 days from the symptom onset (median = 2 days). Almost all (42/45, 93 %) patients showed at least one component of the OTR or SVV tilt that was invariably ipsiversive. In contrast, oVEMPs were abnormal only in 12 (27 %) and cVEMPs in 13 (29 %) patients. Only three patients showed abnormal results in all the tests of the OTR, SVV tilt, and ocular and cervical VEMPs. Abnormal oVEMPs were more common in patients with the OTR than those without (38 vs 6 %, Pearson X test, p = 0.021). In contrast, abnormality of cVEMPs showed no correlation with the presence of OTR (28 vs 31 %, Pearson X test, p = 0.795). In patients with LMI, ipsiversive OTR is invariable, but abnormalities of oVEMPs and cVEMPs were much less common and mostly dissociated even in the patients with abnormal results. This discrepancy in otolithic dysfunction suggests different anatomical substrates and/or dissimilar reciprocal modulation for processing of each otolithic signal in central vestibular structures located in the dorsolateral medulla.
Since the alkynyl moiety is one of the most versatile synthons for many other functional groups, 1,5-diynes (Wurtztype products of propargyl halides) would be valuable synthetic building blocks for the synthesis of complex functional molecules. However, despite the high and similar reactivity of propargyl radicals compared to allyl and benzyl derivative radicals, a photoredox Wurtz-type reaction of propargyl halides has not yet been developed. In this study, we developed the visible-light-induced selective homocoupling of propargyl bromides to form 1,5-diynes. Electrochemical and photophysical experiments showed that the key propargyl radical generation involves a reductive quenching cycle of the photoexcited [Ir(III)]* photocatalyst in the presence of N,N-dicyclohexylmethylamine. The product 1,5-diyne underwent one-step conversion to the functionalized indole derivative via Rhcatalyzed coupling with N-phenylacetamide. These results indicated the high utility of the developed homocoupling method.
Fluoroalkylation is a crucial synthetic process that enables the modification of molecules with fluoroalkyl groups, which can enhance the properties of compounds and have potential applications in medicine and materials science. The utilization of visible light‐induced, metal‐free methods is of particular importance as it provides an environmentally friendly alternative to traditional methods and eliminates the potential risks associated with metal‐catalyst toxicity. This Account describes our studies on visible light‐induced, metal‐free fluoroalkylation processes, which include the use of organic photocatalysts or EDA complexes. We have utilized organophotocatalysts such as Nile red, tri(9‐anthryl)borane, and an indole‐based tetracyclic complex, as well as catalyst‐free EDA chemistry through photoactive halogen bond formation or an unconventional transient ternary complex formation with nucleophilic fluoroalkyl source. A variety of π‐systems including arenes/heteroarenes, alkenes, and alkynes have been successfully fluoroalkylated under the developed reaction conditions.
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