Exploration of Bis(imino)pyridine Iron Alkoxides for the Synthesis of Novel Degradable Polymers

Thesis advisor: Jeffery A. ByersThis dissertation discusses the development of a family of iron complexes and their role in the synthesis of degradable polymers. Chapter one will introduce the different areas of redox-switchable polymerization. In chapter two the synthesis of block copolymers containing a polyester and polyether block is presented. The application redox-switchable polymerization to form a copolymer with two fundamentally distinct backbone functionalities and their characterization is discussed. In chapter three the synthesis of a degradable cross-linked polymer through a novel redox-triggered cross linking event is summarized. In chapter four, a detailed mechanistic study of iron-complex catalyzed epoxide polymerization is examined and a unique mechanistic scheme is proposed. Lastly, in chapter five the synthesis and characterization of a formally iron(I) complex is presented. This complex shows remarkable catalytic activity towards ring-opening polymerization.Thesis (PhD) — Boston College, 2018.Submitted to: Boston College. Graduate School of Arts and Sciences.Discipline: Chemistry

Capgras-like syndrome in a patient with an acute urinary tract infection.

Delusional misidentification syndromes are a group of delusional phenomena in which patients misidentify familiar persons, objects, or themselves, believing that they have been replaced or transformed. In 25%-40% of cases, misidentification syndromes have been reported in association with organic illness. We report an acute episode of Capgras-like delusion lasting 8 days, focused on the idea that people were robots with human bodies, in association with an acute urinary infection. To our knowledge, this is the first case report associating urinary tract infection with Capgras-like syndrome. Awareness of the prevalence of delusional misidentification syndromes associated with acute medical illness should promote diligence on the part of clinicians in recognizing this disorder

P03-36 Bradykinesia and mental slowness in patients with obsessive-compulsive disorder

Background:Clinical and experimental findings suggest that Obsessive-Compulsive Disorder (OCD) is due to an abnormality of the cortico-striato-thalamo-cortical circuit. Bradykinesia and mental slowness can be present in patients with basal ganglia disorders affecting the cortico-striato-thalamo-cortical circuit. Aim of this study is to investigate whether bradykinesia and mental slowness are present in patients with OCD.Methods:Participants comprised 19 non-depressed anti-psychotic free patients with OCD.Bradykinesia was assessed with the motor section of the Unified Parkinson's Disease Rating Scale (UPDRS). Mental slowness was investigated with the WAIS-R and the Y-BOCS. Psychiatric evaluation was performed with: SCID-I, Y-BOCS, HAMD, HAM-A, and MMPI. Cognitive functions were assessed with the WAIS-R.Results:Bradykinesia and mental slowness were present respectively in the 39% and 89% of the patients. Bradykinesia was positively correlated to Y-BOCS mental slowness score (rho=0.48, p< 0.05), and inversely related to the WAIS-R Performance IQ score (rho=-0.65, p< 0.01). Patients with bradykinesia scored significantly lower in the Similarities and Digit symbol coding WAIS-R subscales as compared to non-bradykinetic patients. in our sample pathological doubt was not associated with IQ measures nor with bradykinesia. Twelve out of 19 patients (63%) showed impairments in the nonverbal function scores.Conclusions:The novel findings of this study is that bradykinesia can be present in patients with OCD, and it is correlated with mental slowness and nonverbal performance impairment. These preliminary data support the notion that dysfunction of basal ganglia is possibly present in OCD patients

Theory of mind profile and cerebellar alterations in remitted bipolar disorder 1 and 2: a comparison study

The literature on social cognition abilities in bipolar disorder (BD) is controversial about the occurrence of theory of mind (ToM) alterations. In addition to other cerebral structures, such as the frontal and limbic areas, the processing of socially relevant stimuli has also been attributed to the cerebellum, which has been demonstrated to be involved in the abovementioned disorder. Nevertheless, the cerebellar contribution to ToM deficits in bipolar patients needs to be elucidated further. To this aim, two tests assessing different components of ToM were used to evaluate the ability to appreciate affective and mental states of others in 17 individuals with a diagnosis of BD type 1 (BD1) and 13 with BD type 2 (BD2), both in the euthymic phase, compared to healthy matched controls. Cerebellar grey matter (GM) volumes were extracted and compared between BD1 and controls and BD2 and controls by using voxel-based morphometry. The results showed that BD1 patients were compromised in the cognitive and advanced components of ToM, while the BD2 ToM profile resulted in a more widespread compromise, also involving affective and automatic components. Both overlapping and differing areas of cerebellar GM reduction were found. The two groups of patients presented a pattern of GM reduction in cerebellar portions that are known to be involved in the affective and social domains, such as the vermis and Crus I and Crus II. Interestingly, in both BD1 and BD2, positive correlations were detected between lower ToM scores and decreased volumes in the cerebellum. Overall, BD2 patients showed a more compromised ToM profile and greater cerebellar impairment than BD1 patients. The different pattern of structural abnormalities may account for the different ToM performances evidenced, thus leading to divergent profiles between BD1 and BD2

Comparison of cerebellar grey matter alterations in bipolar and cerebellar patients: evidence from Voxel-based analysis

The aim of this study was to compare the patterns of cerebellar alterations associated with bipolar disease with those induced by the presence of cerebellar neurodegenerative pathologies to clarify the potential cerebellar contribution to bipolar affective disturbance. Twenty-nine patients affected by bipolar disorder, 32 subjects affected by cerebellar neurodegenerative pathologies, and 37 age-matched healthy subjects underwent a 3T MRI protocol. A voxel-based morphometry analysis was used to show similarities and differences in cerebellar grey matter (GM) loss between the groups. We found a pattern of GM cerebellar alterations in both bipolar and cerebellar groups that involved the anterior and posterior cerebellar regions (p = 0.05). The direct comparison between bipolar and cerebellar patients demonstrated a significant difference in GM loss in cerebellar neurodegenerative patients in the bilateral anterior and posterior motor cerebellar regions, such as lobules I-IV, V, VI, VIIIa, VIIIb, IX, VIIb and vermis VI, while a pattern of overlapping GM loss was evident in right lobule V, right crus I and bilateral crus II. Our findings showed, for the first time, common and different alteration patterns of specific cerebellar lobules in bipolar and neurodegenerative cerebellar patients, which allows us to hypothesize a cerebellar role in cognitive and mood dysregulation symptoms that characterize bipolar disorde

Ultrasound-guided diagnostic breast biopsy methodology: retrospective comparison of the 8-gauge vacuum-assisted biopsy approach versus the spring-loaded 14-gauge core biopsy approach

<p>Abstract</p> <p>Background</p> <p>Ultrasound-guided diagnostic breast biopsy technology represents the current standard of care for the evaluation of indeterminate and suspicious lesions seen on diagnostic breast ultrasound. Yet, there remains much debate as to which particular method of ultrasound-guided diagnostic breast biopsy provides the most accurate and optimal diagnostic information. The aim of the current study was to compare and contrast the 8-gauge vacuum-assisted biopsy approach and the spring-loaded 14-gauge core biopsy approach.</p> <p>Methods</p> <p>A retrospective analysis was done of all ultrasound-guided diagnostic breast biopsy procedures performed by either the 8-gauge vacuum-assisted biopsy approach or the spring-loaded 14-gauge core biopsy approach by a single surgeon from July 2001 through June 2009.</p> <p>Results</p> <p>Among 1443 ultrasound-guided diagnostic breast biopsy procedures performed, 724 (50.2%) were by the 8-gauge vacuum-assisted biopsy technique and 719 (49.8%) were by the spring-loaded 14-gauge core biopsy technique. The total number of false negative cases (i.e., benign findings instead of invasive breast carcinoma) was significantly greater (P = 0.008) in the spring-loaded 14-gauge core biopsy group (8/681, 1.2%) as compared to in the 8-gauge vacuum-assisted biopsy group (0/652, 0%), with an overall false negative rate of 2.1% (8/386) for the spring-loaded 14-gauge core biopsy group as compared to 0% (0/148) for the 8-gauge vacuum-assisted biopsy group. Significantly more (P < 0.001) patients in the spring-loaded 14-gauge core biopsy group (81/719, 11.3%) than in the 8-gauge vacuum-assisted biopsy group (18/724, 2.5%) were recommended for further diagnostic surgical removal of additional tissue from the same anatomical site of the affected breast in an immediate fashion for indeterminate/inconclusive findings seen on the original ultrasound-guided diagnostic breast biopsy procedure. Significantly more (P < 0.001) patients in the spring-loaded 14-gauge core biopsy group (54/719, 7.5%) than in the 8-gauge vacuum-assisted biopsy group (9/724, 1.2%) personally requested further diagnostic surgical removal of additional tissue from the same anatomical site of the affected breast in an immediate fashion for a benign finding seen on the original ultrasound-guided diagnostic breast biopsy procedure.</p> <p>Conclusions</p> <p>In appropriately selected cases, the 8-gauge vacuum-assisted biopsy approach appears to be advantageous to the spring-loaded 14-gauge core biopsy approach for providing the most accurate and optimal diagnostic information.</p

Redefining the MED13L syndrome

Congenital cardiac and neurodevelopmental deficits have been recently linked to the mediator complex subunit 13-like protein MED13L, a subunit of the CDK8-associated mediator complex that functions in transcriptional regulation through DNA-binding transcription factors and RNA polymerase II. Heterozygous MED13L variants cause transposition of the great arteries and intellectual disability (ID). Here, we report eight patients with predominantly novel MED13L variants who lack such complex congenital heart malformations. Rather, they depict a syndromic form of ID characterized by facial dysmorphism, ID, speech impairment, motor developmental delay with muscular hypotonia and behavioral difficulties. We thereby define a novel syndrome and significantly broaden the clinical spectrum associated with MED13L variants. A prominent feature of the MED13L neurocognitive presentation is profound language impairment, often in combination with articulatory deficits