ABSTRACT
Large discrete supertetrahedral clusters of metal chalcogenides are rare due to the difficulty of crystallizing solids in which the negative charge of the cluster is balanced by the positive charges of the countercations. Here, we describe a discrete ligand-free T3 supertetrahedral cluster, [Ga10S16(SH)4]6-, which was successfully synthesized in the presence of the superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) using the neutral surfactant polyethyleneglycol (PEG)-400 as the reaction solvent. Protonated DBUH+ cations are incorporated into the crystal structure of the product, which can be formulated as [C9H17N2]6[Ga10S16(SH)4]. This compound, which represents the first example of a discrete ligand-free T3 cluster of gallium sulfide, was fully characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis, and ultraviolet-visible diffuse reflectance. The results presented here indicate that the use of surfactants as solvents offers potential for the preparation of new compounds containing supertetrahedral clusters.
ABSTRACT
Previous research has demonstrated that children diagnosed with autism spectrum disorder show an abnormal acceleration of head growth during the first year of life. This study attempts to replicate these findings and to determine whether overgrowth is associated with clinical outcome. Measurements of head circumference, body length, and body weight taken during the first 2 years of life were obtained from a sample of 35 children diagnosed with autism spectrum disorder and compared to both national normative data (Centers for Disease Control and Prevention) and a control group of 37 healthy infants. Results demonstrated that compared to national averages, infants who were later diagnosed with autism spectrum disorder had a significantly smaller head circumference at birth to 2 weeks and a significantly larger head circumference by 10 to 14 months. Children with autism spectrum disorder were also significantly longer and heavier beginning at 1 to 2 months. However, when overall length and weight were controlled, head circumference was not bigger in the autistic spectrum disorder group compared to local controls. Correlations between head circumference and clinical outcome were significant for 5 of the 30 clinical variables that were run, suggesting that there appears to be no simple or straightforward relationship between head circumference and clinical outcome. Smaller head circumference at birth to 2 weeks was associated with a greater number of symptoms related to social impairment and a greater total number of autism spectrum disorder symptoms based on the Diagnostic and Statistical Manual of Mental Disorders , Fourth Edition criteria. Larger head circumference at 15 to 25 months was also associated with a greater number of symptoms of social impairment. In addition, greater head circumference change during the first 2 years was associated with poorer performance on the visual reception subtest of the Mullen Scales of Early Learning and a smaller number of stereotyped and repetitive behaviors and interests based on the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition criteria. These findings support previous findings of accelerated brain growth during the first year of life in autism spectrum disorder and question whether growth factors might contribute to both accelerated brain growth and overall body growth.