The pentafluorosulfanyl (SF5) group is more electronegative, lipophilic and sterically bulky relative to the well‐explored trifluoromethyl (CF3) group. As such, the SF5 group could offer access to pharmaceuticals, agrochemicals and optoelectronic materials with novel properties. Here, the first synthesis of phthalocyanines (Pcs), a class of compounds used as dyes and with potential as photodynamic therapeutics, with a SF5 group directly attached on their peripheral positions is disclosed. The key for this work is the preparation of a series of SF5‐containing phthalonitriles, which was beautifully regio‐controlled by a stepwise cyanation via ortho‐lithiation/iodination from commercially available pentafluorosulfanyl arenes. The macrocyclization of the SF5‐containing phthalonitriles to SF5‐substituted Pcs required harsh conditions with the exception of the synthesis of β‐SF5‐substituted Pc. The regiospecificity of the newly developed SF5‐substituted Pcs observed by UV/Vis spectra and fluorescence quantum yields depend on the peripheral positon of the SF5 group.
Rate of respiration is a fundamental vital sign. Accuracy and precision of respiratory rate measurements with contact-free load cell sensors under the bed legs were assessed by breath-by-breath comparison with the pneumotachography technique during two different dynamic breathing tasks in 16 awake human adults resting on the bed. The subject voluntarily increased and decreased the respiratory rate between 4 and 16 breaths/min ( n = 8) and 10 and 40 breaths/min ( n = 8) at every 2 breaths in 6 different lying postures such as supine, left lateral, right lateral, and 30, 45, and 60° sitting postures. Reciprocal phase changes of the upper and lower load cell signals accorded with the respiratory phases indicating respiratory-related shifts of the centroid along the long axis of the bed. Bland-Altman analyses revealed 0.66 and 1.59 breaths/min standard deviation differences between the techniques (limits of agreement: −1.22 to 1.36 and −2.96 to 3.30) and 0.07 and 0.17 breaths/min fixed bias differences (accuracy) (confidence interval: 0.04 to 0.10 and 0.12 to 0.22) for the mean respiratory rates of 10.5 ± 3.7 and 24.6 ± 8.9 breaths/min, respectively, regardless of the body postures on the bed. Proportional underestimation by this technique was evident for respiratory rates >40 breaths/min. Sample breath increase up to 10 breaths improved the precision from 1.59 to 0.26 breaths/min. Abnormally faster and slower respirations were accurately detected. We conclude that contact-free unconstraint respiratory rate measurements with load cells under the bed legs are accurate and may serve as a new clinical and investigational tool. NEW & NOTEWORTHY Four load cells placed under the bed legs successfully captured a centroid shift during respiration in human subjects lying on a bed. Breath-by-breath comparison of the breaths covering a wide respiratory rate range by pneumotachography confirmed reliability of the contact-free unconstraint respiratory rate measurements by small standard deviations and biases regardless of body postures. Abnormally faster and slower respirations were accurately detected. This technique should be an asset as a new clinical and investigational tool.
Metal β-tetrakis(tert-butyl)phthalocyanines are the most commonly used phthalocyanines due to their high solubility, stability, and accessibility. They are commonly used as a mixture of four regioisomers, which arise due to the tert-butyl substituent on the β-position, and to the best of our knowledge, their regioselective synthesis has yet to be reported. Herein, the C4h-selective synthesis of β-tetrakis(tert-butyl)metallophthalocyanines is disclosed. Using tetramerization of α-trialkylsilyl phthalonitriles with metal salts following acid-mediated desilylation, the desired metallophthalocyanines were obtained in good yields. Upon investigation of regioisomer-free zinc β-tetrakis(tert-butyl)phthalocyanine using spectroscopy, the C4h single isomer described here was found to be distinct in the solid state to zinc β-tetrakis(tert-butyl)phthalocyanine obtained by a conventional method.
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