One size does not fit all: Impact of hand size on ease of use of instruments for minimally invasive surgery.

BACKGROUND: Consideration of ergonomic factors is important for the practice of safe and efficient minimally invasive surgery (MIS). Surgeons with smaller glove sizes have previously been reported to have increased difficulties with some minimally invasive instruments. We aim to investigate hand anthropometrics and their relationship to surgeon comfort when using MIS instruments. METHODS: Male and female surgeons from two centres were surveyed on their experience of handling MIS instruments and images obtained of the dorsal and palmar aspects of their dominant hand. Photographs of hands were transformed to calibrated coordinates to enable anthropometric measurements of finger length and width as well as palm width and hand span photogrammetrically. Surgeon-perceived discomfort, fatigue, pressure points and techniques to mitigate difficulty handling instruments were compared to hand measurements. RESULTS: Questionnaires were completed by 58 surgeons; 20 (34%) were consultants, 17 (29%) were women. Glove size ranged from 6 to 8 (median 7.5). Male participants had significantly larger hands than females in all measured dimensions. Female surgeons and those with smaller finger and hand dimensions were significantly more likely to experience difficulty or discomfort across a range of variables when using MIS instruments. CONCLUSIONS: Surgeons with smaller hands reported increased problems handling MIS instruments. This represents an issue of equity in surgery, with women being more significantly affected than men. Hand size varies greatly between surgeons and anthropometric variability should be considered in design of MIS instruments.

Semi-automated analysis of supraclavicular thermal images increases speed of brown adipose tissue analysis without increasing variation in results.

Interest in brown adipose tissue remains high a decade after it was determined to be present outside of the neonatal period. In vivo imaging, however, has remained a challenge due to the lack of a imaging modality suitable for large healthy-volunteer studies, post-prandial investigations and vulnerable groups, such as children. Infrared thermography is increasingly accepted as a valid, non-invasive and flexible alternative but there is a wide approach to analysis between different groups. Defining the region of interest with anatomical borders rather than using a simple polygon may have advantages in terms of consistency but makes image analysis slower, limiting some applications. Our novel semi-automated method, using a custom-built graphical user interface, allows an 86% improvement in speed of image analysis (54.9 (38.3-71.4) seconds/image) without increases in variation between analysers or with repeated analysis. The improved efficiency demonstrated makes feasible larger studies, longer imaging periods or increased image acquisition frequency, providing an opportunity to study novel features of brown adipose tissue function.

Students' Views towards Sars-Cov-2 Mass Asymptomatic Testing, Social Distancing and Self-Isolation in a University Setting during the COVID-19 Pandemic: A Qualitative Study.

We aimed to explore university students' perceptions and experiences of SARS-CoV-2 mass asymptomatic testing, social distancing and self-isolation, during the COVID-19 pandemic. This qualitative study comprised of four rapid online focus groups conducted at a higher education institution in England, during high alert (tier 2) national COVID-19 restrictions. Participants were purposively sampled university students (n = 25) representing a range of gender, age, living circumstances (on/off campus), and SARS-CoV-2 testing/self-isolation experiences. Data were analysed using an inductive thematic approach. Six themes with 16 sub-themes emerged from the analysis of the qualitative data: 'Term-time Experiences', 'Risk Perception and Worry', 'Engagement in Protective Behaviours', 'Openness to Testing', 'Barriers to Testing' and 'General Wellbeing'. Students described feeling safe on campus, believed most of their peers are adherent to protective behaviours and were positive towards asymptomatic testing in university settings. University communications about COVID-19 testing and social behaviours need to be timely and presented in a more inclusive way to reach groups of students who currently feel marginalised. Barriers to engagement with SARS-CoV-2 testing, social distancing and self-isolation were primarily associated with fear of the mental health impacts of self-isolation, including worry about how they will cope, high anxiety, low mood, guilt relating to impact on others and loneliness. Loneliness in students could be mitigated through increased intra-university communications and a focus on establishment of low COVID-risk social activities to help students build and enhance their social support networks. These findings are particularly pertinent in the context of mass asymptomatic testing programmes being implemented in educational settings and high numbers of students being required to self-isolate. Universities need to determine the support needs of students during self-isolation and prepare for the long-term impacts of the pandemic on student mental health and welfare support services.

Skeletal and Dental Habilitation of Residual Alveolar and Maxillary Clefts.

ABSTRACT: Management of residual clefts of the alveolus and maxilla requires the coordinated effort of multiple members of the craniofacial team including surgeon, orthodontist, and when teeth are hypoplastic or absent, the prosthodontist to achieve complete habilitation. Such cooperation among specialists begins early in the patient's life and continues through completion of care.Although numerous publications on this topic exist, few present definitive multidisciplinary reconstructive outcomes with longterm results. In this review paper, the authors present our comprehensive, multidisciplinary protocols, experience, and techniques as they have evolved with over 35 years of practice at our Craniofacial Center.Details of our updated protocols for each intervention and procedure, including our current thoughts on appropriate timing, follow up and advantages from the incorporation of current technologies are discussed. Close cooperation among specialists at all stages of care, the use of evolving technology, and adherence to, and modification where indicated, of time honored team protocols enables us to consistently achieve successful functional and esthetic outcomes, while minimizing complications.

Reduced brown adipose tissue-associated skin temperature following cold stimulation in children and adolescents with type 1 diabetes.

BACKGROUND: Brown adipose tissue (BAT) is essential to maintain body temperature. Its ability to convert chemical energy in glucose and free fatty acids to heat is conferred by a unique protein, UCP-1. BAT activity is greatest in children and adolescents, declining through adulthood. Blood glucose concentrations outside the normal nondiabetic range are common in type 1 diabetes and hyperglycaemia leads to insulin resistance in muscle and white adipose tissue, but whether this applies to BAT, is not known. METHOD: To investigate the effect of type 1 diabetes on BAT activity, we measured the supraclavicular temperature of 20 children with type 1 diabetes and compared them to 20 age-matched controls, using infrared thermography. RESULTS: The diabetes group had lower stimulated supraclavicular temperatures (diabetes group: 35.03 (34.76-35.30)°C; control group: 35.42 (35.16-35.69)°C; p = 0.037) and a reduced response in relative temperature following cold stimulation, after adjusting for BMI (diabetes group: 0.11 (0.03-0.18)°C; control group: 0.22 (0.15-0.29)°C; p = 0.034). In the diabetes group, there was no association between glycaemic measures and supraclavicular temperatures, but the method of insulin delivery may significantly affect the change in supraclavicular temperature with stimulation (injections: 0.01 (-0.07-0.09)°C; pump: 0.15 (0.04-0.26)°C; p = 0.028). CONCLUSIONS: While further work is needed to better understand the glucose-insulin-BAT relationship, one possible explanation for the reduced supraclavicular temperature is that exogenous, unlike endogenous, insulin, is not suppressed by the activity of the sympathetic nervous system, preventing lipolysis-driven activation of BAT.

Finding Comfortable Routes for Ambulance Transfers of Newborn Infants.

Early inter-hospital ambulance transport of premature babies is associated with more severe brain injury. The mechanism is unclear, but they are exposed to excessive noise and vibration. Smart-routing may help minimise these exposure levels and potentially improve outcomes.An app for Android smartphones was developed to collect vibration, noise and location data during ambulance journeys. Four smartphones, with the app installed, were provided to the local neonatal transport group to attach to their incubator trolleys. An example of route comparison was performed on the roads used between Nottingham City Hospital (NCH) and Leicester Royal Infirmary (LRI).Almost 1,700 journeys were recorded over the space of a year. 39 of these journeys travelled from NCH to LRI, comprising of 9 different routes. Analysis was performed on all recorded data which travelled along each road. For routes from NCH to LRI, the route with least vibration was also the quickest. Noise levels, however, were found to increase with vehicle speed. Ambulance drivers in the study did not tend to take the quickest, smoothest or quietest route.Android smartphones are a practical method of gathering information about the in-ambulance environment. Routes were found to vary in vibration, noise and speed, suggesting these could be minimised. The next step is to combine recorded and clinical data to try and define an ideal neonatal comfort metric which can then be fed into the routing. Roll-out of the app around the UK is also planned.Clinical relevance-Transferring preterm neonatal infants to specialist units lead to worse outcomes. By reducing the levels of vibration and noise the infants are exposed to during transport, we hope to improve outcomes.

Growth Spectrum Complexity Dictates Aromatic Intensity in Coriander (Coriandrum sativum L.).

Advancements in availability and specificity of light-emitting diodes (LEDs) have facilitated trait modification of high-value edible herbs and vegetables through the fine manipulation of spectra. Coriander (Coriandrum sativum L.) is a culinary herb, known for its fresh, citrusy aroma, and high economic value. Studies into the impact of light intensity and spectrum on C. sativum physiology, morphology, and aroma are limited. Using a nasal impact frequency panel, a selection of key compounds associated with the characteristic aroma of coriander was identified. Significant differences (P < 0.05) were observed in the concentration of these aromatics between plants grown in a controlled environment chamber under the same photosynthetic photon flux density (PPFD) but custom spectra: red (100%), blue (100%), red + blue (RB, 50% equal contribution), or red + green + blue (RGB, 35.8% red: 26.4% green: 37.8% blue) wavelengths. In general, the concentration of aromatics increased with increasing numbers of wavelengths emitted alongside selective changes, e.g., the greatest increase in coriander-defining E-(2)-decenal occurred under the RGB spectrum. This change in aroma profile was accompanied by significant differences (P < 0.05) in light saturated photosynthetic CO2 assimilation, water-use efficiency (Wi), and morphology. While plants grown under red wavelengths achieved the greatest leaf area, RB spectrum plants were shortest and had the highest leaf:shoot ratio. Therefore, this work evidences a trade-off between sellable commercial morphologies with a weaker, less desirable aroma or a less desirable morphology with more intense coriander-like aromas. When supplemental trichromatic LEDs were used in a commercial glasshouse, the majority of compounds, with the exception of linalool, also increased showing that even as a supplement additional wavelength can modify the aromatic profile increasing its complexity. Lower levels of linalool suggest these plants may be more susceptible to biotic stress such as herbivory. Finally, the concentration of coriander-defining aromatics E-(2)-decenal and E-(2)-hexenal was significantly higher in supermarket pre-packaged coriander leaves implying that concentrations of aromatics increase after excision. In summary, spectra can be used to co-manipulate aroma profile and plant form with increasing spectral complexity leading to greater aromatic complexity and intensity. We suggest that increasing spectral complexity progressively stimulates signaling pathways giving rise to valuable economic traits.

Improving newborn heart rate assessment using a simple visual timer.

OBJECTIVE: Newborn resuscitation relies on accurate heart rate (HR) assessment, which, during auscultation, is prone to error. We investigated if a 6 s visual timer (VT) could improve HR assessment accuracy during newborn simulation. DESIGN: Prospective observational study of newborn healthcare professionals. SETTING: Three-phase developmental approach: phase I: HR auscultation during newborn simulation using a standard clock timer (CT) or the VT; phase II: repeat phase I after using a bespoke training app (NeoRate); phase III: following the Newborn Life Support course, participants assessed random HRs using the CT or VT. MAIN OUTCOME MEASURES: HR accuracy (within ±10 beats/min, correct HR category, i.e. <60, 60-100 and >100 beats/min), assessment time and error-free rates were compared. RESULTS: Overall, 1974 HR assessments were performed with participants more accurate using the VT for ±10 beats/min (70% CT vs 86% VT, p<0.001) and correct HR category (78% CT vs 84% VT, p<0.01). The VT improved accuracy across all three phases. Additionally, following app training in phase II, the HR accuracy of both the CT and VT improved. The VT resulted in faster HR assessment times of 11 s (IQR 9-13) compared with the CT at 15 s (IQR 9-23, p<0.001). Error-free scenarios increased from 24% using the CT to 57% using the VT (p<0.001), with a shorter assessment time (CT 116 s (IQR 65-156) vs VT 53 s (IQR 50-64), p<0.001). CONCLUSION: Using a VT to assess simulated newborn HR combined with a training app significantly improves accuracy and reduces assessment time compared with standard methods. Evaluation in the clinical setting is required to determine potential benefits.

Actinide 2-metallabiphenylenes that satisfy Hückel's rule.

Aromaticity and antiaromaticity, as defined by Hückel's rule, are key ideas in organic chemistry, and are both exemplified in biphenylene1-3-a molecule that consists of two benzene rings joined by a four-membered ring at its core. Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) π-electron system have so far been associated only with organic compounds4,5. In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead6. Here we report the synthesis and characterization of, to our knowledge, the first 2-metallabiphenylene compounds. Single-crystal X-ray diffraction studies reveal that these complexes have nearly planar, 11-membered metallatricycles with metrical parameters that compare well with those reported for biphenylene. Nuclear magnetic resonance spectroscopy, in addition to nucleus-independent chemical shift calculations, provides evidence that these complexes contain an antiaromatic cyclobutadiene ring and an aromatic benzene ring. Furthermore, spectroscopic evidence, Kohn-Sham molecular orbital compositions and natural bond orbital calculations suggest covalency and delocalization of the uranium f2 electrons with the carbon-containing ligand.

Brown Adipose Tissue Response to Cold Stimulation Is Reduced in Girls With Autoimmune Hypothyroidism.

OBJECTIVE: The interaction between thyroid status and brown adipose tissue (BAT) activation is complex. We assessed the effect of autoimmune hypothyroidism (ATD) in female children on BAT activation, measured using infrared thermography. DESIGN: Twenty-six female participants (14 with ATD and 12 healthy controls) between 5 and 17 years of age attended a single study session. Thermal images were taken of the supraclavicular region before, and after, the introduction of a cool stimulus. RESULTS: Participants with ATD had lower resting (hypothyroid, 34.9 ± 0.7°C; control, 35.4 ± 0.5°C; P = 0.03) and stimulated (hypothyroid, 35.0 ± 0.6°C; control, 35.5 ± 0.5°C; P = 0.04) supraclavicular temperatures compared with controls, but there was no difference between groups in the temperature increase with stimulation. BAT activation, calculated as the relative temperature change comparing the supraclavicular temperature to a sternal reference region, was reduced in participants with ATD (hypothyroid, 0.1 ± 0.1°C; control, 0.2 ± 0.2°C; P = 0.04). Children with ATD were frequently biochemically euthyroid due to replacement therapy, but, despite this, increased relative supraclavicular temperature was closely associated with increased TSH (r = 0.7, P = 0.01) concentrations. CONCLUSIONS: Girls with ATD had an attenuated thermogenic response to cold stimulation compared with healthy controls, but, contrary to expectation, those with suboptimal biochemical control (with higher TSH) showed increased BAT activation. This suggests that the underlying disease process may have a negative effect on BAT response, but high levels of TSH can mitigate, and even stimulate, BAT activity. In summary, thyroid status is a complex determinant of BAT activity in girls with ATD.

Facial Gender Affirmation Surgery: Craniomaxillofacial Imaging.

Facial procedures directed at gender affirmation are uniquely tailored to the individual patient and may affect soft tissue and skeletal structures over the entire face-from the chin through the upper forehead. Complete photographic and radiographic documentation that addresses these areas is important from the perspectives of surgical planning, evaluation of outcomes, research purposes, and communication between patient and provider, and amongst treating professionals. This work outlines pertinent skeletal anatomy that is uniquely addressed in gender affirmation procedures and means by which it can be effectively imaged. It provides historical insight into the evolution of computerized-tomography-based imaging. The authors provide detailed protocols for photodocumentation and computerized-tomography based skeletal imaging at their center.

Caffeine exposure induces browning features in adipose tissue in vitro and in vivo.

Brown adipose tissue (BAT) is able to rapidly generate heat and metabolise macronutrients, such as glucose and lipids, through activation of mitochondrial uncoupling protein 1 (UCP1). Diet can modulate UCP1 function but the capacity of individual nutrients to promote the abundance and activity of UCP1 is not well established. Caffeine consumption has been associated with loss of body weight and increased energy expenditure, but whether it can activate UCP1 is unknown. This study examined the effect of caffeine on BAT thermogenesis in vitro and in vivo. Stem cell-derived adipocytes exposed to caffeine (1 mM) showed increased UCP1 protein abundance and cell metabolism with enhanced oxygen consumption and proton leak. These functional responses were associated with browning-like structural changes in mitochondrial and lipid droplet content. Caffeine also increased peroxisome proliferator-activated receptor gamma coactivator 1-alpha expression and mitochondrial biogenesis, together with a number of BAT selective and beige gene markers. In vivo, drinking coffee (but not water) stimulated the temperature of the supraclavicular region, which co-locates to the main region of BAT in adult humans, and is indicative of thermogenesis. Taken together, these results demonstrate that caffeine can promote BAT function at thermoneutrality and may have the potential to be used therapeutically in adult humans.

Patient-reported Quality of Life Following Stereotactic Body Radiotherapy and Conventionally Fractionated External Beam Radiotherapy Compared with Active Surveillance Among Men with Localized Prostate Cancer.

BACKGROUND: Evidence supporting the efficacy of stereotactic body radiotherapy (SBRT) for localized prostate cancer is accumulating, but comparative studies of patient-reported quality of life (QOL) following SBRT versus conventionally fractionated external beam radiotherapy (EBRT) or active surveillance (AS) are limited. OBJECTIVE: To compare QOL of patients pursuing SBRT and EBRT versus AS. DESIGN, SETTING, AND PARTICIPANTS: A population-based cohort of 680 men with newly diagnosed localized prostate cancer was prospectively enrolled from 2011 to 2013. INTERVENTION: SBRT, EBRT without androgen deprivation therapy, or AS. OUTCOME MEASUREMENTS AND STATISTICAL ANALYSIS: QOL was prospectively assessed before treatment (baseline), and at 3, 12, and 24mo after treatment using the validated Prostate Cancer Symptom Indices, which contain four domains: sexual dysfunction, urinary obstruction/irritation, urinary incontinence, and bowel problems. Propensity weighting via logistic regression models was used to balance baseline characteristics, and the mean QOL scores of EBRT and SBRT patients were compared against AS patients as the control group. RESULTS AND LIMITATIONS: Compared with AS patients, EBRT patients had worse urinary obstructive/irritative symptoms and sexual dysfunction at 3mo, and worse bowel symptoms at 3 and 24mo. SBRT patients had similar scores as AS patients in all domains and across all time points; however, due to small sample size, worse sexual function and urinary incontinence in SBRT patients cannot be ruled out. Further research is needed to assess long-term outcomes. CONCLUSIONS: In a nonrandomized cohort of men with localized prostate cancer, SBRT appeared to result in favorable QOL results through 2yr of follow-up, but worse sexual function and urinary incontinence compared with AS cannot be ruled out completely. Larger studies with longer follow-up are needed to confirm these findings. PATIENT SUMMARY: Stereotactic body radiotherapy (SBRT) and active surveillance appear to have similar quality of life outcomes through 2yr, although worse sexual function and urinary incontinence from SBRT cannot be ruled out completely.

Infrared Thermography.

Historically, brown adipose tissue has been elusive and not easy to detect, hence its relative obscurity in human physiology until its rediscovery in 2009. At that point, it was proven that the symmetrical artefacts frequently detected on positron emission tomography-computed tomography (PET-CT), which resolved if the environment was kept warm, were brown adipose tissue deposits. PET-CT has remained the stalwart of human brown adipose tissue research and is still considered the gold standard. However, PET-CT exposes the participant to ionising radiation, limiting studies to large, but retrospective, review of clinical imaging or a small-scale, but prospective, design. Within this context, alternative imaging modalities have been sought. Due to the heat-generating properties of brown adipose tissue, infrared thermography is a natural candidate for measuring its activity and the supraclavicular depot is relatively superficial, allowing detection of the heat signature. Infrared thermography is a non-invasive, non-contact technique for measuring temperature remotely. Recent developments in image analysis techniques have facilitated the use of infrared thermography to study brown adipose tissue activation in populations, and in ways, not previously feasible.

The use of infrared thermography in the measurement and characterization of brown adipose tissue activation.

Interest in brown adipose tissue has increased in recent years as a potential target for novel obesity, diabetes and metabolic disease treatments. One of the significant limitations to rapid progress has been the difficulty in measuring brown adipose tissue activity, especially in humans. Infrared thermography (IRT) is being increasingly recognized as a valid and complementary method to standard imaging modalities, such as positron emission tomography-computed tomography (PET/CT). In contrast to PET/CT, it is non-invasive, cheap and quick, allowing, for the first time, the possibility of large studies of brown adipose tissue (BAT) on healthy populations and children. Variations in study protocols and analysis methods currently limit direct comparison between studies but IRT following appropriate BAT stimulation consistently shows a change in supraclavicular skin temperature and a close association with results from BAT measurements from other methods.

A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium(vi) monosulphide, uranium(vi) η2-disulphide, and uranium(iv) phosphine sulphide complexes.

Three new uranium species (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S), (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(η2-S2), and (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(S[double bond, length as m-dash]PMe3) were synthesized and fully characterized by a combination of NMR, IR, and UV/vis-NIR spectroscopies, elemental analysis, and cyclic voltammetry. The solid state structures of (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S) and (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(η2-S2) were also determined. The compound (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S) is the first neutral uranium complex with a terminal sulphido ligand, and (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(S[double bond, length as m-dash]PMe3) is the first uranium compound with a coordinated phosphine sulphide ligand. The phosphine sulphide adduct, (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(S[double bond, length as m-dash]PMe3), can be synthesized either by reaction of the uranium(iv) complex (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(thf) with S[double bond, length as m-dash]PMe3 or by the reaction of the uranium(vi) terminal sulphido complex (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S) with PMe3.

Thermal Imaging Is a Noninvasive Alternative to PET/CT for Measurement of Brown Adipose Tissue Activity in Humans.

Obesity and its metabolic consequences are a major cause of morbidity and mortality. Brown adipose tissue (BAT) utilizes glucose and free fatty acids to produce heat, thereby increasing energy expenditure. Effective evaluation of human BAT stimulators is constrained by the current standard method of assessing BAT-PET/CT-as it requires exposure to high doses of ionizing radiation. Infrared thermography (IRT) is a potential noninvasive, safe alternative, although direct corroboration with PET/CT has not been established. Methods: IRT and 18F-FDG PET/CT data from 8 healthy men subjected to water-jacket cooling were directly compared. Thermal images were geometrically transformed to overlay PET/CT-derived maximum intensity projection (MIP) images from each subject, and the areas with the most intense temperature and glucose uptake within the supraclavicular regions were compared. Relationships between supraclavicular temperatures (TSCR) from IRT and the metabolic rate of glucose uptake (MR(gluc)) from PET/CT were determined. Results: Glucose uptake on MR(gluc)MIP was found to correlate positively with a change in TSCR relative to a reference region (r2 = 0.721; P = 0.008). Spatial overlap between areas of maximal MR(gluc)MIP and maximal TSCR was 29.5% ± 5.1%. Prolonged cooling, for 60 min, was associated with a further TSCR rise, compared with cooling for 10 min. Conclusion: The supraclavicular hotspot identified on IRT closely corresponded to the area of maximal uptake on PET/CT-derived MR(gluc)MIP images. Greater increases in relative TSCR were associated with raised glucose uptake. IRT should now be considered a suitable method for measuring BAT activation, especially in populations for whom PET/CT is not feasible, practical, or repeatable.

Synthesis, Characterization, and Density Functional Theory Analysis of Uranium and Thorium Complexes Containing Nitrogen-Rich 5-Methyltetrazolate Ligands.

Two nitrogen-rich, isostructural complexes of uranium and thorium, (C5Me5)2U[η(2)-(N,N')-tetrazolate]2 (7) and (C5Me5)2Th[η(2)-(N,N')-tetrazolate]2 (8), containing 5-methyltetrazolate, have been synthesized and structurally characterized by single-crystal X-ray diffraction, electrochemical methods, UV-visible-near-IR spectroscopy, and variable-temperature (1)H NMR spectroscopy. Density functional theory (DFT) calculations yield favorable free energies of formation (approximately -375 kJ/mol) and optimized structures in good agreement with the experimental crystal structures. Additionally, calculated NMR chemical shifts of 7 and 8 are in good agreement with the variable-temperature (1)H NMR experiments. Time-dependent DFT calculations of both complexes yield UV-visible spectroscopic features that are consistent with experiment and provide assignments of the corresponding electronic transitions. The electronic transitions in the UV-visible spectroscopic region are attributed to C5Me5 ligand-to-metal charge transfer. The low-lying molecular orbitals of the tetrazolate ligands (∼2 eV below the HOMO) do not contribute appreciably to experimentally observed electronic transitions. The combined experimental and theoretical analysis of these new nitrogen-rich uranium and thorium complexes indicates the tetrazolate ligand behaves primarily as a σ-donor.

New Twists and Turns for Actinide Chemistry: Organometallic Infinite Coordination Polymers of Thorium Diazide.

Two organometallic 1D infinite coordination polymers and two organometallic monometallic complexes of thorium diazide have been synthesized and characterized. Steric control of these self-assembled arrays, which are dense in thorium and nitrogen, has also been demonstrated: infinite chains can be circumvented by using steric bulk either at the metallocene or with a donor ligand in the wedge.

Primary Overcorrection of the Unilateral Cleft Nasal Deformity: Quantifying the Results.

BACKGROUND: Because primary nasal correction by the time of lip repair has been incorporated into the treatment approach, many patients have benefitted from this combined procedure. However, primary nasal correction cannot guarantee an excellent result. Although overcorrection has been mentioned as a treatment rationale of the unilateral cleft lip nasal deformity, a detailed approach and quantitative evidence of the rationale are rare. This study evaluates whether overcorrection in the primary repair results in a quantitative improvement in nasal appearance. PATIENTS AND METHODS: In this retrospective study, the inclusion criteria were patients with complete unilateral cleft lip and palate who underwent primary lip and nose repair by the age of 3 to 4 months. Primary nasal overcorrection was achieved by application of muscle to septal base suture, alar cinching suture and Tajima reversed U incision method. Patients were further divided into an overcorrected (n = 19) and nonovercorrected group (n = 19). The following parameters were identified on basilar photos of all patients taken at least 12 months after repair, ratios of cleft to noncleft side in each patient were taken and the mean for each parameter calculated: Ac angle (ACA/ACA'), alar height (AH/AH'), alar width (AW/AW'), nostril height (NH/NH`), nostril width (NW/NW'), and columellar deviation from the midline (CD/NW). The means of the overcorrected and nonovercorrected groups were then compared using the t test. RESULTS: From all investigated measuremens, Alar height (AH/AH': overcorrected, 0.983 to nonovercorrected, 0.941; P = 0.03) and nostril height ratio (NH/NH') (NH/NH': covercorrected, 0.897 to nonovercorrected, 0.680; P = 0.003) showed statistically significant differences favoring the overcorrected group at least 12 months after surgery. CONCLUSIONS: Primary nasal overcorrection including muscle to columella base suture, alar cinch suture, and Tajima method resulted in quantitatively more long-term symmetric alae and nostril height compared to nonovercorrected patients.