Rh(I) and Organo-Rh(III) Complexes of meso-Triarylbiphenylcorrole.

Rhodium complexes of biphenylcorrole are reported, and the molecular structures of the complexes are unambiguously confirmed by single-crystal X-ray analysis. The adj-CCNN core of the dicarbacorrole efficiently stabilizes a rhodium metal ion in its two different oxidation states. It is pertinent to point out that the Rh(I) metal complex attains square-planar geometry while organo-Rh(III) forms an octahedral complex. Furthermore, density functional theory studies corroborate the experimental findings.

CTP-based estimated ischemic core: A comparative multicenter study between Olea and RAPID software.

BACKGROUND AND PURPOSE: CTP is increasingly used to assess eligibility for endovascular therapy (EVT) in patients with large vessel occlusions (LVO). There remain variability and inconsistencies between software packages for estimation of ischemic core. We aimed to use heterogenous data from four stroke centers to perform a comparative analysis for CTP-estimated ischemic core between RAPID (iSchemaView) and Olea (Olea Medical). METHODS: In this retrospective multicenter study, patients with anterior circulation LVO who underwent pretreatment CTP, successful EVT (defined TICI ≥ 2b), and follow-up MRI included. Automated CTP analysis was performed using Olea platform [rCBF < 25% and differential time-to-peak (dTTP)>5s] and RAPID (rCBF < 30%). The CTP estimated core volumes were compared against the final infarct volume (FIV) on post treatment MRI-DWI. RESULTS: A total of 151 patients included. The CTP-estimated ischemic core volumes (mean ± SD) were 18.7 ± 18.9 mL on Olea and 10.5 ± 17.9 mL on RAPID significantly different (p < 0.01). The correlation between CTP estimated core and MRI final infarct volume was r = 0.38, p < 0.01 for RAPID and r = 0.39, p < 0.01 for Olea. Both software platforms demonstrated a strong correlation with each other (r = 0.864, p < 0.001). Both software overestimated the ischemic core volume above 70 mL in 4 patients (2.6%). CONCLUSIONS: Substantial variation between Olea and RAPID CTP-estimated core volumes exists, though rates of overcalling of large core were low and identical. Both showed comparable core volume correlation to MRI infarct volume.

Homocarbaporphyrinoids: The m-o-m and p-o-p Terphenyl Embedded Expanded Porphyrin Analogues and Their RhI Complexes.

Stable homocarbaporphyrinoids were successfully synthesized by incorporating the m-o-m and p-o-p terphenyl units into the porphyrin core. The distinct bonding modes of terphenyl in the macrocycle generated two structural isomers with two and four carbon atoms in the macrocyclic environment. The core was utilized to stabilize the RhI ion. The spectral and structural analyses revealed that the restricted (m-o-m) and allowed (p-o-p) conjugation in the macrocyclic core provide overall non-aromatic characteristics both to the free bases and their complexes.

Bis-4,4'-biphenyl Ring Embedded Octaphyrin with Three Distinct Conformational Structures.

Three distinct conformational structures of carbaoctaphyrins were prepared by incorporating bis-4,4'-biphenyl units in the macrocyclic core. The free-base form adopts a figure-eight conformation, whereas the protonation triggers a conformational change with a pyrrole ring inversion and acquires an open-framework structure. The insertion of bis-RhI metal ion in the macrocyclic core affords a singly twisted conformational structure. Furthermore, the local aromaticity in the bis-4,4'-biphenyl ring dominates the overall macrocyclic aromaticity in all three forms, and thus adopts nonaromatic characteristics. These results are supported by spectral as well as theoretical studies, and they are unambiguously confirmed by X-ray crystal analyses.

Smaragdyrins and Sapphyrins Analogues.

Porphyrins and expanded porphyrins have attracted the attention of chemists for a long time in view of their diverse applications in catalysis; as anion, cation, and neutral substrate receptors; as ligands to coordinate large metal ions; as nonlinear optical materials, MRI contrasting agents, and sensitizers for photodynamic therapy (PDT); and more recently as models for aromaticity (both Hückel and Möbius). A diverse range of synthetic expanded porphyrins containing up to 96π electrons have been reported, and their properties have been exploited for various applications. The present Review is only confined to 22π electron expanded porphyrins containing five pyrrole/heterocyclic rings such as sapphyrins and smaragdyrins. Even though these two macrocycles contain 22π electrons and five pyrrole/heterocyclic rings, they are structurally different. In sapphyrins, the five pyrrole/heterocyclic rings are connected through four meso-carbon bridges and one direct pyrrole-pyrrole bond, whereas in smaragdyrins, the five pyrrole/heterocyclic rings are connected through three meso-carbon bridges and two direct pyrrole-pyrrole bonds. The chemistry of sapphyrins has been well-established in recent years due to the availability of easy and efficient synthetic methods. On the other hand, smaragdyrins are not explored significantly because of their unstable nature. However, recently it was shown that smaragdyrins can be stabilized if one of the pyrrole rings is replaced with a furan ring to afford stable oxasmaragdyrin. The availability of oxasmaragdyrin allowed the exploration of smaragdyrin in recent years. Thus, an attempt has been made in this Review to describe the chemistry of both sapphyrins and smaragdyrins in terms of their synthesis, characterization, metal ion coordination, and anion-recognition properties.

Evaluation of Circulating Plasma VEGF-A, ET-1 and Magnesium Levels as the Predictive Markers for Proliferative Diabetic Retinopathy.

Diabetic retinopathy (DR) is the most common cause for preventable blindness in India. The onset of micro and macrovascular complications in T2DM is multifactorial and difficult to predict. The status of micronutrients, several inflammatory cytokines, elevated triacylglycerols, oxidative stress etc., are being studied extensively. Hypomagnesemia plays a pivotal role in worsening of insulin resistance. Although, Vascular Endothelial Growth Factor-A (VEGF-A) and Endothelin-1 (ET-1) are known to be elevated in DR, yet few reports cite their role, especially in Indian population. In this study, we included thirty subjects with T2DM in each of the three groups namely, T2DM cases without retinopathy, Non Proliferative DR (NPDR) and Proliferative DR (PDR) retinopathy. The glycemic status, circulating plasma VEGF-A, ET-1 levels, serum magnesium and lipids were estimated and compared among the groups. An ROC was drawn to evaluate VEGF-A, ET-1 and serum magnesium levels as the predictive markers for PDR. On comparison VEGF-A, ET-1 and serum magnesium levels showed a significant difference among the three groups. PDR cases had higher circulating levels of VEGF-A, ET-1 and low serum magnesium levels when compared to others. ROC for VEGF-A and ET-1 showed an optimum cut-off of 1521 ng/ml (AUC 0.975) and 16 pg/ml (AUC 0.96) respectively. A negative ROC was drawn to check the lower cut-off limit for serum magnesium; we documented an optimum cut off of 1.7 mg/dl (AUC 0.837). ET-1, VEGF-A and serum Magnesium levels are significantly altered in PDR and can be used as the predictive markers of PDR.

Impact of specialist management on survival from radiation-associated angiosarcoma of the breast.

BACKGROUND: Radiation-associated angiosarcoma of the breast (RAAS) is a rare complication of adjuvant radiotherapy associated with poor survival. The British Sarcoma Group guidelines recommend that all angiosarcomas are referred to a sarcoma multidisciplinary team, although there is no recommendation that patients are managed within a sarcoma service. The aims of this study were to compare survival, complete excision rates and local recurrence rates of patients managed within a sarcoma service and those managed within local hospitals. METHODS: All patients with RAAS referred to a regional sarcoma service between 1998 and 2015 were identified from prospective databases. Patient records, and radiology, pathology and operation notes were reviewed retrospectively. RESULTS: Thirty-six patients were operated on with curative intent; 26 were managed by the sarcoma service (of whom 21 underwent radical excision of the irradiated field followed by chest wall reconstruction) and ten were managed locally. Median age was 69·5 (range 43-85) years. Disease-specific survival was significantly longer in patients managed by the sarcoma service than in those managed locally: median 91·1 (range 69·2-113·0) versus 48·8 (18·6-79·1) months respectively (P = 0·012). Overall survival rates were similar (P = 0·112). There was no difference in complete excision rate (18 of 26 in sarcoma service versus 5 of 10 in local services; P = 0·456), although the local recurrence rate was significantly lower among patients managed by the sarcoma service (9 of 26 versus 8 of 10; P = 0·015). CONCLUSION: Specialist management of RAAS leads to fewer local recurrences and improved disease-specific survival. Early referral and management within specialist units is recommended.

Electrical Control of the Zeeman Spin Splitting in Two-Dimensional Hole Systems.

Semiconductor holes with strong spin-orbit coupling allow all-electrical spin control, with broad applications ranging from spintronics to quantum computation. Using a two-dimensional hole system in a gallium arsenide quantum well, we demonstrate a new mechanism of electrically controlling the Zeeman splitting, which is achieved through altering the hole wave vector k. We find a threefold enhancement of the in-plane g-factor g_{∥}(k). We introduce a new method for quantifying the Zeeman splitting from magnetoresistance measurements, since the conventional tilted field approach fails for two-dimensional systems with strong spin-orbit coupling. Finally, we show that the Rashba spin-orbit interaction suppresses the in-plane Zeeman interaction at low magnetic fields. The ability to control the Zeeman splitting with electric fields opens up new possibilities for future quantum spin-based devices, manipulating non-Abelian geometric phases, and realizing Majorana systems in p-type superconductor systems.

24π Core-Modified Nonfused Pentaphyrin with Möbius Aromaticity.

Syntheses of core-modified 24π pentaphyrin 7 and 20π homoporphyrin 8 are reported. The freebase form of 7 exhibits optical and 1 H NMR spectroscopic behavior corresponding to a 4nπ nonaromatic topology at 298 K. However, upon lowering the temperature to 188 K, 7 exhibits weak aromaticity because of a small conformational change. Protonation of the imine pyrrolic nitrogen atoms results in sharpening of the absorption band with more than 100 nm red shift and two-fold increase in ϵ values. The 1 H NMR spectra show large shielding and deshielding of specific protons accompanied by twisting of pyrrole and thiophene rings from the mean plane of the macrocycle. These observations suggest a major structural change upon protonation. The single-crystal X-ray structure of protonated 7 a reveals a severe twisting of the macrocycle, especially at the ethene bridge, and the two thiophene rings adjacent to the ethene bridge are pointed above and below the plane of the ethene bridge (49.07° and 49.08°). The nucleus-independent chemical shift (NICS) values calculated at the center of the macrocycle for the freebase and protonated derivatives of 7 a and 7 b are -5.6, -8.3 ppm and -5.3, -8.4 ppm, respectively. The anisotropy-induced current density (AICD) plots suggest a clockwise circulation of π electrons. Taken together, the changes occurring in the optical spectra, 1 H NMR spectra, single-crystal X-ray structure and NICS calculation reflect a Möbius aromatic topology for protonated 7. However, the homoporphyrin 8 remains nonaromatic both in the freebase and protonated form.

Rhodium(III) and Iridium(III) Bipyricorrole Complexes: Syntheses, Structures, and Properties.

Rhodium(III) and iridium(III) bipyricorrole complexes have been unprecedentedly reported. Single-crystal X-ray diffraction studies unambiguously evinced the molecular structures of metal complexes in octahedral geometry. The monoanionic platform of bipyricorrole effectively stabilizes metal ions in their higher oxidation states. It is worth mentioning that the fluorescence quantum yield of the rhodium(III) complex is 3-fold higher than that of free-base bipyricorrole.

Microwave enhanced advanced oxidation treatment of dairy manure.

The microwave enhanced advanced oxidation process (MW-AOP) was used to treat dairy manure in a continuous-flow 915 MHz microwave wastewater treatment system. The treatment efficiency increased with an increase in temperature, as well as hydrogen peroxide dosage. The settling property was also improved in all treated sets, regardless of temperature applied. The system operated at temperatures >100 °C had a much higher soluble chemical oxygen demand than at temperatures <100 °C. The highest soluble carbonaceous compounds, orthophosphate and ammonia were obtained at 110 °C and 0.6%H2O2 per % of total solids content. The process should be operated at higher temperatures and higher hydrogen peroxide dosages for maximizing solids disintegration, nutrient release and energy efficiency. An energy fingerprint correlating the cumulative energy consumption and temperature rise was developed. The results demonstrated that the custom designed MW-AOP system is suitable for the effective treatment of dairy manure. The system can readily be scaled up and integrated into a dairy farm manure treatment and resource recovery system.

Evaluation of Preanalytical Quality Indicators by Six Sigma and Pareto`s Principle.

Preanalytical steps are the major sources of error in clinical laboratory. The analytical errors can be corrected by quality control procedures but there is a need for stringent quality checks in preanalytical area as these processes are done outside the laboratory. Sigma value depicts the performance of laboratory and its quality measures. Hence in the present study six sigma and Pareto principle was applied to preanalytical quality indicators to evaluate the clinical biochemistry laboratory performance. This observational study was carried out for a period of 1 year from November 2015-2016. A total of 1,44,208 samples and 54,265 test requisition forms were screened for preanalytical errors like missing patient information, sample collection details in forms and hemolysed, lipemic, inappropriate, insufficient samples and total number of errors were calculated and converted into defects per million and sigma scale. Pareto`s chart was drawn using total number of errors and cumulative percentage. In 75% test requisition forms diagnosis was not mentioned and sigma value of 0.9 was obtained and for other errors like sample receiving time, stat and type of sample sigma values were 2.9, 2.6, and 2.8 respectively. For insufficient sample and improper ratio of blood to anticoagulant sigma value was 4.3. Pareto`s chart depicts out of 80% of errors in requisition forms, 20% is contributed by missing information like diagnosis. The development of quality indicators, application of six sigma and Pareto`s principle are quality measures by which not only preanalytical, the total testing process can be improved.

Mechanisms for Strong Anisotropy of In-Plane g-Factors in Hole Based Quantum Point Contacts.

In-plane hole g factors measured in quantum point contacts based on p-type heterostructures strongly depend on the orientation of the magnetic field with respect to the electric current. This effect, first reported a decade ago and confirmed in a number of publications, has remained an open problem. In this work, we present systematic experimental studies to disentangle different mechanisms contributing to the effect and develop the theory which describes it successfully. We show that there is a new mechanism for the anisotropy related to the existence of an additional B_{+}k_{-}^{4}σ_{+} effective Zeeman interaction for holes, which is kinematically different from the standard single Zeeman term B_{-}k_{-}^{2}σ_{+} considered until now.

Detection and Control of Spin-Orbit Interactions in a GaAs Hole Quantum Point Contact.

We investigate the relationship between the Zeeman interaction and the inversion-asymmetry-induced spin-orbit interactions (Rashba and Dresselhaus SOIs) in GaAs hole quantum point contacts. The presence of a strong SOI results in the crossing and anticrossing of adjacent spin-split hole subbands in a magnetic field. We demonstrate theoretically and experimentally that the anticrossing energy gap depends on the interplay between the SOI terms and the highly anisotropic hole g tensor and that this interplay can be tuned by selecting the crystal axis along which the current and magnetic field are aligned. Our results constitute the independent detection and control of the Dresselhaus and Rashba SOIs in hole systems, which could be of importance for spintronics and quantum information applications.

Carbatriphyrin(3.1.1)-A Distinct Coordination Approach of BIII to Generate Organoborane and Weak C-H⋠⋠⋠B Interactions.

Carbatriphyrin(3.1.1) is the structural isomer of biphenylcorrole and achieved by switching the bonding mode of biphenyl unit from 3,3' to 2,3' which turns the corrole into a triphyrin analogue. The presence of a m-arene unit in the framework restricts the overall conjugation and thus leads to a nonaromatic macrocycle. The protonation experiments afford a trifluoroacetate ion complex. The coordination chemistry reveals that the bottom approach of boron(III) ion forms weak C-H⋅⋅⋅B interactions, however a top approach stabilizes the organoborane complex and the product distribution relies on the basicity of the proton scavengers. These results are unambiguously confirmed by single-crystal X-ray analyses.

Impact of providing patients with copies of their medical correspondence: a randomised controlled study.

BACKGROUND: In Australia, correspondence is routinely sent to general practitioners following a specialist consultation. Written communication is an important way to enhance patient experiences and understanding, yet most patients do not receive copies of their medical correspondence. AIMS: To determine whether providing clinic correspondence and endoscopy reports to patients leads to improved understanding, satisfaction or anxiety. METHODS: This is a prospective, randomised controlled study conducted at an Australian tertiary hospital from October 2013 to February 2015. New adult referrals to the general gastroenterology clinic requiring an urgent endoscopic procedure were eligible for the study. The intervention group received a copy of their clinic correspondence and endoscopy report, while the control group received neither. Participants completed questionnaires, including visual analogue scales and the Hospital Anxiety and Depression Scale, at three time points. Primary outcomes were patient understanding, anxiety and satisfaction. RESULTS: A total of 70 participants was included in the study. There was no reduction in anxiety levels (P = 0.52), no increase in understanding (P = 0.73) or any increase in satisfaction (P = 0.33) in participants receiving correspondence. However, 97% of participants indicated that they wished to receive correspondence in the future, and 94% of participants in the correspondence group reported that receiving correspondence had helped them to understand their medical condition. CONCLUSION: Patients wish to receive copies of their correspondence and feel it improves their understanding of their medical condition. Although we were unable to demonstrate a measurable reduction in anxiety, increase in understanding or satisfaction, we recommend that patients be offered the choice of receiving copies of their clinic correspondence and endoscopy reports.

Putative Role of Cardio Metabolic Risk Among Poorly Controlled Asthmatics in South Indian Population.

Mortality and morbidity attributed to asthma remains to be the biggest nightmare worldwide. Hence, the study was aimed to compare the cardio metabolic risk factors as assessed by Body mass index (BMI), waist hip ratio (WHR), serum triacylglycerol and uric acid in well controlled and poorly controlled asthmatics and to correlate these parameters with the severity of asthma. A case control study was conducted on 90 subjects who were segregated into well controlled asthmatics (n = 30) and poorly controlled asthmatics (n = 30) who were diagnosed based on Global initiative for Asthma management guidelines and healthy volunteers (n = 30). Centrifuged fasting venous blood samples were used for biochemical analysis, pulmonary function test, BMI, and waist hip ratio (WHR) were measured. The statistical analysis was done using SPSS version 17. There was a significant increase in BMI, WHR, lipid profile, serum uric acid and decrease in forced expiratory volume (FEV1), forced vital capacity (FVC), and FEV1/FVC in poorly controlled asthmatics. There was a significant association between FEV1 and serum uric acid, BMI and Triacylgycerol in poorly controlled asthmatics. Poorly controlled asthmatics have greater risk of developing cardiometabolic problems. Serum uric acid can be used as one of the severity markers in asthma to assess cardio metabolic risk.

meso-Aryl [20]π Homoporphyrin: The Simplest Expanded Porphyrin with the Smallest Möbius Topology.

An unstable conjugated homoporphyrin was successfully stabilized by introducing meso-aryl substitutents. It was evident from the moderate diatropic ring current found by NMR analysis that the newly formed 20π conjugated free base and its protonated form exhibited Möbius aromatic character. Furthermore, complexation as a ligand with an RhI ion afforded a unique binding mode and retained the Möbius aromaticity. Overall, these compounds are the smallest Möbius aromatic molecules, as confirmed by spectral and crystal-structure analysis and supported by theoretical studies.

[40]π Fused and Nonfused Core-Modified Nonaphyrins: Syntheses and Structural Diversity.

The synthesis of fused and nonfused core-modified 40π nonaphyrins are reported. Spectroscopic and X-ray structural studies reveal a twisted figure-eight conformation in the freebase form that is nonaromatic. Structural changes occur, from figure-eight to open extended conformation, upon protonation, thereby adopting 4nπ Hückel antiaromatic character, which is reflected in spectroscopic and theoretical studies. Such a structural change also induces ring inversions of specific heterocyclic rings by 180°.

[32]π Fused Core-Modified Heptaphyrin with Möbius Aromaticity.

A new fused core-modified 32π heptaphyrin with Möbius aromatic character is reported. The (1)H NMR data indicated a weak Möbius aromaticity at 298 K; however, at 213-183 K, the molecule predominates [4n]π Möbius conformation with strong diatropic ring current, which was further confirmed by X-ray analysis. The protonation experiment led to preservation of the Möbius aromaticity at 298 K. Nevertheless, the experimental results were further supported by theoretical studies. Overall, this study represents the first example of Möbius aromatic fused core-modified expanded porphyrin.