Isoeffect calculations based on linear quadratic equations for head and neck cancers

BackgroundThe linear quadratic model has led to various methods for the calculation of isoeffect relationships in radiotherapy. In this model, the tissue sensitive parameters α and β usually appear as a ratio, α/β. These parameters are used to describe the response of normal tissues to radiation insult. Different radiation induced biological end points in specific tissues and organs are associated with the characteristics of the α/β ratio. The linear quadratic model has been used clinically to address questions relating to changes in fractions in treatment schedules.AimThe process of treating cancer with ionizing radiation is complex and subject to dosimetric errors which may potentially result in early or late complications. Our objective was to correct such errors through the application of the incomplete repair linear quadratic model.Materials/MethodsRepair mechanisms are affected if, owing to dosimetric error, excess dose is delivered in single or multiple fractions. Corrections for such errors were simulated, for different clinical situations, in order to avoid late fibrosis in head and neck cancers.ResultsNSD, CRE, and TDF approach could not predict, onset of proliferation, overall treatment time, late and early complications, but linear quadratic model calculations predicts isoeffective schedules successfully with above parameters.ConclusionsIn head and neck cancers, a number of parameters influence the results of treatment. Isoeffect calculations show the risk factors responsible for fibrosis and spinal cord damage and therefore may be used to calculate dose reductions for all remaining fractions, rather than applying shielding

From antiferromagnetic to ferromagnetic exchange in a family of oxime-based Mn(III) dimers:a magneto-structural study

The reaction of Mn(ClO4)(2)center dot 6H(2)O, a derivatised phenolic oxime (R-saoH(2)) and the ligand tris(2-pyridylmethyl)amine (tpa) in a basic alcoholic solution leads to the formation of a family of cluster compounds of general formula [(Mn2O)-O-III(R-sao)(tpa)(2)](ClO4)(2) (1, R = H; 2, R = Me; 3, R = Et; 4, R = Ph). The structure is that of a simple, albeit asymmetric, dimer of two Mn-III ions bridged through one mu-O2- ion and the -N-O- moiety of the phenolic oxime. Magnetometry reveals that the exchange interaction between the two MnIII ions in complexes 1, 3 and 4 is antiferromagnetic, but that for complex 2 is ferromagnetic. A theoretically developed magneto-structural correlation reveals that the dominant structural parameter influencing the sign and magnitude of the pairwise interaction is the dihedral Mn-O-N-Mn (torsion) angle. A linear correlation is found, with the magnitude of J varying significantly as the dihedral angle is altered. As the torsion angle increases the AF exchange decreases, matching the experimentally determined data. DFT calculations reveal that the (dyz)vertical bar pi vertical bar d(yz) interaction decreases as the dihedral angle increases leading to ferromagnetic coupling at larger angles

Acute mental health presentations before and during the COVID-19 pandemic

Background: A number of community based surveys have identified an increase in psychological symptoms and distress but there has been no examination of symptoms at the more severe end of the mental health spectrum. // Aims: We aimed to analyse numbers and types of psychiatric presentations to inform planning for future demand on mental health services in light of the COVID-19 pandemic. // Method: We analysed electronic data between January and April 2020 for 2534 patients referred to acute psychiatric services, and tested for differences in patient demographics, symptom severity and use of the Mental Health Act 1983 (MHA), before and after lockdown. We used interrupted time-series analyses to compare trends in emergency department and psychiatric presentations until December 2020. // Results: There were 22% fewer psychiatric presentations the first week and 48% fewer emergency department presentations in the first month after lockdown initiated. A higher proportion of patients were detained under the MHA (22.2 v. 16.1%) and Mental Capacity Act 2005 (2.2 v. 1.1%) (χ2(2) = 16.3, P < 0.0001), and they experienced a longer duration of symptoms before seeking help from mental health services (χ2(3) = 18.6, P < 0.0001). A higher proportion of patients presented with psychotic symptoms (23.3 v. 17.0%) or delirium (7.0 v. 3.6%), and fewer had self-harm behaviour (43.8 v. 52.0%, χ2(7) = 28.7, P < 0.0001). A higher proportion were admitted to psychiatric in-patient units (22.2 v. 18.3%) (χ2(6) = 42.8, P < 0.0001) after lockdown. // Conclusions: UK lockdown resulted in fewer psychiatric presentations, but those who presented were more likely to have severe symptoms, be detained under the MHA and be admitted to hospital. Psychiatric services should ensure provision of care for these patients as well as planning for those affected by future COVID-19 waves

Switching the orientation of Jahn-Teller axes in oxime-based Mn(III) dimers and its effect upon magnetic exchange:a combined experimental and theoretical study

A family of Mn-III dimers of general formula [Mn-2(III)(R-sao)(2)(dpa)(2)](ClO4)(2) (1-5) has been synthesised using derivatised phenolic oximes (R-saoH(2), where R = H, Me, Et, Ph) in combination with di-(2-picolyl)-amine (dpa). Their structures reveal a double-oxime bridged [Mn-III(NO)](2) magnetic core in which the Jahn-Teller axes lie perpendicular to the bridging plane, in contrast to two previously reported family members (6, 7). The switch in the orientation of the Jahn-Teller axes is enforced through the use of the chelating ligand which is present in 1-5 and absent in 6-7. Dc magnetic susceptibility measurements reveal that the exchange interactions between the MnIII metal centres in 1-5 are antiferromagnetic in contrast to that observed for 6 and 7 which are ferromagnetic. DFT calculations performed on complexes 1-6 reproduce both the sign and strength of the J values found experimentally. Molecular orbital analysis unlocks a common mechanism of magnetic coupling based upon the orientation of the Jahn-Teller axis, with the magneto-structural correlation also dependent upon the Mn-N-O-Mn angles - with ferromagnetic interactions at smaller dihedral angles

Suitability of point kernel dose calculation techniques in brachytherapy treatment planning

Brachytherapy treatment planning system (TPS) is necessary to estimate the dose to target volume and organ at risk (OAR). TPS is always recommended to account for the effect of tissue, applicator and shielding material heterogeneities exist in applicators. However, most brachytherapy TPS software packages estimate the absorbed dose at a point, taking care of only the contributions of individual sources and the source distribution, neglecting the dose perturbations arising from the applicator design and construction. There are some degrees of uncertainties in dose rate estimations under realistic clinical conditions. In this regard, an attempt is made to explore the suitability of point kernels for brachytherapy dose rate calculations and develop new interactive brachytherapy package, named as BrachyTPS, to suit the clinical conditions. BrachyTPS is an interactive point kernel code package developed to perform independent dose rate calculations by taking into account the effect of these heterogeneities, using two regions build up factors, proposed by Kalos. The primary aim of this study is to validate the developed point kernel code package integrated with treatment planning computational systems against the Monte Carlo (MC) results. In the present work, three brachytherapy applicators commonly used in the treatment of uterine cervical carcinoma, namely (i) Board of Radiation Isotope and Technology (BRIT) low dose rate (LDR) applicator and (ii) Fletcher Green type LDR applicator (iii) Fletcher Williamson high dose rate (HDR) applicator, are studied to test the accuracy of the software. Dose rates computed using the developed code are compared with the relevant results of the MC simulations. Further, attempts are also made to study the dose rate distribution around the commercially available shielded vaginal applicator set (Nucletron). The percentage deviations of BrachyTPS computed dose rate values from the MC results are observed to be within plus/minus 5.5&#x0025; for BRIT LDR applicator, found to vary from 2.6 to 5.1&#x0025; for Fletcher green type LDR applicator and are up to -4.7&#x0025; for Fletcher-Williamson HDR applicator. The isodose distribution plots also show good agreements with the results of previous literatures. The isodose distributions around the shielded vaginal cylinder computed using BrachyTPS code show better agreement (less than two per cent deviation) with MC results in the unshielded region compared to shielded region, where the deviations are observed up to five per cent. The present study implies that the accurate and fast validation of complicated treatment planning calculations is possible with the point kernel code package

The forgotten father in obstetric medicine

The role of fathers prior to conception, during pregnancy, and in the post-partum period has generally not been a key consideration for Obstetric Physicians. However, this view may need challenging. This paper outlines the key importance of fathers in all phases of obstetric medical care. We review the contribution of paternal factors such as genetics, health, and lifestyle to fetal development, pregnancy complications, and maternal and neonatal wellbeing. The role of fathers in complex care decisions during pregnancy is also reviewed. Postpartum, fathers have a substantial role in shaping the future of the family unit through encouraging breastfeeding and creating a supportive environment for motherhood. This review proposes areas for future research and recommends an evidence-based change in practice in obstetric medicine that focuses on recognizing the role of fathers in the pregnancy journey

Reductive activation of N 2 using a calcium/potassium bimetallic system supported by an extremely bulky diamide ligand

An extremely bulky xanthene bridged diamide ligand ((NON)-N-TCHP = 4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) has been developed and used to prepare two monomeric diamido-calcium complexes [((NON)-N-TCHP)Ca(D)(n)] (D = THF, n = 2, 3; D = toluene, n = 1, 4). Reduction of 4 with 5% w/w K/KI under an N-2 atmosphere gave the first well-defined, hetero-bimetallic s-block complex of activated dinitrogen, [{K((NON)-N-TCHP)Ca}(2)(mu-eta(2):eta(2)-N-2)] 5, presumably via a transient calcium(i) intermediate

Molybdenum Carbonyl Assisted Reductive Tetramerization of CO by Activated Magnesium(I) Compounds: Squarate Dianion vs. Metallo-Ketene Formation

Reactions of a dimagnesium(I) compound, [{(DipNacnac)Mg}2] (DipNacnac = [HC(MeCNDip)2]-, Dip = 2,6-diisopropylphenyl), pre-activated by coordination with simple Lewis bases (4-dimethylaminopyridine, DMAP; or TMC, :C(MeNCMe)2), with 1 atmosphere of CO in the presence of one equivalent of Mo(CO)6 at room temperature, led to the reductive tetramerisation of the diatomic molecule. When the reactions were carried out at room temperature, there is an apparent competition between the formation of magnesium squarate, [{(DipNacnac)Mg}(C4O4){-Mg(DipNacnac)}]2, and magnesium metallo-ketene products, [{(DipNacnac)Mg}{-(C4O4)Mo(CO)5}{Mg(D)(DipNacnac)}], which are not inter-convertible. Repeating the reactions at 80 °C led to the selective formation of the magnesium squarate, implying that this is the thermodynamic product. In an analogous reaction, in which THF is the Lewis base, only the metallo-ketene complex, [{(DipNacnac)Mg}{-(C4O4)Mo(CO)5}{Mg(THF)(DipNacnac)}] is formed at room temperature, while a complex product mixture is obtained at elevated temperature. In contrast, treatment of a 1:1 mixture of the guanidinato magnesium(I) complex, [(Priso)Mg‒Mg(Priso)] (Priso = [Pri2NC(NDip)2]-), and Mo(CO)6, with CO gas in a benzene/THF solution, gave a low yield of the squarate complex, [{(Priso)(THF)Mg}(C4O4){-Mg(THF)(Priso)}]2, at 80 °C. Computational analyses of the electronic structure of squarate and metallo-ketene product types corroborate the bonding proposed, from experimental data, for the C4O4 fragments of these systems

What controls the magnetic interaction in bis-μ-alkoxo mniii dimers? a combined experimental and theoretical exploration

The synthesis and magnetic characterisation of a series of bis-mu-alkoxide bridged MnIII dinuclear complexes of general formula [MnIII2(mu-OR)2(biphen)2(ROH)x(L)y] (where R=Me, Et; H2biphen=2,2\u27-biphenol and L=terminally bonded N-donor ligand) is described, doubling the literature basis set for this type of complex. Building on these findings we have categorised all known mu-OR bridged MnIII dinuclear complexes into one of three classifications with respect to their molecular structures. We have then employed DFT and MO calculations to assess all potential magneto-structural correlations for this class of compound in order to identify the structural requirements for constructing ferromagnetic family members. Our analysis indicates that the most influential parameter which governs the exchange interaction in this class of compounds is the relative orientation of the JT axes of the MnIII atoms. A perpendicular orientation of the JT axes leads to a large ferromagnetic contribution to the exchange. These results also suggest that a large ferromagnetic interaction and a large anisotropy are unlikely to co-exist in such structural types