Neutral Phosphorus-Based Beryllium Scorpionate Complexes as Spectroscopic Probes for Base Strength and Electron Donation.

The synthesis and properties of tris(diisopropylphosphanylmethyl)phenylborate ([TP(Pr)]) beryllium complexes [TP(Pr)]Be with = Cl, Br, I, CN, SCN, OCN, N, and CFSO are described. In these compounds, the NMR coupling constant can be used as a sensitive probe for the basicity and electron-donating properties of the anions in solution.

Formation, Structure and Reactivity of a Beryllium(0) Complex with Mg-Be Bond Polarization.

Attempts to create a novel Mg-Be bond by reaction of [(BDI*)MgNa] with Be[N(SiMe)] failed; BDI*=HC[(tBu)C=N(DIPeP)], DIPeP=2,6-EtC-phenyl. Even at elevated temperatures, no conversion was observed. This is likely caused by strong steric shielding of the Be center.

Glioblastoma-instructed microglia transition to heterogeneous phenotypic states with phagocytic and dendritic cell-like features in patient tumors and patient-derived orthotopic xenografts.

Background: A major contributing factor to glioblastoma (GBM) development and progression is its ability to evade the immune system by creating an immune-suppressive environment, where GBM-associated myeloid cells, including resident microglia and peripheral monocyte-derived macrophages, play critical pro-tumoral roles. However, it is unclear whether recruited myeloid cells are phenotypically and functionally identical in GBM patients and whether this heterogeneity is recapitulated in patient-derived orthotopic xenografts (PDOXs). A thorough understanding of the GBM ecosystem and its recapitulation in preclinical models is currently missing, leading to inaccurate results and failures of clinical trials.

The driving force behind tool-stone selection in the African Middle Stone Age.

In the Stone Age, the collection of specific rocks was the first step in tool making. Very little is known about the choices made during tool-stone acquisition. Were choices governed by the knowledge of, and need for, specific properties of stones? Or were the collected raw materials a mere by-product of the way people moved through the landscape? We investigate these questions in the Middle Stone Age (MSA) of southern Africa, analyzing the mechanical properties of tool-stones used at the site Diepkloof Rock Shelter.

Gauging ambiphilicity of pseudo-halides beryllium-trispyrazolylborato compounds.

The ambiphilicity of pseudo-halides has been the object of extensive debate. Herein, we use a series of trispyrazolylborato beryllium pseudo-halido complexes [TpBe(X')] with X' = CN, N, NCO and NCS to explore the origins of the preferred isomers. Thus, we have synthesised and characterised through NMR and IR spectroscopy as well as single crystal X-ray diffraction these complexes.

Beryllium-Mediated Halide and Aryl Transfer onto Silicon.

The reactivity of hexamethylcyclotrisiloxane (D ) towards BeCl , BeBr , BeI and [Be Ph ] was investigated. While BeCl only showed unselective reactivity, BeBr , BeI and [Be Ph ] cleanly react to the trinuclear complexes [Be Br (OSiMe Br) ], [Be I (OSiMe I) ] and [Be Ph (OSiMe Ph) ]. These unprecedented bromide, iodide and phenyl transfer reactions from a group II metal onto silicon offer a versatile access to previously unknown diorgano bromo and iodo silanolates.

A Preference for Heterolepticity - Schlenk Type Equilibria in Organometallic Beryllium Systems.

The reaction of homoleptic beryllium halide with diphenyl beryllium complexes leads to the clean formation of heteroleptic beryllium Grignard compounds [(L) BePhX] (X=Cl, Br, I; L=C-, N-, O-donor ligand). The influence of ligands and solvent on these compounds, their formation and exchange equilibria in solution were investigated, together with the factors determining the complex constitution.

Bismuth in Dynamic Covalent Chemistry: Access to a Bowl-Type Macrocycle and a Barrel-Type Heptanuclear Complex Cation.

Dynamic covalent chemistry (DCvC) is a powerful and widely applied tool in modern synthetic chemistry, which is based on the reversible cleavage and formation of covalent bonds. One of the inherent strengths of this approach is the perspective to reversibly generate in an operationally simple approach novel structural motifs that are difficult or impossible to access with more traditional methods and require multiple bond cleaving and bond forming steps. To date, these fundamentally important synthetic and conceptual challenges in the context of DCvC have predominantly been tackled by exploiting compounds of lighter p-block elements, even though heavier p-block elements show low bond dissociation energies and appear to be ideally suited for this approach.

Glioblastoma-instructed microglia transition to heterogeneous phenotypic states with phagocytic and dendritic cell-like features in patient tumors and patient-derived orthotopic xenografts.

Background: A major contributing factor to glioblastoma (GBM) development and progression is its ability to evade the immune system by creating an immune-suppressive environment, where GBM-associated myeloid cells, including resident microglia and peripheral monocyte-derived macrophages, play critical pro-tumoral roles. However, it is unclear whether recruited myeloid cells are phenotypically and functionally identical in GBM patients and whether this heterogeneity is recapitulated in patient-derived orthotopic xenografts (PDOXs). A thorough understanding of the GBM ecosystem and its recapitulation in preclinical models is currently missing, leading to inaccurate results and failures of clinical trials.

Reactivity of Diphenylberyllium as a Brønsted Base and Its Synthetic Application.

Diphenylberyllium [Be Ph ] is shown here to react cleanly as a Brønsted base with a vast variety of protic compounds. Through the addition of the simple molecules tBuOH, HNPh and HPPh , as well as the more complex 1,3-bis-(2,6-diisopropylphenyl)imidazolinium chloride, one or two phenyl groups in diphenylberyllium were protonated. As a result, the long-postulated structures of [Be (OtBu) ] and [Be(μ-NPh )Ph] have finally been verified and shown to be static in solution.

Radiotherapy for nasopharyngeal cancer.

Nasopharyngeal cancers are a rarity in France. Radiotherapy is the cornerstone of treatment, frequently combined with chemotherapy. The technical modality of radiotherapy is complex in this disease, which is located in the vicinity of numerous organs at risk.

Therapeutic maps for a sensor-based evaluation of deep brain stimulation programming.

Programming in deep brain stimulation (DBS) is a labour-intensive process for treating advanced motor symptoms. Specifically for patients with medication-refractory tremor in multiple sclerosis (MS). Wearable sensors are able to detect some manifestations of pathological signs, such as intention tremor in MS.

Tumour motion management in lung cancer: a narrative review.

Respiratory motion is one of the geometrical uncertainties that may affect the accuracy of thoracic radiotherapy in the treatment of lung cancer. Accounting for tumour motion may allow reducing treatment volumes, irradiated healthy tissue and possibly toxicity, and finally enabling dose escalation. Historically, large population-based margins were used to encompass tumour motion.

Long-term outcomes and safety after reirradiation in locally recurrent nasopharyngeal carcinoma in a non-endemic area.

Purpose: To determine outcomes and toxicities after reirradiation for locally recurrent nasopharyngeal carcinoma (rNPC) and to apply a prognostic index in a non-endemic region.

Methods: We retrospectively reported progression-free survival (PFS), overall survival (OS), and treatment-related toxicities in patients treated with curative intent for locally rNPC. We applied the prognostic model for OS and grade 5 radiotherapy (RT)-related toxicities published by Li et al.

[Degenerative cervical spine diseases: fusion vs. total disc replacement : What can be done when?].

Motion preserving surgery within the cervical spine may be performed by special implants, for example, c spine disc prosthesis or total disc replacement (cTDR), or by simple decompression of the cervical nerve roots. However, also fusion surgery may be performed with good results. Here, we summarize indications as well as contraindications for motion preserving techniques and indications for fusion surgery.

Optimisation of reconstruction, volumetry and dosimetry for Tc-SPECT and Y-PET images: Towards reliable dose-volume histograms for selective internal radiation therapy with Y-microspheres.

Purpose: In Selective Internal Radiation Therapy (SIRT), Tc-MAA SPECT images are commonly used to predict microspheres distribution but recent works used Y-microspheres PET images. Nevertheless, evaluation of the predictive power of Tc-MAA has been hampered by the lack of reliable comparisons between Tc-SPECT and Y-PET images. Our aim was to determine the "in situ" optimisation procedure in order to reliably compare Tc-SPECT and Y-PET images and achieve optimal personal dosimetry.

Long-term stability of an injection-molded zirconia bone-level implant: A testing protocol considering aging kinetics and dynamic fatigue.

Objective: Separately addressing the fatigue resistance (ISO 14801, evaluation of final product) and aging behavior (ISO 13356, standardized sample) of oral implants made from yttria-stabilized zirconia proved to be insufficient in verifying their long-term stability, since (1) implant processing is known to significantly influence transformation kinetics and (2) aging, up from a certain level, is liable to decrease fatigue resistance. Therefore, the aim of this investigation was to apply a new testing protocol considering environmental conditions adequately inducing aging during dynamic fatigue.

Methods: Zirconia implants were dynamically loaded (10 cycles), hydrothermally aged (85°, 60 days) or subjected to both treatments simultaneously.

Establishing Local Diagnostic Reference Levels in IR Procedures with Dose Management Software.

Purpose: To obtain local diagnostic reference levels (DRLs) in diagnostic and therapeutic IR procedures with dose management software to improve radiation protection.

Materials And Methods: Dose data of various vascular and nonvascular IR procedures performed within 18 months were collected and analyzed with dose management software. To account for different levels of complexity, procedures were subdivided into simple, standard, and difficult procedures as graded by interventional radiologists.

Glycemia, Treatment Satisfaction, Cognition, and Sleep Quality in Adults and Adolescents with Type 1 Diabetes When Using a Closed-Loop System Overnight Versus Sensor-Augmented Pump with Low-Glucose Suspend Function: A Randomized Crossover Study.

Background: We compared glycemia, treatment satisfaction, sleep quality, and cognition using a nighttime Android-based hybrid closed-loop system (Android-HCLS) with sensor-augmented pump with low-glucose suspend function (SAP-LGS) in people with type 1 diabetes.

Materials And Methods: An open-label, prospective, randomized crossover study of 16 adults (mean [SD] age 42.1 [9.

Exploration of the Performance of a Hybrid Closed Loop Insulin Delivery Algorithm That Includes Insulin Delivery Limits Designed to Protect Against Hypoglycemia.

Background: Hypoglycemia remains a risk for closed loop insulin delivery particularly following exercise or if the glucose sensor is inaccurate. The aim of this study was to test whether an algorithm that includes a limit to insulin delivery is effective at protecting against hypoglycemia under those circumstances.

Methods: An observational study on 8 participants with type 1 diabetes was conducted, where a hybrid closed loop system (HCL) (Medtronic™ 670G) was challenged with hypoglycemic stimuli: exercise and an overreading glucose sensor.

Post-operative imaging in deep brain stimulation: A controversial issue.

In deep brain stimulation (DBS), post-operative imaging has been used on the one hand to assess complications, such as haemorrhage; and on the other hand, to detect misplaced contacts. The post-operative determination of the accurate location of the final electrode plays a critical role in evaluating the precise area of effective stimulation and for predicting the potential clinical outcome; however, safety remains a priority in postoperative DBS imaging. A plethora of diverse post-operative imaging methods have been applied at different centres.