Our model incorporates key features known to contribute to pulmonary vascular function in health and disease, including anatomical structure and multiple contributions from gravity. The model suggests that dynamic measurements obtained from catheterization potentially distinguish between distal and proximal vasculopathy typical of pulmonary arterial hypertension and chronic thromboembolic pulmonary hypertension. However, the model suggests a non-linear relationship between these data and vascular structural changes typical of pulmonary arterial hypertension and chronic thromboembolic pulmonary hypertension which may impede analysis of these metrics to distinguish between cohorts.The digitization of healthcare and its usage in the delivery of healthcare have experienced exponential growth across the world in recent times. India’s fast-growing diabetes population has been exerting immense pressure on the country’s healthcare infrastructure. Various innovative and evolving technologies are converging to impact the trajectory of digital health in diabetes. The diabetes community has been adopting various technologies such as connected glucose meters, continuous glucose monitoring systems, continuous subcutaneous insulin infusion, closed-loop systems, digitalization of health data, and diabetes-related apps for the prevention and management of the condition. India has provided some excellent examples in exploiting the potential of digital transformation in revamping the diabetes ecosystem. Yet, there are still various hurdles in technology development, healthcare delivery, as well as concerns related to data privacy, digital divide, policies by the government, role of stakeholders, attitude, and absorption by healthcare professionals, and hospitals. This article provides an overview of the digital diabetes technologies currently practiced in India and recommends the need for strong technology adaptation and policy interventions for an ideal roadmap of digitalization of diabetes care in the Indian milieu.Among gynecologic malignancies, ovarian cancer (OC) has the poorest survival rate, and its clinical management remains challenging due to the high rate of recurrence and chemoresistance. Improving survival for these patients is critical, although this requires the ability to translate preclinical studies to actual patient care bench to bedside and back. Our objective was to develop a preclinical model that accurately represents tumor biology and its microenvironment. We utilized SKOV-3, OVCAR-8, and CS-99 cell lines to show that this model was suitable for in vitro assessment of cell proliferation. We tested OC cells independently and in co-culture with cancer associated fibroblasts (CAFs) or immune cells. Additionally, we used patient-derived ovarian carcinoma and carcinosarcoma samples to show that the system maintains the histologic morphology of the primary tissue after 7 days. Moreover, we tested the response to chemotherapy using both cell lines and patient-derived tumor specimens and confirmed that cell death was significantly higher in the treated group compared to the vehicle group. Finally, we immune profiled the 3-D model containing patient tissue after several days in the bioreactor system and revealed that the immune populations are still present. Our data suggest that this model is a suitable preclinical model to aid in research that will ultimately impact the treatment of patients with gynecologic cancer.Synthetic phosphatidylinositol phosphate (PtdInsP n ) derivatives play a pivotal role in broadening our understanding of PtdInsP n metabolism. However, the development of such tools is reliant on efficient enantioselective and regioselective synthetic strategies. Here we report the development of a divergent synthetic route applicable to the synthesis of deuterated PtdIns4P and PtdIns5P derivatives. The synthetic strategy developed involves a key enzymatic desymmetrisation step using Lipozyme TL-IM®. In addition, we optimised the large-scale synthesis of deuterated myo-inositol, allowing for the preparation of a series of saturated and unsaturated deuterated PtdIns4P and PtdIns5P derivatives. Experiments in MCF7 cells demonstrated that these deuterated probes enable quantification of the corresponding endogenous phospholipids in a cellular setting. Overall, these deuterated probes will be powerful tools to help improve our understanding of the role played by PtdInsP n in physiology and disease.In photosensitizers, long triplet excited state lifetimes are key to their efficient electron transfer or energy transfer processes. Herein, we report a novel class of cyclic trimeric BODIPY arrays which were efficiently generated from easily accessible meso-mesityldipyrrinone and arylboronic acids in one pot. Arylboronic acid, for the first time, was used to provide a boron source for BODIPY derivatives. Due to the well-defined and orthogonally aligned BODIPY cores as verified by X-ray crystallography, these BODIPY arrays show strong exciton coupling effects and efficient intersystem crossings, and are novel heavy-atom-free photosensitizers with a long-lived triplet excited state (lifetime up to 257.5 μs) and good reactive oxygen species generation efficiency (up to 0.72) contributed by both 1O2 and O2 -˙ under light irradiation.Hydroformylation catalyzed by transition metals is one of the most important homogeneously catalyzed reactions in industrial organic chemistry. Millions of tons of aldehydes and related chemicals are produced by this transformation annually. However, most of the applied procedures use rhodium catalysts. In the procedure described here, a copper-catalyzed hydroformylation of alkenes has been realized. Remarkably, by using a different copper precursor, the aldehydes obtained can be further hydrogenated to give the corresponding alcohols under the same conditions, formally named as hydroxymethylation of alkenes. Under pressure of syngas, various aldehydes and alcohols can be produced from alkenes with copper as the only catalyst, in excellent regioselectivity. Additionally, an all-carbon quaternary center containing ethers and formates can be synthesized as well with the addition of unactivated alkyl halides. A possible reaction pathway is proposed based on our results.Recent computational methods have made strides in discovering well-structured cyclic peptides that preferentially populate a single conformation. However, many successful cyclic-peptide therapeutics adopt multiple conformations in solution. In fact, the chameleonic properties of some cyclic peptides are likely responsible for their high cell membrane permeability. Thus, we require the ability to predict complete structural ensembles for cyclic peptides, including the majority of cyclic peptides that have broad structural ensembles, to significantly improve our ability to rationally design cyclic-peptide therapeutics. Here, we introduce the idea of using molecular dynamics simulation results to train machine learning models to enable efficient structure prediction for cyclic peptides. Using molecular dynamics simulation results for several hundred cyclic pentapeptides as the training datasets, we developed machine-learning models that can provide molecular dynamics simulation-quality predictions of structural ensembles for all the hundreds of thousands of sequences in the entire sequence space. The prediction for each individual cyclic peptide can be made using less than 1 second of computation time. Even for the most challenging classes of poorly structured cyclic peptides with broad conformational ensembles, our predictions were similar to those one would normally obtain only after running multiple days of explicit-solvent molecular dynamics simulations. The resulting method, termed StrEAMM (Structural Ensembles Achieved by Molecular Dynamics and Machine Learning), is the first technique capable of efficiently predicting complete structural ensembles of cyclic peptides without relying on additional molecular dynamics simulations, constituting a seven-order-of-magnitude improvement in speed while retaining the same accuracy as explicit-solvent simulations.The first chiral phosphoric acid (CPA) catalyzed cycloaddition-elimination cascade reaction of 2-naphthol- and phenol-derived enecarbamates with azonaphthalenes has been established, providing a highly atroposelective route to an array of axially chiral aryl-C3-benzoindoles in excellent yields with excellent enantioselectivities. The success of this strategy derives from the stepwise process involving CPA-catalyzed asymmetric formal [3 + 2] cycloaddition and subsequent central-to-axial chirality conversion by elimination of a carbamate. In addition, the practicality of this reaction had been verified by varieties of transformations towards functionalized atropisomers.Here, the locus of functionalisation on graphene-related materials and the progress of the reaction is shown to depend strongly on the starting feedstock. Five characteristically different graphite sources were exfoliated and functionalized using a non-destructive chemical reduction method. These archetypical examples were compared via a model reaction, grafting dodecyl addends, evaluated with TGA-MS, XPS and Raman data. A general increase in grafting ratio (ranging from 1.1 wt% up to 25 wt%) and an improvement in grafting stoichiometry (C/R) were observed as flake radius decreased. Raman spectrum imaging of the functionalised natural flake graphite identified that grafting is directed towards flake edges. This behaviour was further corroborated, at atomistic resolution, by functionalising the graphene layers with bipyridine groups able to complex single platinum atoms. The distribution of these groups was then directly imaged using aberration-corrected HAADF-STEM. Platinum atoms were found to be homogeneously distributed across smaller graphenes; in contrast, a more heterogeneous distribution, with a predominance of edge grafting was observed for larger graphites. These observations show that grafting is directed towards flake edges, but not necessary at edge sites; the mechanism is attributed to the relative inaccessibility of the inner basal plane to reactive moieties, resulting in kinetically driven grafting nearer flake edges. This phenomenology may be relevant to a wide range of reactions on graphenes and other 2d materials.Conjugation of unprotected carbohydrates to surfaces or probes by chemoselective ligation reactions is indispensable for the elucidation of their numerous biological functions. In particular, the reaction with oxyamines leading to the formation of carbohydrate oximes which are in equilibrium with cyclic N-glycosides (oxyamine ligation) has an enormous impact in the field. Although highly chemoselective, the reaction is rather slow. Here, we report that the oxyamine ligation is significantly accelerated without the need for a catalyst when starting with glycosyl amines. Reaction rates are increased up to 500-fold compared to the reaction of the reducing carbohydrate. For comparison, aniline-catalyzed oxyamine ligation is only increased 3.8-fold under the same conditions. Glycosyl amines from mono- and oligosaccharides are easily accessible from reducing carbohydrates via the corresponding azides by using Shoda’s reagent (2-chloro-1,3-dimethylimidazolinium chloride, DMC) and subsequent reduction. Furthermore, glycosyl amines are readily obtained by enzymatic release from N-glycoproteins making the method suited for glycomic analysis of these glycoconjugates which we demonstrate employing RNase B.