Electron donor-acceptor complex enabled photocascade strategy for the synthesis of -dihydrofuro[3,2-]chromen-4-one scaffolds radical conjugate addition of pyridinium ylide.

A visible-light-induced photocascade strategy is disclosed for the synthesis of -dihydrofuro[3,2-]chromen-4-one scaffolds. The photocascade consists of electron donor-acceptor (EDA) complex enabled formation of arylidene coumarinone, followed by 1,4-radical conjugate addition (1,4-RCA) of an generated pyridinium ylide radical (PyYR) towards diastereoselective formation of the -dihydrofuro[3,2-]chromen-4-one scaffold in good to excellent yield. Thorough mechanistic investigations comprising photophysical, spectroscopic, electrochemical and DFT studies provide further insights into the reaction mechanism.

Assessment of Diaphragmatic Dysfunction in Mechanically Ventilated Patients with Ultrasonography.

Introduction: The reliability of the diaphragm thickening fraction in predicting weaning failure in mechanically ventilated patients in the intensive care unit (ICU), as well as the relationship between the patients' diaphragmatic inspiratory excursion and diaphragmatic thickness.

Materials And Methods: Fifty mechanically ventilated patients participated in this hospital-based cross-sectional prospective study in a tertiary care teaching hospital. Patients who had been on a mechanical ventilator for at least 7 days and whose legal guardian was willing to provide consent were also included in the research.

Predicting the mechanical properties of pristine and defective carbon nanotubes using a random forest model.

Data-driven models have lately emerged as a faster and less time-consuming method for computing material properties than computationally expensive conventional molecular dynamics and density functional theory-based simulations. Here, we developed a random forest (RF) model for comprehensively predicting mechanical properties such as stress and Poisson's ratio under varying strain and ultimate tensile strain of pristine and defective carbon nanotubes (CNTs). The variations in stress and Poisson's ratio with the strain of CNTs with a 0.

Manganese catalyzed chemo-selective synthesis of acyl cyclopentenes: a combined experimental and computational investigation.

Cyclopentenes serve as foundational structures in numerous natural products and pharmaceuticals. Consequently, the pursuit of innovative synthetic approaches to complement existing protocols is of paramount importance. In this context, we present a novel synthesis route for acyl cyclopentenes through a cascade reaction involving an acceptorless-dehydrogenative coupling of cyclopropyl methanol with methyl ketone, followed by a radical-initiated ring expansion rearrangement of the formed vinyl cyclopropenone intermediate.

Divergent Synthesis of Pyrazoles via Manganese Pincer Complex Catalyzed Acceptorless Dehydrogenative Coupling Reactions.

This report detailed the synthesis of multi-substituted pyrazoles through the acceptorless dehydrogenative coupling (ADC) reaction catalyzed by a well-defined manganese(I)-pincer complex. Symmetrically substituted pyrazoles were synthesized by reacting 1,3-diols with hydrazines. Unsymmetrically substituted pyrazoles were selectively made via the ADC of primary alcohols with methyl hydrazones.

Catalytic acceptorless dehydrogenative borylation of styrenes enabled by a molecularly defined manganese complex.

In this study, we employed a 3d metal complex as a catalyst to synthesize alkenyl boronate esters through the dehydrogenative coupling of styrenes and pinacolborane. The process generates hydrogen gas as the sole byproduct without requiring an acceptor, rendering it environmentally friendly and atom-efficient. This methodology demonstrated exceptional selectivity for dehydrogenative borylation over direct hydroboration.

Visiblelight-induced ternary electron donor-acceptor complex enabled synthesis of 2-(2-hydrazinyl) thiazole derivatives and the assessment of their antioxidant and antidiabetic therapeutic potential.

A mild and eco-friendly visible-light-induced synthesis of 2-(2-hydrazinyl) thiazole from readily accessible thiosemicarbazide, carbonyl, and phenacyl bromide in the absence of a metal catalyst and/or any extrinsic photosensitizer is reported. This approach only requires a source of visible light and a green solvent at room temperature to produce the medicinally privileged scaffolds of hydrazinyl-thiazole derivatives in good to outstanding yields. Experimental studies support the formation of a visible-light-absorbing, photosensitized colored ternary EDA complex.

Ruthenium-Catalyzed Reductive Coupling of Epoxides with Primary Alcohols via Hydrogen Transfer Catalysis.

Herein, we report the ruthenium-catalyzed synthesis of β-alkylated secondary alcohols via the regioselective ring-opening of epoxides with feedstock primary alcohols. The reaction utilized alcohol as the carbon source and the terminal reductant. Kinetic and labeling experiments elucidate the hydrogen transfer catalysis that operates via tandem Markovnikov selective transfer hydrogenation of terminal epoxides and hydrogen transfer-mediated cross-coupling of the resulting alcohol with primary alcohol substrates.

Influence of Triazole Substituents of Bis-Heteroleptic Ru(II) Probes toward Selective Sensing of Dihydrogen Phosphate.

A series of seven new bis-heteroleptic Ru(II) probes (-) along with two previously reported probes ( and ) containing a similar anion binding triazole unit (hydrogen bond donor) functionalized with various substituents are employed in a detailed comparative investigation for the development of superior selective probes for HPO. Various solution- and solid-state studies, such as H-DOSY NMR, dynamic light scattering (DLS), single-crystal X-ray crystallography, and transmission electron microscopy (TEM), have established that the selective sensing of HPO by this series of probes is primarily due to supramolecular aggregation driven enhancement of MLCT emission. Intestingly, and , having an electron-deficient (π-acidic) aromatic pentafluorophenyl substituent are found to be superior probes for HPO in comparison to the other aryl- and polyaromatic-substituted analogues (-, , and ), in terms of a higher enhancement of the MLCT emission band, a greater binding constant, and a lower detection limit.

Cu(II)-Metallacryptands Self-Assembled to Vesicular Aggregates Capable of Encapsulating and Transporting an Anticancer Drug Inside Cancer Cells.

Crystallographically characterized M L type cationic Cu(II)-metallacryptands [MC(X)] derived from a series of bis-pyridyl-bis-urea ligands (L ; X = O, S, C) are self-assembled to single-layered vesicular aggregates in DMSO, DMSO/water, and DMSO/DMEM (biological media). One such vesicle is MC(O)-vesicle that is demonstrated to be able to load and release (pH responsive) an anticancer drug, namely doxorubicin hydrochloride (DOX). DOX-loaded MC(O)-vesicle is also successfully transported within MDA-MB-231 cells-a highly aggressive human breast cancer cell line.

Design and Synthesis of Zn -Coordination Polymers Anchored with NSAIDs: Metallovesicle Formation and Multi-drug Delivery.

A series of coordination polymers synthesized from a bis-pyridyl linker, namely 4,4'-azopyridine (L), selected non-steroidal-anti-inflammatory drugs (NSAIDs), namely diclofenac (Dic), ibuprofen (Ibu), flurbiprofen (Flu), mefenamic acid (Mefe), and naproxen (Nap), and Zn(NO ) were characterized by single crystal X-ray diffraction. One of the coordination polymers, namely CP3 derived from Flu, was able to form metallovesicles in DMSO, DMSO/H O and DMSO/DMEM (biological media) as revealed by TEM, AFM and DLS. Metallovesicle formation by CP3 was further supported by loading a fluorescent dye, namely calcein, as well as an anti-cancer drug, doxorubicin hydrochloride (DOX), as revealed by UV-vis and emission spectra, and fluorescence microscopy.

Self-Assembly of Spherical Organic Molecules to Form Hollow Vesicular Structures in Water for Encapsulation of an Anticancer Drug and Its Release.

Developing hierarchical supramolecular structures is important for better understanding of various biological functions and possibly generating new materials for biomedical applications. Herein, we report the first examples of functional vesicles derived from cationic spherical organic molecules (C -C ) which were readily synthesized by reacting a C -symmetric tris-benzimmidazole derivative (possessing a 1,3,5-ethyl substituted aromatic core) with 1,3,5-substituted tris-bromomethyl benzene derivatives. Vesicle formation by C -C was probed by high-resolution microscopy (TEM and AFM), dynamic light scattering (DLS) and fluorescence microscopic imaging of calcein-loaded vesicles.

Rational Approach Towards Designing Metallogels From a Urea-Functionalized Pyridyl Dicarboxylate: Anti-inflammatory, Anticancer, and Drug Delivery.

A structural rationale was adopted to design a series of metallogels from a newly synthesized urea-functionalized dicarboxylate ligand, namely, 5-[3-(pyridin-3-yl)ureido]isophthalic acid (PUIA), that produces metallogels upon reaction with various metal salts (Cu , Zn , Co , Cd , and Ni salts) at room temperature. The gels were characterized by dynamic rheology and transmission electron microscopy (TEM). The existence of a coordination bond in the gel state was probed by FTIR and H NMR spectroscopy in a Zn metallogel (i.

Rationally Developed Metallogelators Derived from Pyridyl Derivatives of NSAIDs Displaying Anti-Inflammatory and Anticancer Activities.

Metal-ligand coordination involving hydrogen-bond-functionalized ligands was employed rationally to get an easy access to a series of metallogelators derived from 3-pyridyl derivatives of nonsteroidal anti-inflammatory drugs [e.g., ibuprofen, sulindac, and flurbiprofen designated as 3-pyIBU, 3-pySUL, and 3-pyFLR, respectively] and biogenic metal centers [Zn(II), Cu(II), Mn(II), and Ag(I)].

Exfoliated Nanosheets of a Cu Coordination Polymer Modulate Enzyme Activity of α-Chymotrypsin.

A 2D coordination polymer derived from 5-azidoisophthalic acid (AIA) and Cu(NO ) was designed with the aim of modulating the activity of a digestive enzyme α-chymotrypsin (ChT). The coordination polymer namely {[Cu (μ-AIA) (H O)]⋅2 H O} (CP1) was successfully synthesized and fully characterized by single-crystal X-ray diffraction (SXRD). An exfoliated nanosheet (ENS) of CP1 was readily produced by overnight stirring of hand-ground CP1 crystals dispersed in DMSO.

Supramolecular Hydrogel Derived from a C-Symmetric Boronic Acid Derivative for Stimuli-Responsive Release of Insulin and Doxorubicin.

A C-symmetric triazine based triboronic acid (HG1) was designed and synthesized. HG1 was found to give hydrogel in DMSO-water (1:9). The hydrogel was rheo-reversible and thermoreversible over a few cycles.

A case of symptomatic tailgut duplication cyst(retro-rectal cystic hamartoma) in an adult male.

Tailgut duplication cyst (retro-rectal cystic hamartoma) is a rare congenital developmental lesion arising from post-natal primitive gut remnants. Tailgut cysts are found more commonly in middle-aged females. It may be asymptomatic or symptomatic in complicated cases.

Hand-Ground Nanoscale Zn -Based Coordination Polymers Derived from NSAIDs: Cell Migration Inhibition of Human Breast Cancer Cells.

Increased levels of intracellular prostaglandin E (PGE ) have been linked with the unregulated cancer cell migration that often leads to metastasis. Non-steroidal anti-inflammatory drugs (NSAIDs) are known inhibitors of cyclooxygenase (COX) enzymes, which are responsible for the increased PGE concentration in inflamed as well as cancer cells. Here, we demonstrate that NSAID-derived Zn -based coordination polymers are able to inhibit cell migration of human breast cancer cells.

Multifunctional single-layered vesicles derived from Cu(ii)-metal-organic-polyhedra.

Cu(ii) metal-organic-polyhedra (MOP) derived from a tris-pyridyl ligand gave stable single-layered vesicles capable of encapsulating an anti-cancer drug (doxorubicin - DOX) and its pH responsive release. While encapsulation of DOX was further confirmed by MTT assay and cellular imaging, α-chymotrypsin inhibition assay corroborated well with the single crystal structures of the MOP. The MOP derived vesicles reported herein not only represent the rare examples of such hierarchical architectures derived from MOP but also provide the first example of multifunctional organic-inorganic synthetic bio-membranes.

Nanoscale Mn -Coordination Polymers for Cell Imaging and Heterogeneous Catalysis.

A mixed ligand approach was exploited to synthesize a new series of Mn -based coordination polymers (CPs), namely, CP1 {[Mn(μ-dpa)(μ-4,4'-bp)]⋅MeOH} , CP2 {[Mn (μ-dpa) (2,2'-bp) ]} , CP3 {[Mn (μ-dpa) (1,10-phen) ]⋅2 H O} , CP4 {[Mn(μ-dpa)(μ-4,4'-bpe) ]⋅H O} , CP5 {[Mn (μ-dpa) (μ-4,4'-bpe) ]⋅1/2  DEF} , and CP6 {[Mn(μ-dpa)(μ-4,4'-bpe) ]⋅1/2  DMA} (dpa=3,5-dicarboxyphenyl azide, 2,2'-bp=2,2'-bipyridine, 1,10-phen=1,10-phenanthroline, 4,4'-bpe=1,2-bis(4-pyridyl)ethylene, 4,4'-bp=4,4'-bipyridine, DEF=N,N-diethylformamide, DMA=N,N-dimethylacetamide), to develop multifunctional CPs. Various techniques, such as single-crystal X-ray diffraction (SXRD), FTIR spectroscopy, elemental analysis, and thermogravimetric analysis, were employed to fully characterize these CPs. The majority of the CPs displayed a four-connected sql topology, whereas CP4 and CP6 exhibited a two-dimensional SnS network architecture, which was further entangled in a polycatenation mode.

Congenital malrotation of the liver in an asymptomatic adult: a rare entity.

Congenital malformations of the liver are rare occurrences. We are reporting a case of malrotation of the liver. The patient was asymptomatic and had undergone a non-contrast CT scan of the upper abdomen, which showed malrotation of the liver.

Metallogels from Coordination Complexes, Organometallic, and Coordination Polymers.

A supramolecular gel results from the immobilization of solvent molecules on a 3D network of gelator molecules stabilized by various supramolecular interactions that include hydrogen bonding, π-π stacking, van der Waals interactions, and halogen bonding. In a metallogel, a metal is a part of the gel network as a coordinated metal ion (in a discrete coordination complex), as a cross-linking metal node with a multitopic ligand (in coordination polymer), and as metal nanoparticles adhered to the gel network. Although the field is relatively new, research into metallogels has experienced a considerable upsurge owing to its fundamental importance in supramolecular chemistry and various potential applications.

FNAC Versus Core Needle Biopsy: A Comparative Study in Evaluation of Palpable Breast Lump.

Introduction: Breast carcinoma is the most common malignant tumour and the leading cause of carcinoma death in women in world. The main purpose of FNAC or CNB of breast lumps is to confirm cancer preoperatively and to avoid unnecessary surgery in specific benign conditions.

Aims And Objective: The objective of the study was to compare between Fine Needle Aspiration Cytology (FNAC) and Core Needle Biopsy (CNB) in the diagnosis of breast carcinoma with final histological diagnosis from excision specimen as it is gold standard.