Nucleation-Growth Versus Spinodal Decomposition in Fe-Cr Alloys: An Experimental Verification by Atom Probe Tomography and Small Angle Neutron Scattering.

Identifying the operative mode of phase separation [spinodal decomposition (SD) or nucleation-growth (NG)] remains an extremely important area of research. The present work examines this critically in the Fe-Cr system using atom probe tomography (APT) and small angle neutron scattering (SANS), and establishes the framework to distinguish the two different modes of α' phase separation in thermally aged Fe-35 at% Cr and Fe-20 at% Cr alloys. Independent APT analysis determines the mode of phase separation on the basis of (i) the presence/absence of periodic chemical fluctuation through radial distribution function analysis and (ii) interphase interface characteristics (diffuse/sharp). SANS analysis, in contrast, yields virtually indistinguishable correlation peaks for both the modes, which necessitates further investigation of the several different aspects of SANS profiles in the light of APT results. For the first time, key features of SANS profiles have been identified that can unambiguously distinguish SD from NG in the Fe-Cr system: (i) nature of temporal evolution of FWHM of the correlation peak and (ii) appropriate value of γ for fitting with the dynamic scaling model (γ = 6 for SD, Fe-35 at% Cr alloy; γ = 4 for NG, Fe-20 at% Cr alloy).

Weakly coordinating tert-amide assisted Rh(III)-catalyzed C4-cyanation of indoles: application in photophysical studies.

A rhodium(III)-catalyzed indole C4-selective cyanation is described using the bench-stable, user-friendly electrophilic cyanation agent N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) as a coupling partner. A suitably positioned weakly coordinating tert-amide group was utilized for this site selectivity. The developed protocol proceeded with a broad scope. [Cp*Rh(MeCN)3][SbF6]2 was found to be an effective Rh(III) catalyst for this transformation. An initial study was carried out to know the photophysical properties of the C4-cyanated indole frameworks.

Biomimetic chlorine-induced polyene cyclizations harnessing hypervalent chloroiodane-HFIP assemblies.

While bromo- and iodocyclizations have recently been successfully implemented, the challenging chlorocyclizations have been scantly investigated. We present a selective and generally applicable concept of chlorination-induced polyene cyclization by utilizing HFIP-chloroiodane networks mimicking terpene cyclases. A manifold of different alkenes was converted with excellent selectivities (up to d.r. >95 : 5). The cyclization platform was even extended to several structurally challenging terpenes and terpenoid carbon frameworks.

Pd(II)-Catalyzed Oxidative Naphthylation of 2-Pyridone through N-H/C-H Activation Using Diarylacetylene as an Uncommon Arylating Agent.

A Pd(II)-catalyzed straightforward oxidative naphthylation of unmasked 2-pyridone derivatives is described using a twofold internal alkyne as a coupling partner. The reaction proceeds through N-H/C-H activation to provide polyarylated N-naphthyl 2-pyridones. An unusual oxidative annulation at the arene C-H bond of the diarylalkyne leads to the formation of polyarylated N-naphthyl 2-pyridones, where the 2-pyridone-attached phenyl ring of the naphthyl ring is polyaryl-substituted. Mechanistic studies and DFT calculations suggest a plausible mechanism based on N-H/C-H activation. The N-naphthyl 2-pyridone derivatives were studied to explore encouraging photophysical properties.

Enzyme-like polyene cyclizations catalyzed by dynamic, self-assembled, supramolecular fluoro alcohol-amine clusters.

Terpene cyclases catalyze one of the most powerful transformations with respect to efficiency and selectivity in natural product (bio)synthesis. In such polyene cyclizations, structurally highly complex carbon scaffolds are built by the controlled ring closure of linear polyenes. Thereby, multiple C,C bonds and stereocenters are simultaneously created with high precision. Structural pre-organization of the substrate carbon chain inside the active center of the enzyme is responsible for the product- and stereoselectivity of this cyclization. Here, we show that in-situ formed fluorinated-alcohol-amine supramolecular clusters serve as artificial cyclases by triggering enzyme-like reactivity and selectivity by controlling substrate conformation in solution. Because of the dynamic nature of these supramolecular assemblies, a broad range of terpenes can be produced diastereoselectively. Mechanistic studies reveal a finely balanced interplay of fluorinated solvent, catalyst, and substrate as key to establishing nature's concept of a shape-selective polyene cyclization in organic synthesis.

Cu(II)-Catalyzed Construction of Heterobiaryls using 1-Diazonaphthoquinones: A General Strategy for the Synthesis of QUINOX and Related P,N Ligands.

An efficient and straightforward method was developed for the synthesis of heterobiaryls using easily available N-oxides and diazonaphthoquinones under cheap Cu(II) catalysis. The developed method offered QUINOX and related congeners in a simple manner. A wide scope of important heterobiaryls was achieved with high site selectivity. The synthesized naphthols were transformed into the privileged related P,N ligands. Suitable resolution methods can directly afford the corresponding axially chiral heterobiaryls.

A Combinatorial Approach to Reliable Quantitative Analysis of Small Nano-Sized Precipitates: A Case Study with α' Precipitates in Fe-20 at% Cr Alloy.

The quantitative characterization of small nano-sized precipitates poses genuine challenges and is often deficient in accuracy due to the inherent limitations inevitably associated with the individual experimental techniques. A convenient solution is to utilize multiple complementary techniques. The present work demonstrates an effective way to reliably quantify nano-sized precipitates using a combination of complementary techniques of atom probe tomography (APT), small angle neutron scattering (SANS), and transmission electron microscopy (TEM). As a case study, the size (radius, r), number density (NP), volume fraction (ϕ), and chemical composition of Cr-rich α' precipitates are determined in Fe­20 at% Cr alloy, thermally aged at 773 K for 1,000 h. This combinatorial approach utilizes the strength of each technique in such a way that the overall accuracy of quantitative precipitation analysis improves significantly. For example, the superior spatial resolution makes TEM the appropriate technique to estimate the size and size distribution of the precipitates, while APT provides the chemical composition. Similarly, SANS analysis incorporates both the size and the compositional information thus derived independently and provides statiscally averaged quantitative analysis overcoming the field-of-view limitations of both TEM and APT. This combinatorial approach improves the accuracy of quantification and provides the true representation of the microstructure.

Straightforward Construction and Functionalizations of Nitrogen-Containing Heterocycles Through Migratory Insertion of Metal-Carbenes/Nitrenes.

Nitrogen-containing heterocycles are widely found in various biologically active substrates, pharmaceuticals, natural products and organic materials. Consequently, the continuous effort has been devoted towards the development of straightforward, economical, environmentally acceptable, efficient and ingenious methods for the synthesis of various N-containing heterocycles and their functionalizations. Arguably, one of the most prominent direct strategy is regioselective C-H bond functionalizations which provide the step and atom economical approaches in the presence of suitable coupling partners. In this context, site-selective migratory insertion of metal carbenes/nitrenes to the desired C-H bonds has proven as a useful tool to access various functionalized nitrogen heterocycles. In this personal account, we highlight some of our contemporary development toward constructing N-containing heterocycles and their direct functionalizations via transition metal catalysed C-H bond functionalizations based on migratory insertion of metal-carbenes and nitrenes.

Structural Characterization of the Hidden Peptide SHPRH-146aa Encoded by Non-Coding circ-SHPRH to Act as Tumor Suppressor.

Circular RNAs belong to the class of non-coding RNA molecules, though surprisingly some of them have protein-coding potentials. However, the circular RNA circ-SHPRH is known to code for an unusual protein known as SHPRH-146aa. However, the molecular level details of the protein are not yet identified. It was proposed that the protein has its role in glioblastoma. Therefore, in this work, an attempt was made to decipher the various structural features of SHPRH-146aa. The binding interactions of the protein SHPRH-146aa with its partner protein DTL were also analyzed. The main aim of the work was to decipher the characteristics features of this unusual protein and the region on SHPRH-146aa that would form different types of non-covalent binding interactions both among itself as well as with its binding partner. In this work, we tried to elucidate the various structural and physico-chemical features of the protein as well as its mode of interactions with its binding partner. The study would therefore pave the pathway to design future wet lab experiments to delineate the appropriate structural features of the protein as well as its association with glioblastoma and neuro-degenerative diseases.

Transition Metal-Catalysed Direct C-H Bond Functionalizations of 2-Pyridone Beyond C3-Selectivity.

2-Pyridone is a ubiquitous motif in natural products, drug molecules, ligands in catalysis and organic materials. There is a necessity of direct step-economic methods for the construction of 2-pyridone based molecules. Strategically, the primary developments have led to the C3-functionalizations due to the inherent reactivity of this center. Despite this, many elegant transition metal-catalysed methods have been established to introduce versatile functional groups at the C4, C5 and C6-position via direct C-H bond functionalizations. This minireview focuses on the categorized introduction of different functional groups at the 2-pyridone scaffolds beyond C3-selectivity and discusses substrate scope, limitations and plausible mechanistic details.

Rh(iii)-Catalyzed tandem indole C4-arylamination/annulation with anthranils: access to indoloquinolines and their application in photophysical studies.

An efficient Rh(iii)-catalyzed straightforward strategy was developed for the tandem C4 arylamination/annulation of indole derivatives with anthranil to provide indoloquinoline moieties. This method is simple and regioselective with a wide scope and functional group tolerance. Mechanistic studies revealed the important role of the newly installed azacycle in the conversion of O-protected aldoximes to their cyano derivatives. Studies were carried out to explore the promising photophysical properties of the obtained indoloquinoline derivatives.

RhIII -Catalyzed Synthesis of Highly Substituted 2-Pyridones using Fluorinated Diazomalonate.

A RhIII -catalyzed strategy was developed for the rapid construction of highly substituted 2-pyridone scaffolds using α,ß-unsaturated oximes and fluorinated diazomalonate. The reaction proceeds through direct, site-selective alkylation based on migratory insertion and subsequent cyclocondensation. A wide substrate scope with different functional groups was explored. The requirement of fluorinated diazomalonate was explored for this transformation. The developed methodology was further extended with the synthesis of the bioactive compound.

Magnetic ordering of the martensite phase in Ni-Co-Mn-Sn-based ferromagnetic shape memory alloys.

The magnetic state of low temperature martensite phase in Co-substituted Ni-Mn-Sn-based ferromagnetic shape memory alloys (FSMAs) has been investigated, in view of numerous conflicting reports of occurrences of spin glass (SG), superparamagnetism (SPM) or long range anti-ferromagnetic (AF) ordering. Combination of DC magnetization, AC susceptibility and small angle neutron scattering (SANS) studies provide clear evidence for AF order in the martensitic phase of Ni45Co5Mn38Sn12 alloy and rule out SPM and SG orders. Identical studies on another alloy of close composition, Ni44Co6Mn40Sn10, point to the presence of SG order in the martensitic phase and the absence of SPM behavior, contrary to earlier reports. SANS results do show the presence of nanometre-sized clusters but they are found to grow in size from 3 nm at 30 K to 11 nm at 300 K, and do not correlate with magnetism in these alloys.

Revisiting Temporal Evolution of Cu-Rich Precipitates in Fe-Cu Alloy: Correlative Small Angle Neutron Scattering and Atom-Probe Tomography Studies.

Binary Fe-Cu alloys are effective prototypes for investigating radiation-induced formation and growth of nanometric Cu-rich precipitates (CRPs) in nuclear reactor pressure vessels. In this report, the temporal evolution of CRPs during thermal aging of Fe-Cu binary alloys has been investigated by using complementary techniques such as atom probe tomography (APT) and small-angle neutron scattering (SANS). We report a detailed quantitative evolution of a rarely observed morphological transformation of Cu precipitates from spherical to ellipsoid with a significant change (approximately two times) in aspect ratio, an effect known to be associated with the 9R-3R structural transition of the precipitates. It is demonstrated through APT that the precipitates remain spherical up to 8 h, however, they subsequently convert to oblate ellipsoid upon further aging. SANS analysis also detected signs of this morphological transition in reciprocal space. Furthermore, SANS quantifies evolution of the precipitates and corroborates well with the APT results. Interestingly, the power-law exponent of the temporal evolution for mean size and number density agree reasonably well with the Lifshitz-Slyozov-Wagner model, in spite of the complex morphological evolution of the precipitates.

RhIII -Catalyzed Straightforward Synthesis of Benzophenanthroline and Benzophenanthrolinone Derivatives using Anthranils.

An efficient pot-economic and step-economic RhIII -catalyzed site-selective direct amination/annulation strategy was developed for the synthesis of benzophenanthroline derivatives using quinoline N-oxides and anthranils. The method was further extended to the synthesis of nitrogen-containing extended π-conjugated benzophenanthrolinone derivatives. Late-stage functionalizations of cinchonidine and cinchophen derivatives and synthesis of a bioactive quinolino-indole were achieved.

RhIII -Catalyzed Direct C8-Arylation of Quinoline N-Oxides using Diazonaphthalen-2(1H)-ones: A Practical Approach towards 8-aza BINOL.

An efficient RhIII -catalyzed redox-neutral method for the direct C8-arylation of quinoline N-oxides using diazonaphthalen-2(1H)-one as coupling partner has been demonstrated. The developed method is simple, scalable and straightforward with a wide range of substrate scope. The applicative potential was extended with a late-stage functionalization and straightforward synthesis of 8-azaBINOL derivative. A plausible reaction pathway was proposed after carrying out preliminary control studies.

A Mild Rhodium Catalyzed Direct Synthesis of Quinolones from Pyridones: Application in the Detection of Nitroaromatics.

A rhodium catalyzed direct regioselective oxidative annulation by double C-H activation is described to synthesize highly substituted quinolones from pyridones. The reaction proceeds at mild conditions with broad scope and wide functional group tolerance. These novel quinolones were explored to recognize nitroaromatic compounds.

Copper-Catalyzed Direct, Regioselective Arylamination of N-Oxides: Studies To Access Conjugated π-Systems.

An efficient copper(I)-catalyzed direct regioselective arylamination of various heterocyclic N-oxides was achieved successfully under redox-neutral conditions using anthranils as arylaminating reagents. The developed protocol is simple, straightforward, and economic with a broad range substrate scope. The dual functional groups in the final molecules were utilized to construct structurally and functionally diverse nitrogen-containing organic π-conjugated systems.

Copper-Catalyzed Regioselective Cascade Alkylation and Cyclocondensation of Quinoline N-Oxides with Diazo Esters: Direct Access to Conjugated π-Systems.

An inexpensive copper-catalyzed cascade regioselective alkylation, followed by cyclocondensation of quinoline N-oxides with α-diazo esters has been achieved successfully to provide heteroarene-containing conjugated π-systems. The developed method is simple, straightforward, and economical with a broad range of substrate scope. The dual role of copper catalyst in the C-H bond functionalization and in Lewis acid-promoted cyclization was explored.

C6-Selective Direct Alkylation of Pyridones with Diazo Compounds under Rh(III)-Catalyzed Mild Conditions.

A Rh(III)-catalyzed highly efficient C6-alkylation of 2-pyridones has been achieved successfully with α-diazo carbonyl compounds. The developed method is simple, mild, and highly regioselective with a broad range of substrate scope. The regioselectivity is guided by the pyridyl substituent attached to the nitrogen center of the pyridone ring. The directing group can be easily removed, and the only formed byproduct is nitrogen. Furthermore, other similar heterocyclic scaffolds can also be functionalized regioselectively under the developed conditions.