Application of a distinctly bent, trinuclear, end-to-end azide bridged, mixed valence cobalt(iii/ii/iii) complex in the fabrication of photosensitive Schottky barrier diodes.

A mixed-valence trinuclear cobalt(iii)-cobalt(ii)-cobalt(iii) complex, [(µ-1,3-N3)Co3L(N3)3]·MeOH has been synthesized using a tetradentate N2O2 donor 'reduced Schiff base' ligand, H2L {1,3-bis(2-hydroxybenzylamino)2,2-dimethylpropane} and azide as anionic co-ligand. The complex has been characterised by elemental analysis, IR, UV-vis spectroscopy and single-crystal X-ray diffraction studies etc. The cobalt(iii)-cobalt(ii)-cobalt(iii) skeleton in the complex is non-linear and non-centrosymmetric. The redox behavior of the complex was studied by using Cyclic Voltammetry (CV). The complex is found to be a semiconductor material as confirmed by determining the band gap of this complex by experimental as well as theoretical studies. The band gap in the solid state has been determined experimentally. The conductivity of the synthesized complex based device improves considerably in illumination conditions from the non-illuminated conditions. The complex has also been used to fabricate Schottky barrier diodes.

The (o-p-o)-Terphenyl Embedded Calix[2]phyrin(2.2.1.1.1) and Its Cu(II) Complex.

The introduction of a higher arene unit as a structural motif is unprecedented in calixphyrin chemistry. Herein, the syntheses, spectral and structural characterization of heretofore anonymous terphenylene unit (o-p-o) incorporated calixphyrin with fused sp2 meso carbons is reported. The explicitly tailored macrocyclic core is utilized to stabilize the Cu(II) metal ion. The molecular structures of the calixbenziphyrin and Cu(II) complex are unambiguously confirmed by single-crystal X-ray analysis. Moreover, theoretical supports uphold experimental conclusions.

Breaking Global Diatropic Current to Tame Diradicaloid Character: Thiele's Hydrocarbon Under Macrocyclic Constraints.

A diradical/biradical character of organic derivatives is one of the key aspects of contemporary research focusing on the fundamental studies followed by potential applicability relying on the unique optical, electronic, or magnetic properties assigned to unpaired electrons. A precise involvement of two p-phenylenes into a cyclophane-like conjugated, diatropic system creates a flexible molecule with the two different characters of both subunits (benzene and quinone) imprinting into the structure a Kekulé delocalized system. A dynamic of both carbocyclic subunits, and their mutual interaction generates a singlet open-shell state (J=-1.25 kcal/mol) as documented spectroscopically (NMR and EPR). The extended theoretical analysis has proved a correlation between dihedral angle and the diradicaloid character that shifts from a closed-shell singlet to an open-shell state, eventually showing the y0=0.86 for 78 degrees and ΔEST=-0.34 kcal/mol.

Advent and features of pyriporphyrinoids: an overview of a pyridine-based porphyrin analogue.

Pyriporphyrinoids have recently attracted a significant proliferation of attention due to their versatile characters, which stem from structural motifs in which the pyridine moiety is involved. The evolution of pyriporphyrin chemistry revealed the subtle modifications of the macrocyclic core that tweak the electronic structure as compared to the parental macrocycle. The amendment of π-electronic organization inside the core manifests exceptional photophysical and coordination properties that cover a vast range of seemingly contradictory fields. In fundamental chemistry, the pyridine unit acts as a modulator of π-conjugated porphyrinoid systems, resulting in aromaticity swapping. From the applied chemistry perspective, these macrocycles are primarily utilized as (i) sensors, (ii) NIR absorbing photoacoustic dyes, (iii) electrochemical catalysts, (iv) singlet biradicaloid generation and (v) contributors to generate metal complexes with intriguing binding modes. Surprisingly, despite their prominence, pyriporphyrinoids are inadequately investigated, while pyridine unit-embedded calixphyrin, calixpyridinopyrrole and calixpyridine are barely reported. This review article illustrates the controlled formation of specific porphyrinic scaffolds with pyridine unit(s) and diverse functionalized heterocyclic and/or carbocyclic building block(s), and demonstrates a substantial influence on the macrocyclic properties.

Development of hierarchical copper sulfide-carbon nanotube (CuS-CNT) composites and utilization of their superior carrier mobility in efficient charge transport towards photodegradation of Rhodamine B under visible light.

In this work, the synthesis of visible light sensitive copper sulfide (CuS) nanoparticles and their composites with carbon nanotubes (T-CuS) via a solvothermal technique is reported. The synthesized nanoparticles (NPs) and their composites were significantly characterized by powder X-ray diffraction (PXRD), scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, UV-vis spectroscopy, photoluminescence (PL) spectroscopy and thermogravimetric analysis (TGA). The effect of carbon nanotubes (CNTs) on the crystallinity, microstructures, photo-absorption, photo-excitation, thermal stability and surface area of CuS was investigated. The current-voltage (I vs. V) characteristics of both CuS and T-CuS based Schottky diodes were measured to determine the charge transport parameters like photosensitivity, conductivity, mobility of charge carriers, and transit time. The photocatalytic performance of bare CuS and T-CuS in the decomposition of Rhodamine B dye was studied using a solar simulator. The T-CuS composite showed higher photocatalytic activity (94%) compared to bare CuS (58%). The significance of charge carrier mobility in transferring photo-induced charges (holes and electrons) through complex networks of composites and facilitating the photodegradation process is explained. Finally, the reactive species responsible for the Rhodamine B degradation were also identified.

Harnessing the hydrogen evolution reaction (HER) through the electrical mobility of an embossed Ag(I)-molecular cage and a Cu(II)-coordination polymer.

A structurally characterized porous Ag(I)-molecular cage AgMOC and a Cu(II)-coordination polymer CuCP with a pre-synthesized ligand 1,3-bis(((E)-2-methoxybenzylidene)amino)propan-2-ol and its parental amine with thiocyanate are reported to harness electrical mobility-driven hydrogen evolution activity. Porosity-induced electrically conductive AgMOC emerges as a better electrocatalyst with a Tafel slope of 104 mV per decade over Cu(II)-polymer's slope of 128 mV per decade. The electrochemical stability and durability of the designed electrocatalysts in harnessing the HER activity are also examined under experimental conditions.

Rh(I) and Organo-Rh(III) Complexes of meso-Triarylbiphenylcorrole.

Rhodium complexes of biphenylcorrole are reported, and the molecular structures of the complexes are unambiguously confirmed by single-crystal X-ray analysis. The adj-CCNN core of the dicarbacorrole efficiently stabilizes a rhodium metal ion in its two different oxidation states. It is pertinent to point out that the Rh(I) metal complex attains square-planar geometry while organo-Rh(III) forms an octahedral complex. Furthermore, density functional theory studies corroborate the experimental findings.

Effect of Higher Carrier Mobility of the Reduced Graphene Oxide-Zinc Telluride Nanocomposite on Efficient Charge Transfer Facility and the Photodecomposition of Rhodamine B.

The synthesis of solar-light-responsive zinc telluride (ZnTe) nanoparticles and their composite with reduced graphene oxide (rGO-ZnTe) via a simple hydrothermal reaction is reported. The synthesized nanostructures were comprehensively characterized by a combination of X-ray diffraction and photoelectron spectroscopy, electron microscopy, UV-vis spectroscopy, photoluminescence spectroscopy and thermogravimetric analysis. The effects of graphene oxide on the crystallinity, microstructure, photo-excitation, light absorption, surface area and thermal stability of ZnTe were studied. The current-voltage (I-V) characteristics for both as-synthesized ZnTe and rGO-ZnTe composite-based Schottky devices were measured to estimate the charge transport parameters such as dc conductivity, photosensitivity, carrier's mobility and lifetime. The photocatalytic performance of both the materials in the degradation of an azo dye (Rhodamine B) was subsequently investigated using simulated solar light. The rGO-ZnTe composite exhibited a higher photocatalytic activity (66%) as compared to the as-synthesized ZnTe (23%), essentially due to the synergy between rGO sheets and ZnTe nanoparticles. The role of the carrier's mobility in the transportation of photo-induced charges (electrons and holes) through the complex network of the composite materials and thus facilitating the photo-degradation process is explained. In the end, the responsible reactive species for the decomposition of Rhodamine B was also interpreted.

Designing water vapor fuelled brine-silk cocoon protein bio-battery for a self-lighting kettle and water-vapor panels.

Water vapor increases the electrical conductivity of silk cocoons, human hair, jute, and corn silk. This phenomenon is unclear. In the present study, XPS analysis of cocoons showed that water vapor reduces the surface presence of low-energy carbon species (C-C, C-H). In contrast, electron-dense, high-energy carbon species (C-N, C=C, C=O) remained unchanged, possibly enhancing surface charge hopping. While water vapor improves the conduction, the deficiency of charge carrier diminishes the effect. We increase the charge carrier by soaking the cocoon in an aqueous solution of common salt (NaCl) to amplify the current. Salt treatment followed by 2-min exposure to water vapor results in a sharp upward spike in the current (3.6 ± 1.07 mA, n = 12; mean ± SE) from the baseline (0.06 ± 0.02 mA, n = 12). After 1 h, it maintains an average value of 0.39 ± 0.12 mA; n = 12, indicating an upward shift in the baseline. Every time the cocoon charges with water vapor, the next charging cycle initiates after the cocoon dries up. Inspired by the cocoon ecology, we demonstrate an alternating 'water vapor-dry air' cycle for rapid charging and discharging of the cocoon battery. Finally, we designed a prototype of a self-lighting kettle and water-vapor panels for futuristic homes using a 'brine-silk cocoon protein bio-battery,' where moist waste heat generates electricity.

Devastating salt-wasting crisis in a four-month-old male child with congenital adrenal hyperplasia, highlighting the essence of neonatal screening.

Congenital adrenal hyperplasia (CAH) is a rare condition usually referred to as a group of genetic disorders resulting due to a deficiency of steroid enzymes required by adrenal glands to produce cortisol and mineralocorticoid hormones. It has an autosomal recessive mode of inheritance and is further categorized into two types-Classic and Non-Classic. Non-Classic CAH is a more common milder form that presents late after puberty. Classic CAH, although more severe, is rare and detected at birth and is associated with the life-threatening adrenal crisis in both sexes and virilization of the external genitalia in females (46, XX) patients, whereas in males, no overt abnormality of the external genitalia is present. We present a case of a four-month-old male child with the classic form of CAH who was brought with complaints of loose stools, projectile non bilious vomiting, decreased urine output, and failure to feed for 3 days. The child had a clinical presentation of salt wasting with hypoglycemia and hyperpigmentation of his genitalia. The USG findings revealed increased anteroposterior diameter of renal pelvis indicative of a growth in the suprarenal area. 17-hydroxyprogesterone (17-OHP) was found to be elevated confirming the diagnosis. He was treated with hydrocortisone with gradual improvement in his glucose and electrolytes. The patient was discharged home on replacement therapy consisting of oral prednisolone and fludrocortisone acetate and followed up as outpatient with significant improvement in the clinical findings. The fact that the child was not screened for CAH at birth led to the critical consequences of the disease in this case. To prevent life-threatening adrenal crisis and help perform appropriate sex assignments for affected female patients, newborn screening (NBS) programs for the classical form of CAH should be made mandatory even in low- and middle-income countries.

De novo synthesis of hybrid d-f block metal complex salts for electronic charge transport applications.

The advent of d-d type complex salts for designing smart functional materials with versatile utility inspired us to develop a novel type of M(II)-Ce(IV) complex salts [M(II) = Cu and Zn ions]. In this study, we present for the first time a holistic approach to design and prepare metal complex salts of the novel hybrid d-f block type, [Cu(bpy)2]2[Ce(NO3)6]2 (1), [Cu(phen)2(NO3)]2[Ce(NO3)6](HNO3) (2), [Zn(bpy)2(NO3)][ClO4] (3), and [Zn(phen)2(NO3)]2 [Ce(NO3)6] (4); [bpy = 2,2'-bipyridine; phen = 1,10-phenanthroline]. The intrinsic structural and morphological properties of the compounds have been revealed by employing a suite of analytical and spectroscopic methods. X-ray structural analysis reveals that the copper(II) centres in the cationic complex units of 1 and 2 adopt a highly distorted tetrahedral and a rare bicapped square pyramidal coordination geometry, respectively. The zinc(II) ions in both 3 and 4 adopt the rare bicapped square pyramidal geometry while the cerium(IV) ions in 1, 2 and 4 exist in a dodecahedral geometry. Investigation of supramolecular interactions reveals that intermolecular O⋯H and O⋯π short contacts bind the complex units in 1, while predominant π⋯π interactions, along with O⋯H and O⋯π short contacts, produce the binding force among the complex units in 2. We further employed the complex salts (1-4) to construct Schottky devices to reveal the role of these new complex salts in the charge-transport phenomenon. The carrier mobilities (µ) for salts 1-4 were determined to be 1.76 × 10-6, 9.02 × 10-6, 1.86 × 10-8, and 4.31 × 10-8 m2 V-1 s-1, with respective transit times (τ) of 439, 85, 4.17 × 103, and 1.79 × 103 ns, which suggest that complex salt 2 is the best candidate with the highest transport properties among all the complex salts. A crystal engineering perspective sheds light on the charge-transport properties of the complex salts, emphasizing the attribution of the best performance of 2 to its predominant π⋯π interactions. The synthesis of this new type of complex salts, their physicochemical properties and their charge-transport applications envisage great promise for the development of novel crystalline materials with smart functionalities.

Recent Advances in the Design and Syntheses of Porphyrinoids by Embedding Higher Analogues of Arene and Pyridine Units.

Due to enthralling applications in various fields and augmenting fundamental wisdom, π-conjugated macrocycles in general and porphyrin systems in particular are constantly explored. Subtle modifications of porphyrin structure can amend the rudimentary properties. Pursuing innovative properties provides impetus to underpin arene or pyridine moiety embedded porphyrin derivatives. There have been several reviews related to arene incorporated carbaporphyrinoids; however, recent developments of porphyrin analogues by introducing higher analogues of arenes and pyridine units are not adequately inspected. This mini-review mainly focuses on biphenyl, bipyridine, terphenyl, and mixed arene pyridine embedded porphyrin analogues and their coordination chemistry.

PtCl2 mediated peripheral transformation of carbatriphyrin(3.1.1) into a meso-fused ß-ß' dimer and its monomer analogue.

An unprecedented formation of a meso-fused ß-ß' carbaporphyrin dimer and its monomer with a keto group was described. These analogues were synthesized from carbatriphyrin(3.1.1.) by a metal assisted strategy using PtCl2 salt in a single step without any prefunctionalized precursors. Upon dimerization, the monomeric ligand with a dianionic core is transformed into a dimeric structure with unique trianionic cores.

Isosmaragdyrin with an N3C2 core: stabilization of Rh(i) and organo-Pt(ii) complexes.

Isosmaragdyrin with an N3C2 core is successfully achieved by introducing a 2,6-di-m-phenylpyridine unit. The core is utilized to stabilize the Rh(i) ion in the N-Rh(i)-N bonding mode and the Pt(ii) ion in the (N^C)N fashion to form an unsymmetrical pincer-type organometallic complex.

Structurally Isomerized Bis-Biphenyl Moieties Embedded in Hexaphyrin(3.1.1.3.1.1) and Octaphyrin(1.1.1.0.1.1.1.0).

An o-p-biphenyl moiety-incorporated 32π hexaphyrin(3.1.1.3.1.1) is successfully achieved. Replacing ortho with meta connectivity in the biphenyl unit of hexaphyrin leads to the formation of its structural isomer, octaphyrin(1.1.1.0.1.1.1.0). Spectral and structural analyses reveal the lack of planarity in hexaphyrin and the presence of an m-arene unit in octaphyrin, thus affording nonaromatic characteristics.

Bis-4,4'-biphenyl Ring Embedded Octaphyrin with Three Distinct Conformational Structures.

Three distinct conformational structures of carbaoctaphyrins were prepared by incorporating bis-4,4'-biphenyl units in the macrocyclic core. The free-base form adopts a figure-eight conformation, whereas the protonation triggers a conformational change with a pyrrole ring inversion and acquires an open-framework structure. The insertion of bis-RhI metal ion in the macrocyclic core affords a singly twisted conformational structure. Furthermore, the local aromaticity in the bis-4,4'-biphenyl ring dominates the overall macrocyclic aromaticity in all three forms, and thus adopts nonaromatic characteristics. These results are supported by spectral as well as theoretical studies, and they are unambiguously confirmed by X-ray crystal analyses.

Di-( m- m- m)terphenyl-Embedded Decaphyrin and Its Bis-Rh(I) Complex.

A new rectangular-shaped carbadecaphyrin was successfully synthesized by introducing a terphenylene unit ( m- m- m) in the macrocyclic core. The terphenylene moiety offers an open framework with multiple binding pockets to stabilize two Rh(I) ions in the core. The photophysical and structural studies reveal the non-aromatic character of the ligand and its bis-Rh(I) complex.

Homocarbaporphyrinoids: The m-o-m and p-o-p Terphenyl Embedded Expanded Porphyrin Analogues and Their RhI Complexes.

Stable homocarbaporphyrinoids were successfully synthesized by incorporating the m-o-m and p-o-p terphenyl units into the porphyrin core. The distinct bonding modes of terphenyl in the macrocycle generated two structural isomers with two and four carbon atoms in the macrocyclic environment. The core was utilized to stabilize the RhI ion. The spectral and structural analyses revealed that the restricted (m-o-m) and allowed (p-o-p) conjugation in the macrocyclic core provide overall non-aromatic characteristics both to the free bases and their complexes.

Aligned Chitosan-Gelatin Cryogel-Filled Polyurethane Nerve Guidance Channel for Neural Tissue Engineering: Fabrication, Characterization, and In Vitro Evaluation.

Recent trends in peripheral nerve regeneration are directed toward the development of nerve guidance channels to assist the regeneration of the nerves across critical size defects. Advanced nerve guidance channels (aNGCs) should possess multifunctional properties to direct the axonal regeneration from proximal to distal end, allow the concentration of growth factors secreted by the injured nerve end, and attenuate the ingrowth of scar tissue at the site of injury. The design of the nerve guidance channel (NGC) is critical for providing the necessary topographical, chemotactic, as well as haptotactic cues for efficient nerve regeneration. In this study, we have designed and fabricated clinically relevant aNGCs comprising an antioxidant polyurethane (PUAO) conduit filled with aligned chitosan-gelatin (CG) cryogel filler for peripheral nerve regeneration. The effects of temperature, polymer concentration, and cross-linker concentration on the physicochemical properties of the CG cryogel filler were studied. The synthesized scaffolds were evaluated by scanning electron microscopy (SEM) and compression testing to obtain the matrix best suited to form the aNGC. The nanofibrous PUAO conduit was fabricated by electrospinning with a wall thickness of 114.16 ± 26.91 µm, which was filled with CG (1.2/6.4%)-aligned cryogel matrix to obtain the aNGCs. The aNGCs with 2.01 ± 0.04 mm internal diameter, 15 mm length, and internal CG filler with a pore diameter of 29.60 ± 9.83 µm were fabricated. The aNGCs were evaluated by SEM and in vitro neuronal culture for biocompatibility and cellular alignment. In vitro dorsal root ganglion cultures showed the aligned growth and cellular migration along the aligned pores of aNGCs. With this study, we conclude that this clinically relevant aligned porous aNGC will have a promising effect in repair and regeneration of peripheral nerve injuries.