Phenalenyl-Based Photocatalyst for Bioinspired Oxidative Dehydrogenation of N-Heterocycles and Benzyl Alcohols.

The environmental benefits of molecular oxygen as the oxidizing agent in oxidation reactions that synthesize fine chemicals cannot be overstated. Increased interest in developing robust photocatalysts is stimulated by the fact that the current photocatalytic transformation boom has made previously inaccessible synthetic approaches possible. Motivated by enzymatic catalysis, employing a reusable phenalenyl-based photocatalyst, we have successfully developed oxidative dehydrogenation utilizing molecular oxygen as a greener oxidant. Under photoinduced oxidative dehydrogenation conditions, different types of saturated N-heterocycles and alcohols were successfully dehydrogenated. The versatility of this bioinspired protocol is demonstrated by the fact that a wide variety of N-heteroaromatics, such as quinoline, carbazole, quinoxaline, acridine, and indole derivatives, as well as aldehydes and ketones, were successfully synthesized. Detailed mechanistic studies validate the proposed mechanism. Fluorescence lifetime and CV experiments revealed the crucial role of water on the efficiency of the reaction. The present protocol also provides chemoselectivity and scalability, leading to superior results and allowing for the functionalization of bioactive molecules at a late stage in a sustainable manner.

Catalytic π-π Interactions Triggered Photoinduced Synthesis of Biaryls.

A highly regioselective photocatalytic method to access a variety of biaryl motifs under metal-free conditions has been developed. The organophotocatalyst is involved in π-π stacking interactions with the alkyne species, which promotes this photocatalytic process with thiophene. Mechanistic studies have shed light on these interactions and the overall process. Along with a broad functional-group tolerance and excellent regioselectivity, this protocol has been utilized in the late-stage functionalization of pharmaceuticals and other natural products.

Coordination Chemistry of Bis-Cyclic Alkyl(Amino) Carbene (cAAC)-Supported Di-Phosphorus (P2 ): An Efficient Route to Donor Base-Stabilized Elusive Di-Phosphorus-Monoxide(P2 O)-Gold Complex.

The stability and reactivity studies of heavier di-atomic group-15 congeners of alkynes, e. g., the di-phosphorus (P≡P) compounds have been the topic of huge interest because of their contrasting transient properties and lower stability compared to those of the stable molecular di-nitrogen (N≡N). Herein, we depict the reactivity studies of the bis-cAAC-stabilized di-phosphorus (P2 ) having an inversely polarized phosphaalkene nature featuring the C=P double bonds with Au(I)Cl. Both the mono-, and the di-aurated phosphaalkenes with the formulae [(Me2 -cAAC=P)2 (AuCl)] (2), and [(Me2 -cAAC=P)2 (AuCl)2 ] (3), respectively have been isolated in the solid state. Moreover, for the first time, we have been able to isolate the cAAC-stabilized tetra-aurated elusive di-phosphorus-monoxide (P2 O) with the formula [(Cy-cAAC=P)-O-(P=cAAC-Cy)(AuCl)4 ] (5) in presence of oxygen. Complexes 2-3, 5 have been structurally characterized by single crystal X-ray diffraction, and further studied by NMR spectroscopy. Our findings reveal significant elongation of the CcAAC -P bonds in 2-3, 5, and the presence of aurophilic interaction in 5. Quantum chemical calculations, including density functional theory (DFT), and energy decomposition analysis coupled with natural orbitals for chemical valence (EDA-NOCV) have been performed to study the electron densities distribution and nature of bonding in 2-3, 5.

Fruit waste: a current perspective for the sustainable production of pharmacological, nutraceutical, and bioactive resources.

Fruits are crucial components of a balanced diet and a good source of natural antioxidants, that have proven efficacy in various chronic illnesses. Various kinds of waste generated from fruit industries are considered a global concern. By utilizing this fruit waste, the international goal of "zero waste" can be achieved by sustainable utilization of these waste materials as a rich source of secondary metabolites. Moreover, to overcome this waste burden, research have focused on recovering the bioactive compounds from fruit industries and obtaining a new strategy to combat certain chronic diseases. The separation of high-value substances from fruit waste, including phytochemicals, dietary fibers, and polysaccharides which can then be used as functional ingredients for long-term health benefits. Several novel extraction technologies like ultrasound-assisted extraction (UAE), pressurized liquid extraction (PLE), and supercritical fluid extraction (SFE) could provide an alternative approach for successful extraction of the valuable bioactives from the fruit waste for their utilization as nutraceuticals, therapeutics, and value-added products. Most of these waste-derived secondary metabolites comprise polyphenols, which have been reported to have anti-inflammatory, insulin resistance-treating, cardiovascular disease-maintaining, probiotics-enhancing, or even anti-microbial and anti-viral capabilities. This review summarizes the current knowledge of fruit waste by-products in pharmacological, biological, and probiotic applications and highlights several methods for identifying efficacious bioactive compounds from fruit wastes.

Skeletal rearrangement through photocatalytic denitrogenation: access to C-3 aminoquinolin-2(1H)-ones.

The addition of an amine group to a heteroaromatic system is a challenging synthetic process, yet it is an essential one in the development of many bioactive molecules. Here, we report an alternative method for the synthesis of 3-amino quinolin-2(1H)-one that overcomes the limitations of traditional methods by editing the molecular skeleton via a cascade C-N bond formation and denitrogenation process. We used TMSN3 as an aminating agent and a wide variety of 3-ylideneoxindoles as synthetic precursors for the quinolin-2(1H)-one backbone, which demonstrates remarkable tolerance of sensitive functional groups. The control experiments showed that the triazoline intermediate plays a significant role in the formation of the product. The spectroscopic investigation further defined the potential reaction pathways.

Isolation of (Aryl)-(Imino) Phosphide and (Aryl)-(Phosphaalkene) Amide Complexes of Alkali Metals from Carbene-Phosphinidenes under Reductive-Thermal Rearrangements.

Invited for the cover of this issue are Sudipta Roy and co-workers at the Indian Institute of Science Education and Research (IISER) Tirupati. The image depicts the rearrangement of cyclic alkyl(amino) carbene (cAAC)-supported chloro-phosphinidenes affording two ligands, of which one was used for the solid-state isolation of three cyclic alkyl(amino-boryl) phosphaalkenes and two coinage metal clusters. Read the full text of the article at 10.1002/chem.202302120.

Unified Approach to Diverse Heterocyclic Synthesis: Organo-Photocatalyzed Carboacylation of Alkenes and Alkynes from Feedstock Aldehydes and Alcohols.

We report an organo-photocatalyzed carboacylation reaction that offers a springboard to create chemical complexity in a diversity-driven approach. The modular one-pot method uses feedstock aldehydes and alcohols as acyl surrogates and commercially available Eosin Y as the photoredox catalyst, making it simple and affordable to introduce structural diversity. Several biologically relevant skeletons have been easily synthesized under mild conditions in the presence of visible light irradiation by fostering a radical acylation/cyclization cascade. The proposed reaction mechanism was further illuminated by a number of spectroscopic studies. Furthermore, we applied this protocol for the late-stage functionalization of pharmaceuticals and blockbuster drugs.

Isolation of (Aryl)-(Imino) Phosphide and (Aryl)-(Phosphaalkene) Amide Complexes of Alkali Metals from Carbene-Phosphinidenes under Reductive-Thermal Rearrangements.

Two-electron reduction of cyclic alkyl(amino) carbene (cAAC)-supported chloro-phosphinidene cAAC=P-Cl (1) followed by unprecedented thermal rearrangements afforded the alkali metal complexes of (aryl)-(cyclic alkyl(imino)) phosphides 3 a-3 c, 4 a-4 b through migration of the 2,6-diisopropylphenyl (dipp) group from N to the P centre, and the (aryl)-(cyclic alkyl(phosphaalkene)) amide 5 through cleavage of the CMe2 -N bond followed by energetically favoured 5-exo-tet ring-closure in the presence of the alkali metals Cs (3 a-3 c), K (4 a, 4 b), and Li (5). Compound 3 a was found to be photoluminescent (PL), emitting bright orange light under a laboratory UV lamp of wavelength 365 nm with PL quantum yield (ϕPL ) of 2.6 % (λem =600 nm), and an average lifetime (τ) of 4.8 µs. Reaction of 3 a with CuCl and AgOTf afforded (aryl)-(cyclic alkyl(imino)) phosphide-stabilized tetra-nuclear CuI (6), and octa-nuclear AgI (7) clusters, respectively. Moreover, complexes 3 a-3 c provided a direct route for the stabilization of cyclic alkyl(aminoboryl) phosphaalkenes 8 a-8 c when treated with 1-bromo-N,N,N',N'-tetraisopropylboranediamine.

A skin lesion hair mask dataset with fine-grained annotations.

Occlusion of skin lesions in dermoscopic images due to hair affects the performance of computer-assisted lesion analysis algorithms. Lesion analysis can benefit from digital hair removal or realistic hair simulation techniques. To assist in that process, we have created the largest publicly available skin lesion hair segmentation mask dataset by carefully annotating 500 dermoscopic images. Compared to the existing datasets, our dataset is free of non-hair artifacts like ruler markers, bubbles, and ink marks. The dataset is also less prone to over and under segmentations because of fine-grained annotations and quality checks from multiple independent annotators. To create the dataset, first, we collected five hundred copyright-free CC0 licensed dermoscopic images covering different hair patterns. Second, we trained a deep learning hair segmentation model on a publicly available weakly annotated dataset. Third, we extracted hair masks for the selected five hundred images using the segmentation model. Finally, we manually corrected all the segmentation errors and verified the annotations by superimposing the annotated masks on top of the dermoscopic images. Multiple annotators were involved in the annotation and verification process to make the annotations as error-free as possible. The prepared dataset will be useful for benchmarking and training hair segmentation algorithms as well as creating realistic hair augmentation systems.

Colon Disease Diagnosis with Convolutional Neural Network and Grasshopper Optimization Algorithm.

This paper presents a robust colon cancer diagnosis method based on the feature selection method. The proposed method for colon disease diagnosis can be divided into three steps. In the first step, the images' features were extracted based on the convolutional neural network. Squeezenet, Resnet-50, AlexNet, and GoogleNet were used for the convolutional neural network. The extracted features are huge, and the number of features cannot be appropriate for training the system. For this reason, the metaheuristic method is used in the second step to reduce the number of features. This research uses the grasshopper optimization algorithm to select the best features from the feature data. Finally, using machine learning methods, colon disease diagnosis was found to be accurate and successful. Two classification methods are applied for the evaluation of the proposed method. These methods include the decision tree and the support vector machine. The sensitivity, specificity, accuracy, and F1Score have been used to evaluate the proposed method. For Squeezenet based on the support vector machine, we obtained results of 99.34%, 99.41%, 99.12%, 98.91% and 98.94% for sensitivity, specificity, accuracy, precision, and F1Score, respectively. In the end, we compared the suggested recognition method's performance to the performances of other methods, including 9-layer CNN, random forest, 7-layer CNN, and DropBlock. We demonstrated that our solution outperformed the others.

Stabilisation and reactivity studies of donor-base ligand-supported gallium-phosphides with stronger binding energy: a theoretical approach.

Gallium phosphide is a three-dimensional polymeric material of the hetero-diatomic GaP unit, which has a wurtzite type structure, and captivating application as a light emitting diode (LED). As a result, there is a constant search for suitable precursors to synthesise GaP-based materials. However, the corresponding monomeric species is exotic in nature due to the expected Ga[triple bond, length as m-dash]P multiple bond. Herein, we report on the theoretical studies of stability, chemical bonding, and reactivity of the monomeric gallium phosphides with two donor base ligands having tuneable binding energies. We have performed detailed investigations using density functional theory at three different levels (BP86/def2-TZVPP, B3LYP/def2-TZVPP, M06-2X/def2-TZVPP), QTAIM and EDA-NOCV (BP86-D3(BJ)/TZ2P, M06-2X/TZ2P) to analyse various ligand-stabilised GaP monomers, which revealed the synthetic viability of such species in the presence of stable singlet carbenes, e.g., cAAC, and NHC as ligands [cAAC = cyclic alkyl(amino) carbene, NHC = N-heterocyclic carbene] due to the larger bond dissociation energy compared to a phosphine ligand (PMe3). The calculated bond dissociation energies between a pair of ligands and the monomeric GaP unit are found to be in the range of 87 to 137 kcal mol-1, predicting their possible syntheses in the laboratory. Further, the reactivity of such species with metal carbonyls [Fe(CO)4, and Ni(CO)3] have been theoretically investigated.

Introducing Phenalenyl-Based Organic Lewis Acid as a Photocatalyst to Facilitate Oxidative Azolation of Unactivated Arenes.

By revealing the robust photooxidant properties of phenalenyl-based organic Lewis acid, we have introduced this moiety as an effective organophotocatalyst for the oxidative azolation of unactivated and feedstock arenes. In addition to its tolerance for various functional groups and scalability, this photocatalyst was shown to be promising for the defluorinative azolation of fluoroarenes.

Photoinduced Cerium-Mediated Decarboxylative Alkylation Cascade Cyclization of N-arylacrylamides and N-acryl-2-aryl benzimidazoles.

A mild and versatile cerium-mediated decarboxylative strategy for sequential alkylation/cyclization was developed for the synthesis of quaternary oxindoles and benzimidazo[2,1-a]isoquinolin-6(5H)-ones via photoinduced-LMCT. This operationally simple procedure relies on inexpensive and feedstock carboxylic acids as alkyl radical surrogates and aerial molecular oxygen as the terminal oxidant. This mild and atom economical protocol showed viability with a wide range of alkyl carboxylic acids (1° to 3° acids) as coupling partners and also allows the late-stage modification of pharmaceutically-important acids. Mechanistic studies revealed the reaction to follow radical pathway, while the decarboxylative event was studied by in situ FTIR.

Light-Induced Activation of C-X Bond via Carbonate-Assisted Anion-π Interactions: Applications to C-P and C-B Bond Formation.

We have presented a carbonate anion assisted photochemical protocol for the C-X bond activation. Anion-π interactions have been leveraged to generate aryl radicals from easily accessible aryl halides that are further utilized in C-P and C-B bond formation reactions with excellent reactivity and broad functional group tolerance. Spectroscopic investigations and DFT studies were conducted for mechanistic insights. This inexpensive method alleviates the use of a photocatalyst and the need of preactivation of the substrate for the light-induced activation of C-X bonds.

Genetic characterization of dengue virus from patients presenting multi-serotypic infections in the Northern West Bengal, India.

Northern West Bengal, popularly known as North Bengal, is a dengue-endemic area, which has been severely affected by Dengue in the past few years resulting in massive hospitalizations and deaths. Genetic characterization of the circulating endemic dengue virus (DENV) serotypes is of paramount importance for the epidemiological understanding of the infection and subsequent vaccine development. The present study was conceived to characterize circulating dengue serotypes and to undertake phylogenetic study. EDTA blood samples of all (N = 83) NS1-positive cases of patients with acute febrile illness referred to different health care facilities were collected and processed for RNA isolation followed by the complementary DNA (cDNA) preparation. Serotype determination of dengue infection was done using conventional PCR by targeting the viral C-prM region. Phylogenetic tree was constructed by implementing the Maximum likelihood method. Out of 83 blood samples 17 were detected to be positive for the presence of dengue viral RNA. DENV3 was found to be the predominant serotype in the single-infection cases; however, we have detected multi-serotypic co-infections throughout the study. Joint pain was found to be the most valuable symptom for the prognosis of dengue. Sequence analyses suggested that both DENV1- and DENV3-circulating genotypes are in the genotype III group and remain closely related to the Indian clade. To the best of our knowledge, this is the first report on the genetic characterization of circulating DENVs in North Bengal, which may contribute to the study of dengue epidemic and pathogenesis.

Making and Breaking of C-N Bonds: Applications in the Synthesis of Unsymmetric Tertiary Amines and α-Amino Carbonyl Derivatives.

An operationally simple process has been developed for the synthesis of unsymmetrical amines and α-amino carbonyl derivatives in the absence of a catalyst, ligand, oxidant, or any additives. Contrary to known reductive amination methods, this protocol is amenable to substrates containing other reducible groups. This process effectively results in consecutive cleavage and formation of C-N bonds. DFT studies and Hammett analysis provide useful insight into the mechanism. The role of noncovalent interactions as a stabilizing factor have been examined in the protocol. A wide range of alkyl-bromides have been coupled efficiently with a variety of dimethyl anilines to get unsymmetric tertiary amines with yields up to 90%. This methodology was further extended to the synthesis of α-amino carbonyl derivatives with yields up to 93%.

Phylogenetic, structural, functional characterisation and effect of exogenous spermidine on rice (Oryza sativa) HAK transporters under salt stress.

The HAK (High-affinity K+ ) family members mediate K+ transport that confers normal plant growth and resistance against unfavourable environmental conditions. Rice (Oryza sativa L.) HAK transporters have been extensively investigated for phylogenetic analyses with other plants species with very few of them functionally characterised. But very little information is known about their evolutionary aspects, overall structural, functional characterisation, and global expression pattern of the complete HAK family members in response to salt stress. In this study, 27 rice transporters were phylogenetically clustered with different dicot and monocot family members. Subsequently, the exon-intron structural patterns, conserved motif analyses, evolutionary divergence based different substitution matrix, orthologous-paralogous relationships were studied elaborately. Structural characterisations included a comparative study of secondary and tertiary structure, post-translational modifications, correspondence analyses, normal mode analyses, K+ /Na+ binding affinities of each of the OsHAK gene members. Global expression profile under salt stress showed clade-specific expression pattern of the proteins. Additionally, five OsHAK genes were chosen for further expression analyses in root and shoot tissues of two rice varieties during short-term salinity in the presence and absence of exogenous spermidine. All the information can be used as first-hand data for dissecting the administrative role of rice HAK transporters under various abiotic stresses.

An Institution Based Cross-Sectional Observational Aetiological Study Correlating the Clinico-Pathological Findings in Patients Presenting with Acquired Palmoplantar Keratoderma.

Background: Palmoplantar keratoderma (PPK) is a heterogeneous group of hereditary or acquired disorders characterised by excessive epidermal thickening of the palms and soles. Proper knowledge about the aetiology of the disease and clinico-demographic profile helps in planning management and predicting outcomes. Aims and Objective: To determine the prevalence of different dermatoses and describe their clinico-histological correlation in acquired palmoplantar keratoderma. Materials and Methods: An institution-based cross-sectional study conducted after obtaining Ethics-Committee permission and consent from participants. Patients of any age or gender presenting with acquired PPK were recruited. The calculated sample size was 67 by using the prevalence rate (p) of 22.2%, allowable error (L) of 10%, the confidence level of 95% (z = 1.96), and an infinite population size of 20,000. Patients were evaluated by taking demographic and clinical data in a pre-designed case record form, necessary laboratory investigations and histopathological examination that wereevaluated by three blinded experts. The pooled data were analysed with statistical software. Results: Among the 67 participants, Psoriasis was diagnosed clinically in 39 (58.2%) and histologically in 7 (10.4%), Lichen planus (LP) clinically in 16 (23.9%) and histologically in 9 (13.4%), Pityriasis rubra pilaris (PRP) in 8 (11.9%) patients clinically and 7 (10.4%) histologically and Hyperkeratotic eczema (HKE) in 4 (6%) clinically and 43 (64.2%) histopathologically. There was very poor inter-rater agreement (Kappa = 0.148, SE 0.0047, 95% CI 0.057 to 0.24). The clinico-pathological correlation was found to be agreeable in 17.9% Psoriasis, 56.2% LP and 87.5% PRP. HKE was commonly misdiagnosed as Psoriasis in 65.1% of patients. Conclusion: Hyperkeratotic lesions of the palm and sole often present with overlapping clinical features and a skin biopsy has to be done to aid in diagnosis. Limitation: Stratification of the clinical expertise of clinicians was done during the analysis.

Transforming Non-innocent Phenalenyl to a Potent Photoreductant: Captivating Reductive Functionalization of Aryl Halides through Visible-Light-Induced Electron Transfer Processes.

Herein, we have established a phenalenyl-based molecular scaffold which serves as a potent photoreductant utilizing the empty NBMO in the presence of a base to form a radical anion which, upon photoexcitation, behaves as a stronger reductant and accomplishes the cleavage of strong C-X (X = Cl, Br, I) bonds under milder reaction conditions. The base was found to be involved in a dual role of electron and hydrogen atom donor. Further, the aryl radical formed by the homolysis of C-X bonds in this technique was captured for the Csp2-Csp2 coupling with unactivated arenes. The photoreductant potency of the phenalenyl-based catalytic system was further extended to C-P as well as C-B bond formation reactions. EPR and lifetime studies reveal the formation of a persistent radical having a sufficient lifetime to take part in the reaction by the PET mechanism. Different spectroscopic techniques combined with DFT calculations were utilized for the characterization of active catalytic species and for the elucidation of plausible mechanistic pathways. This not only is the initial report of the application of phenalenyl as a photoreductant but also provides a completely metal-free (alkali and transition metal) approach for the challenging reductive functionalization of aryl halides at room temperature.