Crafting sustainable solutions: architecting biodegradable copolymers through controlled ring-opening copolymerization.

Polylactic acid (PLA) is a biodegradable and biocompatible polymer with versatile applications in packaging and medicine. It is derived from lactic acid and thus represents an eco-friendly option sourced from renewable raw materials. Despite its advantages, PLA exhibits few drawbacks, such as brittleness and relatively high melting and glass transition temperatures. However, these limitations can be addressed through copolymerization with other monomers like ε-caprolactone (ε-CL), resulting in a composite material with improved physical properties. This paper comprehensively reviews achievements in PLA-PCL copolymerization using organometallic catalysts, discussing scientific findings and various copolymer architectures obtained, including random or block configurations. It also demonstrates various sustainable catalysts for achieving the required microstructure under mild reaction conditions without the aid of any external initiator.

Tri-coordinated zinc alkyl complexes with N

A series of tri-coordinated zinc alkyl complexes with the general molecular formula [κ2NE-{NHIRP(Ph)(E)N-Dipp}ZnEt] [R = Dipp (2,6-diisopropylphenyl), E = S (3a), Se (3b) and R = tBu (tert-butyl), E = S (4a), Se (4b)] bearing imino-phosphanamidinate chalcogenide ligands were prepared in good yields from the reaction between the protic imino-phosphanamidinate chalcogenide ligand [NHIRP(Ph)(E)NH-Dipp] [R = Dipp, E = S (1a), Se (1b) and R = tBu, E = S (2a), Se (2b)] and diethylzinc at room temperature. The molecular structures of all the zinc complexes were established by single-crystal X-ray diffraction analysis. In the solid state, all complexes exhibited a distorted trigonal planar geometry around the zinc ion. Metal-chalcogenide (Zn-S/Se) interactions were observed in the coordination sphere. These zinc alkyl complexes were employed as pre-catalysts in the hydroboration reaction of nitriles and esters to obtain the corresponding N,N-diborylamines and boronate esters, respectively, under ambient conditions. A wide substrate scope of nitriles and esters is presented.

Unprecedented ROP of quinazolinones to polyacylamidines using a cesium catalyst.

Unprecedented ring-opening polymerization of quinazolinones to produce novel polyacylamidines, led by a unique cooperation between a cesium metal center and imino-phosphanamidinate ligand, was developed. Morphological studies revealed the formation of a unique macromolecular assembly producing nanofibers in the absence of a templating agent with excellent control of molecular weights and polydispersity index.

Magnesium-Catalyzed Dye-Embedded Polylactide Nanoparticles for the Effective Killing of Highly Metastatic B16F10 Melanoma Cells.

In the current research, dye-embedded polylactic acid (PLA) conjugate materials were synthesized using one-pot ring-opening polymerization (ROP), i.e., (dtHPLA) (2-[(2,4,6-trimethylphenyl) imino]-1(2H)-acenaphthylenone-reduced-PLA) and (dmHPLA) (monoiminoacenaphtheneone-reduced-PLA), and then, nanoparticles (NPs) were engineered in the size range of 150 ± 30 nm. P(dtHPLA) NPs were employed in the treatment of melanoma, an aggressive type of skin cancer, which mandates the development of novel techniques to enhance healing outcomes and eliminate adverse effects related to existing treatments. In addition to exhibiting strong intracellular absorption in the spheroid model, the P(dtHPLA) NPs exhibited a strong cytotoxic effect on B16F10 cells, which resulted in oxidative stress from the generation of reactive oxygen species (ROS) and cell death. Additionally, a live/dead experiment using P(dtHPLA) NPs revealed a notable reduction in cell viability.

Hydrosilylation of nitriles and tertiary amides using a zinc precursor.

We report a competent and selective hydrosilylation of nitriles and tertiary amides catalyzed by the readily available zinc bis(hexamethyldisilazide) under solvent-free and mild conditions, making it a sustainable and desirable alternative to existing methods. Both protocols afforded high conversion, superior selectivity, and a broad substrate scope, from electron-withdrawing to electron-donating and heterocyclic substitutions.

Role of Bis(phosphinimino)methanides as Universal Ligands in the Coordination Sphere of Metals across the Periodic Table.

The coordination chemistry of bis(phosphinimino)methanide ligands is widespread and accompanies a large number of metal ions in the periodic table ranging from lithium to neptunium. This unique class of ligand systems show copious coordination chemistry with the main-group, transition, rare-earth, and actinide metals and are considered to be among the most attractive ligand systems to researchers. The bis(phosphinimino)methanide metal complexes offer an extensive range of applications in various fields and have been demonstrated as one of the universal ligand systems to stabilize the metal ions in not only their usual but also their unusual oxidation states. The main-group and transition metal chemistry using bis(phosphinimino)methanides as ligands was last updated almost a decade ago. In this review, we provide a comprehensive overview of various state-of-the-art bis(phosphinimino)methanide-supported metal complexes by dealing with their synthesis, characterization, reactivity, and catalytic studies which were not included in the last critical reviews.

Amidophosphine Boranes as Hydroboration Reagents for Nitriles, Alkynes, and Carboxylic Acids.

We report here the hydroboration of nitriles, alkynes, and carboxylic acids using amidophosphine boranes {(BH3)(PPh2)-NC(CH3)3}, {(BH3)2(PPh)2N(CH2)C6H5}, and {(BH3)2(PPh2)2N-(BH3)CH2C6H4N} as reducing agents. These compounds were synthesized to replace more commonly used borane reagents. Solid amidophosphine boranes, which were synthesized with ease, demonstrated excellent reactivity and functional group tolerance toward a wide variety of nitriles, alkynes, and carboxylic acids, affording the corresponding ammonium salts, alkenes, and alcohols in good yield.

Zinc Catalyzed Hydroboration of Esters and Nitriles with Pinacolborane.

We developed a bench-stable iminopyridine-ligated zinc complex for the effective catalytic hydroboration of esters and nitriles under solvent-free conditions. Various esters and nitriles bearing different functionalities were selectively reduced to form corresponding alcohols and amines in good yields. Detailed Hammett plots are provided to explain the electronic effects on the phenyl ring.

Highly efficient and well-controlled ROP and copolymerization of cyclic esters using a cesium complex.

A cesium imino-phosphanamidinate, [{NHIDippP(Ph)NDipp}Cs], enabling efficient ring-opening (co)polymerization of rac-LA and ε-CL is disclosed. Owing to the highly controlled polymerization, precise di-block copolymers (PLA-b-PCL) with different block lengths can be produced by a simple one-pot reaction. NMR, GPC, DSC and microscopic analyses confirm the production of di-block copolymers with crystalline properties.

Correction: NHC-Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes.

Correction for 'NHC-Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes' by Adimulam Harinath et al., Org. Biomol. Chem., 2023, https://doi.org/10.1039/d3ob00453h.

NHC-Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes.

An N-heterocyclic carbene-zinc alkyl complex [ImDippZn(CH2CH3)2] (Im = imidazol-2-ylidene and Dipp = 2,6-diisopropylphenyl) acts as a catalyst in the cross-dehydrogenative coupling (CDC) of a wide range of primary and secondary amines and hydrosilanes to yield a substantial quantity of the corresponding aminosilanes with good chemoselectivity at room temperature. A broad substrate scope was observed during the zinc-catalyzed CDC reaction. Two zinc complexes, [{ImMesZn(µ-NHPh)(NHPh)}2] (Mes = mesityl) (3) and [{ImDippZn(CH2CH3)(µ-H)}2] (4), were isolated and structurally characterized as intermediates through controlled reactions to ascertain the CDC mechanism.

Design and synthesis of photostable triphenylamine based neutral AIE nano luminogens: specific and long-term tracking of mitochondria in cells.

With the increasing dependence on fluorescence bioimaging, luminogens with aggregation-induced emission (AIE) properties have gained significant attention due to their excellent photostabilization, minimal photobleaching, high reliability, and superior biocompatibility. Since mitochondria are crucial subcellular organelles in eukaryotic cells with important biological functions, organelle-specific AIE emitters with distinct functions have been highly sought after, but with limited success using simple synthetic methods. Here, we describe a strategy for synthesizing two triphenylamine (TPA) based acrylonitriles, tethered to different donor groups, TPA and phenothiazine (PTZ), respectively, with superior AIE properties using Suzuki coupling. We conducted a systematic and detailed experimental analysis of the structural characteristics of both AIE luminogens, which exhibited excellent photostability, a large Stokes shift, and bright solid-state emission. A cell viability study carried out with F1 and F2 dyes revealed that both luminogens exhibited excellent biocompatibility. Based on fluorescence experiments, F2 displayed excellent AIE characteristics, permeability, biocompatibility, and photostability compared to rhodamine 123, allowing it to selectively stain and track mitochondria in cancer cells over an extended period of time. The Pearson correlation coefficient of F2 and rhodamine 123 was estimated to have an r-value of 0.99. Our findings are expected to provide insight into the synthesis of an extensive archive of AIE-based acrylonitriles with fascinating properties for mitochondrial staining.

N

The synthesis, characterization, and catalytic application of six aluminum alkyl complexes supported by various imino-phosphanamidinate chalcogenide ligands are described. Six different unsymmetrical imino-phosphanamidinate chalcogenide ligands [NHIRP(Ph)(E)NH-Dipp] [R = 2,6-diisopropylphenyl (Dipp), E = S (2a-H), Se (2b-H); R = mesityl (Mes), E = S (3a-H), Se (3b-H); R = tert-butyl (tBu), E = S (4a-H), Se (4b-H)] were prepared by the oxidation of respective imino-phosphanamide ligands (1a, 1b and 1c) with elemental chalcogen atoms (S and Se). The aluminum complexes with imino-phosphanamidinate chalcogenide ligands with the general formulae [κ2NN-{NHIRP(Ph)(E)N-Dipp}AlMe2] [R = Dipp, E = S (5a), Se (5b); R = Mes, E = S (6a), Se (6b)] or [κ2NE-{NHIRP(Ph)(E)N-Dipp}AlMe2] [R = tBu, E = S (7a), Se (7b)] were synthesized in good yields from the reaction of the suitable protic ligands (2a,b-H-4a,b-H) and trimethylaluminum in a 1 : 1 molar ratio in toluene at room temperature. All the protic ligands and aluminum complexes were well characterized by multi-nuclear NMR spectroscopy, and the solid-state structures of 2a,b-H-4a,b-H, 5a,b-6a,b and 7b are established by single crystal X-ray diffraction analysis. The aluminum complexes 5a,b-7a,b were tested as catalysts for the hydroboration of nitriles, alkynes, and alkenes under mild conditions. The catalytic hydroboration reactions of nitriles, alkynes, and alkenes were accomplished with complex 5b at a mild temperature under solvent-free conditions to afford a high yield of the corresponding N,N-diborylamines, vinylboranes and alkyl boronate esters, respectively.

A binuclear aluminium complex as a single competent catalyst for efficient synthesis of urea, biuret, isourea, isothiourea, phosphorylguanidine, and quinazolinones.

The synthesis and characterisation of two mononuclear aluminium alkyl complexes with the general composition [Al(Me)2{Ph2P(E)N(CH2)2N(CH2CH2)2O}] (E = Se (2a); S (2b)), and two binuclear aluminium complexes, [Al(Me)2{Ph2P-(E)N(CH2)2N(CH2CH2)2O}(AlMe3)] (E = Se (3a) and S (3b)), are described. The binuclear aluminium alkyl complex 3a proved to be a proficient catalyst for the addition of simple nucleophiles to heterocumulenes, leading to the synthesis of a variety of products such as urea, biuret, isourea, isothiourea, phosphorylguanidine, and quinazolinone derivatives, in contrast to its mononuclear analogues. Complex 3a is the first example of a single competent catalyst, which is also low-cost and eco-friendly and derived from a main-group metal, under solvent-free conditions either at room temperature or mild temperatures. Complex 3a possessed a wide functional group tolerance including heteroatoms, yielding the corresponding insertion products in good quantities and with high selectivity.

Clinical diversities of patient eye care in para-COVID-19 era in Western Odisha.

Background: Coronavirus disease (COVID-19) pandemic had an unprecedented effect on eye care services. The present study was conducted to assess the varied eye diseases and care around COVID-19 pandemic. Methods: This retrospective study was conducted at BBMCH, Balangir, Ophthalmology Department, Western Odisha, from September 2019 to May 2021 in three phases (i.e., September 2019 to March 2020, April to October 2020, November 2020 to March 2021). The total OPD consultations and emergency eye surgeries conducted around the COVID-19 period were retrieved from direct attendance in the OPD register, references, or tele-consultation. Results: Cumulative OPD eye consultations were found to be 13000, 3700, 7200 in pre-COVID, COVID and post-COVID period, respectively. Marked decrease in OPD cases (70%) was noticed in peak COVID period (April 2020 to October 2020) followed by slight increase during November 2020 to May 2021 i.e., (40% decrease). Allergic conjunctivitis was the commonest presentation in pre-COVID era, as compared to refractive error in COVID period. In post-COVID period, referrals, follow up cases, pending old surgical cases, red eyes formed major chunk of OPD attendance. Only 30% emergency cases underwent surgery during peak COVID, (Trauma cases, lens induced glaucoma, hypermature cataract, MLC cases, and one-eyed patients). But during post-COVID period this rose to 60%. Eight pediatric patients with intracorneal foreign body were given urgent treatment. Conclusion: Due to government guidelines and lockdown restrictions, majority (65%) of patients could not receive adequate treatment. But relaxation of rules in post-COVID period increased patient load to 75%.

Metal/Non-Metal Catalyzed Activation of Organic Nitriles.

Nitrile activation is a prominent topic in recent developments in chemistry, especially in organic, inorganic, biological chemistry, as well as in the natural synthesis of products and in the pharmaceutical industry. The activation of nitriles using both metal and non-metal precursors has attracted several researchers, who are exploring newer ways to synthesize novel compounds. Nitrile activation can be achieved by combining various catalytic double hydroelementation reactions, such as hydrosilylation, hydroboration, and hydrogenation of organonitriles using silanes, pinacolborane, and other sources of hydrogen. These methodologies have garnered considerable attention since they are effective in the reduction of organonitriles, whose end products are extensively applied in synthetic organic chemistry. In this review, we summarize the development of selective hydroborylation, hydrosilylation, dihydroborysilylation, and hydrogenation of organonitriles, as well as their reaction mechanisms and the role of metal complexes in the catalytic cycles. This review article explains various synthetic methodologies applied toward the reduction of organonitriles into corresponding amines.

Aluminium alkyl complexes supported by imino-phosphanamide ligand as precursors for catalytic guanylation reactions of carbodiimides.

Herein, we report the synthesis, characterisation, and application of three aluminium alkyl complexes, [κ2-{NHIRP(Ph)NDipp}AlMe2] (R = Dipp (2a), Mes (2b); tBu (2c), Dipp = 2,6-diisopropylphenyl, Mes = mesityl, and tBu = tert-butyl), supported by unsymmetrical imino-phosphanamide [NHIRP(Ph)NDipp]- [R = Dipp (1a), Mes (1b), tBu (1c)] ligands as molecular precursors for the catalytic synthesis of guanidines using carbodiimides and primary amines. All the imino-phosphanamide ligands 1a, 1b and 1c were prepared in good yield from the corresponding N-heterocyclic imine (NHI) with phenylchloro-2,6-diisopropylphenylphosphanamine, PhP(Cl)NHDipp. The aluminium alkyl complexes 2a, 2b and 2c were obtained in good yield upon completion of the reaction between trimethyl aluminium and the protic ligands 1a, 1b and 1c in a 1 : 1 molar ratio in toluene via the elimination of methane, respectively. The molecular structures of the protic ligands 1b and 1c and the aluminium complexes 2a, 2b and 2c were established via single-crystal X-ray diffraction analysis. Complexes 2a, 2b and 2c were tested as pre-catalysts for the hydroamination/guanylation reaction of carbodiimides with aryl amines to afford guanidines at ambient temperature. All the aluminium complexes exhibited a high conversion with 1.5 mol% catalyst loading and broad substrate scope with a wide functional group tolerance during the guanylation reaction. We also proposed the most plausible mechanism, involving the formation of catalytically active three-coordinate Al species as the active pre-catalyst.

A highly efficient Ti-catalyst for the deoxygenative reduction of esters under ambient conditions: experimental and mechanistic insights from DFT studies.

In this paper, we report the synthesis of dianionic amidophosphineborane-supported titanium chloride [{Ph2P(BH3)N}2C6H4TiCl2] (1) and TiIV alkyl complex [{Ph2P(BH3)N}2C6H4Ti(CH2SiMe3)2] (2) using a salt metathesis reaction. TiIV complex 1 was obtained by the reaction of the bis-borane ligand [{Ph2P(BH3)NH}2C6H4] and TiCl4 in toluene followed by the addition of 2 equivalents of [LiN(SiMe3)2] at ambient temperature. TiIV bis-alkyl complex 2 was isolated from the reaction of complex 1 with 2.5 equivalents of LiCH2SiMe3 in toluene. The solid-state structure of complex 1 is established by single-crystal X-ray diffraction analysis. TiIV bis-alkyl complex 2 has proved to be a competent catalyst in the deoxygenative reduction of aliphatic and aromatic esters with pinacolborane (HBpin) to afford corresponding boryl ethers at room temperature under solvent-free conditions. Catalyst 2 exhibits chemoselectivity toward ester functionalities over halides, heteroatoms, olefins, and amino functional groups. DFT studies demonstrate that the active form of catalyst 2 is capable of easily transferring its hydrides to ester substrates at room temperature. The studies further reveal that the rate-limiting step (RLS) in an ester-to-boryl ether conversion is the cleavage of the C-O bond of an ester. In brief, the titanium-catalysed ester-to-boryl ether conversions are found to be downhill processes having small activation barriers along all mechanistic steps.

Aluminium complexes: next-generation catalysts for selective hydroboration.

Organoboranes obtained from hydroboration reactions are one of the important classes of compounds that could be used to provide valuable synthons for follow-up transformations such as various functional group incorporation or C-C bond forming reactions. For decades, various transition metals were utilised as catalysts in such transformations. Recently Earth-abundant and less toxic main group metals have revived their importance in hydroboration chemistry, among which the suitable candidates are aluminium complexes as catalysts. In this regard, the development of aluminium complexes to achieve more robust catalytic systems with greater efficiency is appreciable.

Catalytic Hydroboration and Reductive Amination of Carbonyl Compounds by HBpin using a Zinc Promoter.

The chemoselective hydroboration of aldehydes and ketones, catalyzed by Zinc(II) complexes [κ2 -(PyCH=NR)ZnX2 ] [R=CPh3 , X=Cl (1) and R=Dipp (2,6-diisoropylphenyl) and X=I (2)], in the presence of pinacolborane (HBpin) at ambient temperature and under solvent-free conditions, which produced the corresponding boronate esters in high yield, is reported. Zinc metal complexes 1 and 2 were derived in 80-90% yield from the reaction of iminopyridine [PyCH=NR] with anhydrous zinc dichloride in dichloromethane at room temperature. The solid-state structures of both zinc complexes were confirmed using X-ray crystallography. Zinc complex 1 was also used as a competent pre-catalyst in the reductive amination of carbonyl compounds with HBpin under mild and solvent-free conditions to afford a high yield (up to 97%) of the corresponding secondary amines. The wider substrate scope of both reactions was explored. Catalytic protocols using zinc as a pre-catalyst demonstrated an atom-economic and green method with diverse substrates bearing excellent functional group tolerance. Computational studies established a plausible mechanism for catalytic hydroboration.