1H NMR Research Articles

Enhancing the Chemical Stability of P12L24 Cage: Transformation of the Chemically Labile Imine Cage into a Robust Carbamate Cage.

Herein, we report enhancement in chemical stability of the imine-based porphyrinic cage P12L24 by converting it into a robust carbamate porphyrinic cage, c-P12L24, through a two-step post-synthetic modification process. First, the imine bonds in P12L24 were reduced to form an amine-based cage, r-P12L24, followed by carbamation using N,N'-carbonyldiimidazole (CDI) to yield c-P12L24. The resulting carbamate cage exhibits high stability under acidic and basic conditions (pH 1-13) and in the presence of moisture. 1H NMR, DOSY NMR, and DFT calculations revealed that reducing the imine bonds to amine increases the framework's flexibility, causing partial structural collapse, whereas the carbamate formation restores structural rigidity. The insertion of a 4.0 nm molecular ruler into the cavity of zinc-metallated c-P12L24 via metal-ligand coordination further confirmed restoration of the cavity size and geometry of the original cage. This enhancement of chemical stability through carbamate formation can pave the way to a wide range of potential applications for the gigantic porphyrinic cage.

A novel pillar-layered MOF with urea linkers as a capable catalyst for synthesis of new 1,8-naphthyridines via the anomeric-based oxidation.

Metal-based catalysts play an essential role in organic chemistry and the chemical industry. This research designed and successfully synthesized a pillar-layered metal-organic framework (MOF) with the urea linkers, namely Basu-HDI, as a novel and efficient heterogeneous catalyst. Various techniques such as FT-IR, EDX, elemental mapping, SEM, XRD, BET, and TGA/DTA studied its structure and morphology. Then, we investigated the synthesis of new 1,8-naphthyridines utilizing Basu-HDI in mild conditions via a one-pot, three-component tandem Knoevenagel/Michael/ cyclization/anomeric-based oxidation reaction. Final products were achieved by anomeric-based oxidation without employing an oxidation agent. Remarkably, this tandem process gave a good range of new 1,8-naphthyridines with high yields in a short reaction time. The pure products were confirmed by FT-IR, 1H NMR, 13C NMR, and mass spectrometry techniques. Moreover, the introduced catalyst showed good efficiency and stability and can be reused four times without significantly reducing efficiency.

Synthesis, Corrosion Inhibition, In Silico ADME, DFT, and Antibacterial Activity of Pyridine‐Based Schiff Base and Its Cu (II) Complex

ABSTRACTHerein, we report the synthesis of an (E)‐N‐(pyridine‐3‐ylmethylene)pyridine‐2‐amine Schiff base (ENppa) and its Cu (II) complex (Cu‐ENppa) using 2‐aminopyridine (2APy) and pyridine‐3‐carbaldehyde (P3C). This study aimed to investigate the ADMET profiles, electronic features, antibacterial and anticorrosion activities of the synthesized ligand, and its Cu (II) complex. The compounds were characterized using various techniques, including CHN analysis, FT‐IR, 1H and 13C NMR, MALDI‐TOF MS, ICP‐MS, SEM, TGA/DTA, UV–visible spectroscopy, and powder X‐ray diffraction (PXRD). The Cu (II) ion exhibited tetrahedral geometry in the complex by coordinating with two nitrogen atoms, one from an imine group and the other from a pyridine ring. UV–visible spectroscopy and magnetic moment data also supported this geometry. TGA/DTA revealed three stages of decomposition at 141°C°C–255°C, 255°C°C–367°C, and 549°C°C–659°C, with CuO as the final residue. PXRD analysis identified ENppa and Cu‐ENppa as nanocrystallites, with crystallinities of 82% and 49%, respectively. Both compounds were highly effective in inhibiting mild steel corrosion in acidic media, with inhibition efficiencies of 97% and 98%, respective for Cu‐ENppa and ENppa. They also exhibited favorable ADME profiles, indicating potential as drug candidates for in silico ADME studies. The antibacterial activity results demonstrated promising efficacy, with Cu‐ENppa showing higher activity than ENppa.

Synthesis and Anti-Inflammatory and Analgesic Potentials of Ethyl 2-(2,5-Dioxo-1-Phenylpyrrolidin-3-yl)-2-Methylpropanoate

Background/Objectives: Inflammation and analgesia are two prominent symptoms and often lead to chronic medical conditions. To control inflammation and analgesia, many marketed drugs are in practice but the majority of them have severe side effects. Methods: This study involved the synthesis of a pivalate-based Michael product and evaluated it for in vitro COX-1, COX-2, and 5-LOX inhibitory potentials using specific assays. Molecular docking studies were also assessed. Based on the in vitro results, the compound was also subjected to in vivo anti-inflammatory and antinociceptive studies. Results: The pivalate-based Michael product (MAK01) was synthesized by an organocatalytic asymmetric Michael addition of ethyl isobutyrate to N-phenylmaleimide with an isolated yield of 96%. The structure of the compound was confirmed through 1H and 13C NMR analyses. The observed IC50 values for COX-1, COX-2, and 5-LOX were 314, 130, and 105 μg/mL, respectively. The molecular docking studies on the synthesized compound showed binding interactions with the minimized pockets of the respective enzymes. In a carrageenan model, a percent reduction in edema when administered at 10 mg/kg (a reduction of 33.3 ± 0.77% at the second hour), 20 mg/kg (a reduction of 34.7 ± 0.74% at the second hour), and 30 mg/kg (a reduction of 40.58% ± 0.84% after the fifth hour) was observed. The compound showed a significant response at concentrations of 50, 100, and 150 mg/kg with latency times of 10.32 ± 0.82, 12.16 ± 0.51, and 12.93 ± 0.45 s, respectively. Conclusion: In this study, we synthesized a pivalate-based Michael product for the first time. Moreover, based on its rationality and potency, it was found to be an effective future medicine for the management of analgesia and inflammation.

Spectroscopic, quantum computational, molecular dynamic simulations, and molecular docking investigation of the biologically important compound-2,6-diaminopyridine

To establish the role in future drug development, 2,6-diamino pyridine (2,6-DAP) was investigated experimentally using computational tools. NMR (1H,13C), FTIR, and UV–Vis spectra were analyzed for the titled compound. The molecular structure was optimized via DFT with the “B3LYP method with 6-311++G(d,p)” The optimized parameters of the structure were assessed with the observed bond characteristics. The vibrational frequencies were studied, PED was carried out, and the calculated vibrational frequency obtained was compared with the experimentally obtained FTIR. NMR (1H,13C) was calculated and compared with the experimentally obtained spectra. UV–vis spectra are calculated in the gaseous phase and different mediums of solvents (methanol, DMSO) by employing the PCM solvent model and TD-DFT method, and the estimated value was compared with experimentally measured data. NBO analysis was done to study the donor-acceptor interaction. The extent of electron charge transfer inside the molecular structure was examined using HOMO–LUMO energy values. The study of excitation analysis led to the creation of E.D.D and H.D.D maps in methanol and DMSO. The AIM and ELF analysis was employed to compute the iso-surface projections, ellipticity, and binding energies. The MEP and Fukui functions evaluate the molecule’s reactive zones. Hirshfeld research was done to analyze interactions among the molecules in the structure of the crystal, and 3D Hirshfeld tops and 2D fingerprint layouts were developed. The molecular docking procedure was used, followed by a 100 ns MD simulation and computation of binding free energy found to delineate the binding affinity of the molecule toward human carbonic anhydrase II (HCA II). Molecular docking studies with several receptor proteins were also conducted to determine the most effective protein-ligand interactions. Biological assessments like drug-likeness also act upon the compound to verify the molecule’s drug-like nature.

Dendritic Molecular Baskets for Selective Binding of Toxic Methotrexate.

We describe the preparation, assembly, recognition characteristics, and bioactivity of dendritic basket 612-. This novel cavitand has a deep aromatic pocket with three (S)-glutamic acid dendrons at the rim to amplify water solubility and prevent self-association. 1H NMR spectroscopy, calorimetry (ITC), and mass spectrometry (ESI-MS) measurements validate the formation of an inclusion complex between 612- and anticancer drug methotrexate (MTX2-) in water (Kd = 9.2 μM). To identify the docking pose, a comparison of computed (DFT and MM) and experimental 1H NMR chemical shifts suggests that MTX2- folds inside 612- (π···π), forming HBs with the peptidic dendrons while anchoring (C-H···π) to the aromatic pocket through its N-methyl group. In consequence, 612- selectively binds MTX2- in competition with structurally similar folic acid and leucovorin (reversal poisoning agent). While the host is biocompatible (HEK293; IC50 > 150 μM) and produces inclusion complex [MTX⊂6]14- in cell media, it experiences limitation in pharmacokinetic sequestration of MTX2- as dihydrofolate reductase's affinity to the drug is suggested to prevail over that of 612-. Nonetheless, considering the basket's biocompatibility, tunability, and chemoselectivity, it stands as the leading candidate in the pursuit of an effective abiotic antidote for methotrexate poisoning.

Non‐Isocyanate Carbamate Acrylates: Synthesis, Characterization, and Applications in UV 3D Printing

ABSTRACTIn this paper, two synthetic routes for non‐isocyanate carbamate acrylates (CAs) were explored. Four amino alcohols reacted with ethylene carbonate respectively forming carbamate alcohols. Additionally, carbamate amines were synthesized through the reaction of diethylene glycol with dimethyl carbonate, followed by the reaction of 4‐methylcyclohexane‐1,3‐diamine. Five kinds of CAs were synthesized via oxa‐Michael addition of carbamate alcohols and aza‐Michael reactions of carbamate amines with neopentyl glycol diacrylate (NPGDA), respectively. The resulting intermediates and final CAs were characterized by electrospray ionization high‐resolution mass spectrometry (ESI‐HRMS), 1H NMR, and FT‐IR spectroscopy. The photopolymerization kinetics of the CAs were investigated using FT‐IR spectroscopy. Under UV irradiation and initiation by 1 wt% 2‐isopropylthioxanthone (ITX) for 30 s, the double bond conversion of the CAs synthesized by oxa‐Michael addition were over 95%. The resulting CAs can be UV cured to form a transparent film with a gel content of 90%–95%, a hardness of 4–5 H, and a flexibility of 1 mm. A formulation consisting of 79 wt% CA2, 20 wt% NPGDA, and 1 wt% ITX was applied for 3D printing to produce various models with smooth surfaces, high precision, and excellent flexibility.

Dendritic Molecular Baskets for Selective Binding of Toxic Methotrexate

We describe the preparation, assembly, recognition characteristics, and bioactivity of dendritic basket 612‐. This novel cavitand has a deep aromatic pocket with three (S)‐glutamic acid dendrons at the rim to amplify water solubility and prevent self‐association. 1H NMR spectroscopy, calorimetry (ITC), and mass spectrometry (ESI‐MS) measurements validate the formation of an inclusion complex between 612‐ and anticancer drug methotrexate (MTX2‐) in water (Kd = 9.2 μM). To identify the docking pose, a comparison of computed (DFT and MM) and experimental 1H NMR chemical shifts suggests that MTX2‐ folds inside 612‐ (π···π), forming HBs with the peptidic dendrons while anchoring (C−H···π) to the aromatic pocket through its N‐methyl group. In consequence, 612‐ selectively binds MTX2‐ in competition with structurally similar folic acid and leucovorin (reversal poisoning agent). While the host is biocompatible (HEK293; IC50 > 150 μM) and produces inclusion complex [MTX⊂6]14‐ in cell media, it experiences limitation in pharmacokinetic sequestration of MTX2‐ as dihydrofolate reductase’s affinity to the drug is suggested to prevail over that of 612‐. Nonetheless, considering the basket’s biocompatibility, tunability, and chemoselectivity, it stands as the leading candidate in the pursuit of an effective abiotic antidote for methotrexate poisoning.

A Genetically Engineered Reporter System Designed for 2H-MRI Allows Quantitative In Vivo Mapping of Transgene Expression.

The ability to obtain quantitative spatial information on subcellular processes of deep tissues in vivo has been a long-standing challenge for molecular magnetic resonance imaging (MRI) approaches. This challenge remains even more so for quantifying readouts of genetically engineered MRI reporters. Here, we set to overcome this challenge with a molecular system designed to obtain quantitative 2H-MRI maps of a gene reporter. To this end, we synthesized deuterated thymidine, d3-thy, with three magnetically equivalent deuterons at its methyl group (-CD3), showing a singlet peak with a characteristic 2H-NMR frequency (δ = 1.7 ppm). The upfield 3.0 ppm offset from the chemical shift of the HDO signal (δ = 4.7 ppm) allows for spectrally resolving the two 2H NMR signals and quantifying the concentration of d3-thy based on the known concentration of a tissue's HDO. Following systemic administration of d3-thy, its accumulation as d3-thy monophosphate in cells expressing the human thymidine kinase 1 (hTK1) transgene was mapped with 2H-MRI. The data obtained in vivo show the ability to use the d3-thy/hTK1 pair as a reporter probe/reporter gene system to quantitatively map transgene expression with MRI. Relying on a structurally unmodified reporter probe (d3-thy) to image the expression of unmutated human protein (hTK1) shows the potential of molecular imaging with 2H-MRI to monitor gene reporters and other relevant biological targets.

Uncommon Phosphonylation of Pyrazine‐2,3‐dicarbonitrile Derivatives via C(sp2)‐CN Bond Cleavage

A direct phosphonylation of the sp2C−CN bond under mild catalytic and non‐catalytic reaction conditions is disclosed. Pyrazine‐2,3‐dicarbonitriles are readily coupled with HPO(OEt)2 to produce the corresponding dialkoxyphosphoryl‐substituted pyrazines. The phosphonylation reaction occurs in the presence of a base (Et3N, Cs2CO3) as nucleophilic substitution of the CN groups. The yield of target diphosphonates depends on the nature of substituents in the 5,6‐positions of the pyrazine ring: it exceeds 90% for di‐5,6‐aryl‐substituted pyrazines and is significantly lower when electron‐donating alkyl (n‐propyl) groups are attached to the 5,6‐positions. It should be noted that for pyrazine‐2,3‐dicarbonitriles bearing vicinal 4‐bromophenyl groups, the nucleophilic phosphonylation leading to C‐‐CN/P‐‐H coupling in the pyrazine ring is predominant over Pd‐catalyzed Hirao’s C‐‐Br/P‐‐H coupling reaction in phenyl rings. Detailed structural characterization, both in solution by means of 1H, 13C and 31P NMR spectroscopy and in the solid state by single crystal X‐ray diffraction, of a series of newly synthesized pyrazine phosphonates is reported.

Unravelling the incorporation mechanisms of water in aluminous orthoenstatite: II. comprehensive 1H, 29Si and 27Al NMR measurements

AbstractAluminum has been shown to significantly enhance the water incorporation capacity of orthoenstatite (OEn), but the incorporation mechanisms remained to be clarified. We performed a comprehensive one- and two-dimensional 1H, 29Si and 27Al NMR study on four hydrous aluminous OEn samples containing 1–8 wt% Al2O3 synthesized at 1.5 GPa and 900 °C to clarify the issue. The combined 1H MAS and static (non-spinning) NMR, 1H double-quantum and triple-quantum MAS NMR, and 27Al→1H CP MAS NMR and HETCOR results, in particular, unambiguously revealed that a large part of the incorporated water are present as proton pairs in Mg vacancies adjacent to Al, with one proton of each pair for the dominant proton pairs exhibiting significantly weaker hydrogen bonding than those in Al-free OEn. Proton pairs in Mg vacancies remote from Al are minor or absent for samples with 4–8 wt% Al2O3, and more abundant for a sample with 1 wt% Al2O3. Isolated protons due to coupled substitutions of Al + H for 1Si and 2Mg (both with weak hydrogen bonding) were also detected, but are less abundant than hitherto considered. The observed NMR peaks match well with those predicted for the corresponding OH defect models from our first-principles calculations. Thus, the enhancement of water solubility by Al for OEn are due to not only coupled substitutions of Al + H for 1Si and 2Mg, but also interactions of Al with proton pairs in Mg vacancies. These mechanisms may also be important in other nominally anhydrous aluminous silicate minerals.

Suppressing Effect of Flavonoid Compounds on Lipids Photooxidation of Sheep Red Blood Cells and Oleic Acid Photooxidation

ABSTRACTPhotosensitizers and pigments in raw meat such as porphyrins, riboflavin, and myoglobin after incorporation with light beam prompt the generation of singlet oxygen (1O2) from triplet oxygen (3O2) and cause oxidative rancidity of meat products. In this study, the results of photooxidation reactions of sheep erythrocyte (red blood cell) model as a model rich in hemoglobin and phospholipids bilayer, and oleic acid model were obtained by 1H NMR spectroscopy, TBARS assay, and iodometric titration. In both models, the rate of lipid photooxidation in the presence of hydroalcoholic extracts of Turmeric (Curcuma longa L.) and Cumin (Cuminum cyminum L.) as natural antioxidants, Butyl hydroxytoluene (BHT) as a synthetic antioxidant, and sodium azide (NaN3) as a well‐known 1O2 scavenger were decreased in the order of NaN3 > Turmeric > Cumin > BHT. It was proven that during the photooxidation process, there is a direct association between the amount of flavonoid compounds and 1O2 scavenging.

Biodegradable Polyurethane Foams Based on Polyols Obtained from Cellulose and Its Hydroxypropyl Derivative

Three methods of cellulose-derived polyol synthesis were elaborated. The suitable substrates were (hydroxypropyl)cellulose or cellulose, which were hydroxyalkylated in reactions with glycidol and ethylene carbonate in triethylene glycol or in water. The products were characterized by IR, 1H NMR, and MALDI ToF spectroscopies. For all polyols, IR spectra showed strong bands at 1060 cm−1 from the ether group formed upon the ring opening of GL and EC. The polyol obtained from (hydroxypropyl)cellulose in the triethylene glycol solvent was accompanied by oligomeric products of glycol hydroxyalkylation and oligomeric glycidol. The polyol obtained by the hydroxyalkylation of cellulose with glycidol and ethylene carbonate in the water contained units of hydroxyalkylated cellulose and products of hydroxyalkylation of water. The physical properties of the obtained polyols, like density, viscosity, and surface tension, were determined. The polyols were then used to obtain rigid polyurethane foams. The foams have apparent density, water uptake, and polymerization shrinkage similar to classic rigid PUFs. The foams showed advantageous thermal resistance in comparison with classic ones. After thermal exposure, their compressive strength improved. The biodegradation of the obtained materials was tested by a respirometric method in standard soil conditions by the measurement of biological oxygen demand and also using the cellulases or the enzymes responsible for cellulose degradation. It has been found that polyols are totally biodegradable within one month of exposure, while the foams obtained thereof are at least 50% biodegraded in the same conditions. The enzymatic biodegradation of the PUFs by the action of microbial cellulase was confirmed.

Modulating the Supramolecular Assembly of α-Cyclodextrin and Anderson-type Polyoxometalate through Covalent Modifications.

A series of unprecedented supramolecular complexes of covalently modified Anderson-type polyoxometalates (POMs) and α-cyclodextrins (α-CDs) have been obtained and characterized in solid state by single-crystal X-ray diffraction, and in aqueous solution using various techniques including 1H DOSY, 2D NOESY 1H NMR, isothermal titration calorimetry (ITC), and electrospray ionization time-of-flight mass spectroscopy (ESI-TOF-MS). It has been demonstrated that the supramolecular assembly process can be modulated by different covalent modification modes of the Anderson POMs, giving rise to a new type of POM/α-CD complexes featuring organic-inorganic pseudo-rotaxane structures, which are in good contrast to those of POM/γ-CD with poly-rotaxane type structures. Moreover, it is delighted to find that these pseudo-rotaxanes of POM/α-CD exhibit stable chirality in aqueous solution, which has not been accomplished in previously reported POM/γ-CD assemblies.

Synthesis, spectroscopic characterization techniques of aromatic iminoaniline derived compound, along with the evaluation of its LNO properties using quantum chemistry

In this research work, we synthesized a Schiff base derivative, N,N-dimethyl-4-{[(4-nitrophenyl)imino]-methyl}aniline, denoted as (n1). The molecule (n1) was characterized using spectroscopic analyses, including FT-IR, NMR 1H, and 13C. Our compound (n1) is an unsaturated molecule, consisting of two benzylic rings connected by a methylimine bridge. The resulting system comprises seven alternating π bonds. At both ends of (n1) and in the para position, there are the N(CH3)2 group with a strong electron-donating effect and the NO2 group with a strong electron-accepting effect. The molecular structure of our compound prompted us to evaluate and study its properties in the field of NLO. The assessment of NLO properties is conducted by determining the Egap and employing density functional theory (DFT) quantum chemistry studies. The optical gap of (n1), measured using the Tauc method, is found to be 2.7 eV, serving as a reference value for the choice of the DFT functional in theoretical calculations. Quantum chemistry studies were carried out using Gaussian09 software, and the results were visualized with GaussView05. CAM-B3lyp functional was chosen for theoretical calculations due to its close agreement with experimental values. The studies confirm that (n1) exhibits significant NLO properties. Additionally, NBO (Natural Bond Orbital) analyses provide insight into the mechanism and trajectory of intramolecular charge transfer in (n1).

Water-Soluble Intracellular Polysaccharides (IPSW-2 to 4) from Phellinus igniarius Mycelia: Fractionation, Structural Elucidation, and Antioxidant Activity

Phellinus igniarius is a medicinal fungus. Nonetheless, research on its water-soluble intracellular polysaccharides (IPSW-2 to 4) fractionation, structural elucidation, and antioxidant activity is limited. In this study, water-soluble intracellular polysaccharides (IPSW-2 to 4) were extracted and fractionated from P. igniarius mycelia, and their antioxidant and structural properties were assessed using GC-FID, GC-MS, FTIR, and NMR spectroscopy (1H and 13C). In the water-eluted P. igniarius polysaccharide fractions (IPS30W, IPS60W, and IPS80W) of anion-exchange chromatography, the polysaccharide content was 79.05%, 68.25%, and 62.06%, with higher yields of 25.07%, 21.38%, and 20.34%, respectively. In contrast, the salt (NaCl) elution fractions (IPS30S1, IPS60S1, IPS60S2, and IPS80S1) of anion-exchange chromatography had lower polysaccharide content and yield. Hence, water elution fractions (IPS30W, IPS60W, and IPS80W) were selected for further purification. After repeated purification using size-exclusion chromatography, IPSW-2 to 4 were obtained with a yield of 8% to 15.83%. The IPSW-2 to IPSW-4 structures were elucidated, and they showed no triple helical conformation. Based on periodate oxidation, Smith degradation, methylation analysis, and 1H and 13C NMR spectroscopy, the primary structures of IPSW-2, IPSW-3, and IPSW-4 were all glucan, with the main chain consisting of (1→6)-α-D-Glcp, (1→3,4)-α-D-Glcp, and (1→3, 6)-α-D-Glcp, with α-D-Glcp as a side chain. Finally, antioxidant analysis showed that IPS30W, IPS60W, and IPS80W were all more capable of scavenging superoxide anions than the polysaccharides of Phyllostachys (13.8%) and floribunda (15.1%) at the same concentration (0.40 mg/mL). This will serve as a guide for the development of functional foods.

Unravelling the incorporation mechanisms of water in aluminous orthoenstatite: I. First-principles calculations

We performed first-principles calculations on the energy, and NMR and polarized infrared (IR) spectra for anhydrous and hydrous aluminous orthoenstatite (OEn) models to help clarify the incorporation mechanisms of Al and OH defects in OEn. Our calculations revealed that proton pairs in M2 vacancies ((2H)M2) adjacent to a tetrahedral Al (AlIV) are energetically more favorable than those remote from Al, and may contribute to the observed correlated 1H NMR peaks near 3.7 and 8.0 ppm, and IR bands near 3550–3570 and 3066 cm−1 (A4 band) for aluminous OEn. Coupled substitutions of AlVI (octahedral Al) + H for 2Mg were found to adopt multiple configurations, and may contribute to the observed IR bands near 3520, 3475 and 3320 cm−1. Coupled substitution of AlIV + H for 1Si may contribute to the observed IR band near 3380–3400 cm−1. 4H in SiB vacancies ((4H)SiB) adjacent to an AlVI were found to be energetically more favorable than those remote from Al, and may be the origin for an IR band observed near 3600–3620 cm−1. These results allow the incorporation mechanisms of water in synthetic and natural aluminous orthopyroxenes to be deciphered from the available NMR and IR data, and suggest that both (2H)M2 defects associated with Al and simultaneous coupled substitutions of Al + H for 2Mg and 1Si contribute to the observed correlation between Al and water incorporation, and the nearly unity AlIV/AlVI ratio. (4H)SiB defects associated with Al may also be present in some synthetic OEn and mantle-derived orthopyroxene.

HOST-GUEST INTERACTIONS FACILITATED BY CHALCOGEN BONDING WITHIN SELENADIAZOLE FUNCTIONALISED PORPHYRIN NANOTUBES.

The structural rigidity of tetrakis(4-pyridyl)porphyrin (TPyP) has been utilised to prepare a robust novel porous coordination polymer of composition Cd2(TPyP)(sez)2 (TPyP = 5,10,15,20-tetra(4-pyridyl)porphyrin, sez = 1,2,5-benzoselenadiazole-5-carboxylate). The coordination polymer may be described as a hexagonal porphyrin nanotube (PNT) and has the potential to bind guest molecules through chalcogen bonding. Single crystal X-ray diffraction (SCXRD) data indicate an internal pore diameter ~9 Å which represents ~35% of the crystal volume. Immersion of the PNTs in solvents such as DMSO and CS2 result in the incorporation of these molecules within the nanotubes with chalcogen bonding between host and guest. The crystallographic guest-inclusion investigations are complemented by solid-state 77Se, 13C, 113Cd and 2H NMR studies which provide insights into dynamic behaviour. The porosity of the crystals was further explored using gas adsorption experiments, indicating the reversible uptake of CO2, CH4, H2 and N2. Structure-function relationships are clearly established from complementary crystallographic, NMR and adsorption investigations.

Design, Synthesis, Antibacterial, and Antifungal Evaluation of a New Series of Quinazoline - Thiazole and/or Quinazoline - Triazole Hybrids as Bioactive Heterocycles.

Herein, a one-pot reaction between cyclohexanone, thiourea, and 2,5-dimethoxybenzaldehyde allowed to prepare hexahydroquinazoline-2(1H)-thione4 firstly, which followed by reacting with hydrazine hydrate to produce the corresponding 2-hydrazinylhexahydroquinazoline 6. Interesting analogs of thiazolo[3,2-a]quinazoline 713 where obtained when hexahydroquinazoline-2(1H)-thione 4 reacted with 1,2-dibromoethane, chloroacetyl chloride, bromoacetic acid, bromoacetic acid/4-chlorobenzaldehyde, 2-bromopropionic acid, ethyl bromo cyanoacetate, and/or bromomalononitrile; respectively. While triazolo[4,3-a] quinazoline 14-16 were created when 2-hydrazinylhexahydroquinazoline 6 reacted with triethyl orthoformate, acetic anhydride, and carbon disulfide respectively. Numerous spectroscopy tests, including FT-IR, NMR (1H &13 C), and MS spectrum, proved all the newly produced analogs. Additionally, the new analogs were examined for their antibacterial and antifungal properties against Escherichia coli, Staphylococcus aureus, and Candida albicans. It was discovered that triazolo[4,3-a] quinazoline analogs 14-16 have superior bacterial and fungal activity when compared to the corresponding conventional doses of Streptomycin andGriseofulvin. Towards Candida albicans; compounds 14, 15, and 16 increase activity with 1.14 %, 1.15 %, and 1.21 %, respectively more than griseofulvin.While, for Staphylococcus aureus; compounds 14, 15, and 16 increase activity with 1.5 %, 1.5 %, and 1.7 %, respectively more than streptomycin. Morever, for Escherichia coli; compounds 14, 15, and 16 increase activity with 1.19 %, 1.21 %, and 1.22 %, respectively more than streptomycin. Finally, structure activity relationships show that quinazoline derivatives exhibit higher activity when fused to pyrazole ring 14-16 as compared when fused thiophene ring 7-13.

A Unique Synthetic Route toward a 1,2‐Dihydrodigermene via Formal α‐Elimination of Bromo and Silyl Groups from a Bromo(phenylsilyl)germane

AbstractA 1,2‐dihydrodigermene bearing Tbb {4‐t‐butyl‐1,3‐bis[bis(trimethylsilyl)methyl]phenyl} groups was successfully synthesized and isolated via formal α‐elimination of bromo and silyl groups from the corresponding Tbb‐substituted boromo(phenylsilyl)germane. This novel synthetic method is conducted under mild conditions, representing a significant advantage in the field concerned. The synthesized 1,2‐dihydrodigermene was characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray crystallography. In the 1H NMR spectrum, the Ge−H unit was found to be less electronically affected from the substituents compared to that of the previously reported 1,2‐dihydrodigermene. Moreover, the UV/vis spectra at various temperatures indicated the formation of the isomeric (dihydrogermyl)germylene. In fact, the 1,2‐dihydrodigermene once isolated reacted with DMAP in solution to afford the corresponding complex of the (dihydrogermyl)germylene.