Amide Groups Research Articles

Aerobic Oxidation of PMB Ethers to Carboxylic Acids.

The first aerobic protocol of direct transformation of p-methoxybenzyl (PMB) ethers to carboxylic acids efficiently with Fe(NO3)3 ⋅ 9H2O and TEMPO as catalysts at room temperature has been developed. The reaction accommodates C-Br bond, terminal/non-terminal C-C triple bond, amide, cyano, nitro, ester, and trifluoromethyl groups. Even highly selective oxidative deprotection of different benzylic PMB ethers has been realized. The reaction has been successfully applied to the total synthesis of natural product, (R)-6-hydroxy-7,9-octadecadiynoic acid, demonstrating the practicality of the method. Based on experimental studies, a possible mechanism involving oxygen-stabilized benzylic cation has been proposed.

Electrochemically‐Enabled Construction of N‐Acyl Iminophosphoranes

AbstractN‐acyl iminophosphoranes have shown significant potentials in various areas. This paper presents two electrochemical strategies for the successful construction of a series of substituted N‐acyl iminophosphoranes using electrochemical activation of hydroxylamines or dioxazolones to generate unprotected amide radicals and radical anions. The simple undivided cell with inexpensive electrode setups (graphite felts, carbon rods, and copper sheets) provides excellent substrates tolerance under mild conditions. This simple electrochemical construction of N‐acyl iminophosphoranes also has good scalability, practicability and extensibility. Furthermore, synthetic transformations of the N‐acyl iminophosphorane products have demonstrated the application potentials of the P=N bond.

Synthesis of a water‐soluble high hydroxymethyl content phenolic resin crosslinker and the associated polyacrylamide weak gel property investigation

AbstractAs an in‐depth profile control agent, water‐soluble phenolic resin crosslinking polyacrylamide weak gel has been widely used in the middle and high water cut stage of water flooding reservoir. In this study, the phenolic resin was synthesized by two‐step alkali catalysis. Factors influencing the synthesis of phenolic resin, including the molar ratio of phenol and formaldehyde, catalyst types, reaction time, were investigated with hydroxylmethyl and aldehyde content as the criterion. When the molar ratio of phenolic resin was 1:2 and NaOH was catalyst, at 80°C for 4 h, the phenolic resin had the highest hydroxymethyl content (49.37%) and the lowest free aldehyde content (2.95%). Weak gel was formed by the reaction of LT002‐polyacrylamide with phenolic resin. Taking the gelation time and strength as criteria, the factors influencing the crosslinking property, including hydroxymethyl content, crosslinker addition, and polyacrylamide concentration were investigated respectively. Under optimal formulation, the property investigation shows that the hydroxymethyl group in the phenolic resin can be crosslinked with the amide group in polyacrylamide, the gelation time is long (50–60 h), and the gelation strength is larger than 5 × 104 mPa s, which is conductive to the plugging of deep oil layers. When the permeability was 5061 × 10−3 μm2, the plugging rate was 72.73%.

Novel dialkylphosphinic acid modified Merrifield resins: Synthesis, characterization, and their adsorption and separation behaviors for zirconium and hafnium

Deep separation of Zr and Hf has always been a great challenging due to their very similar physicochemical properties. In this study, we established a method to synthesize two novel extraction chromatographic resins which graft dialkylphosphinic acid groups through amide group. The dialkylphosphinic acid modified resins were characterized by FT-IR, EA, SEM-EDS, XPS, and BET. Their adsorption and separation behaviors for Zr and Hf were investigated, and the adsorption mechanism was studied. The Zr and Hf adsorption onto Mer-CON-POOH-272 and Mer-CON-POOH-HYY2 both fit pseudo-second order model and Langmuir isotherm model. Mer-CON-POOH-HYY2 has stronger affinity to Zr and Hf than Mer-CON-POOH-272. Mer-CON-POOH-272 has a theoretical maximum loading capacity of 5.663 mg·g−1 Zr and 11.111 mg·g−1 Hf, while Mer-CON-POOH-HYY2 has a higher theoretical maximum loading capacity of 8.376 mg·g−1 Zr and 13.157 mg·g−1 Hf. Dialkylphosphinic acids are the functional groups of Mer-CON-POOH-272 and Mer-CON-POOH-HYY2 that interact with Zr and Hf during adsorption. They adsorb Zr and Hf through cation exchange mechanism, which can be expressed as M(SO4)32– + 2HL ⇌ M(SO4)L2 +.2H+ + 2SO42-. With increasing H2SO4 concentration, the Zr and Hf extraction percentages and their separation efficiency reduce. The DFT calculation reveals that the adsorption process is accompanied by charge transfer. Adsorption occurs mainly at P = O and P-O positions. The affinity of the two resins for Hf is higher than that of Zr, which is the reason why the resin preferentially adsorbs Hf.

Intelligent solar-driven “switch” photothermal hydrogel for clean water harvesting

Water shortage is becoming a huge challenge to mankind. Inspired by pufferfish, we developed an intelligent solar-driven “switch” hydrogel system PEG-PNIPAAm/Fe3O4 hydrogel (PPFH). This hydrogel system is characterized by a uniform porous network structure formed by the integration of hydrophilic PEG, temperature-responsive PNIPAAm polymer and Fe3O4 photothermal nanoparticles. The three-dimensional porous structure provides a higher surface area, offering more adsorption sites for water molecules. The interaction between PPFH and water primarily relies on the hydrogen bonding between the amide groups in PNIPAAm and water molecules, which enhances the hydration of the hydrogel network for rapidly water harvesting. However, when exposed to sunlight, the presence of Fe3O4 nanoparticles causes the ambient temperature to rise rapidly above the LCST, the hydrogen bonding between molecules gradually weakens, while the hydrophobic interactions among the hydrophobic groups in PNIPAAm become stronger, causing the polymer chains to contract and water releasing. The fog capture performance of PPFH can reach up to 3.2 g g−1, and under the irradiation of a sunlight (1 kW m−2), the captured water can be released within 8 min, and the water release efficiency reaches 94 %. This design concept provides the possibility for promoting the widespread implementation of hydrogels-based solar evaporators in practical purification systems in the future, alleviating water shortages issues.

High-Temperature-Resistant Profile Control System Formed by Hydrolyzed Polyacrylamide and Water-Soluble Phenol-Formaldehyde Resin.

To realize the effective profile control of a heavy oil reservoir, hydrolyzed polyacrylamide (HPAM) and water-soluble phenol-formaldehyde resin (PR) were chosen to prepare the profile control system, which gelled at medium or low temperatures and existed stably at high temperatures in the meantime. The effects of phenolic ratios, PR concentration, and HPAM concentration on the formation and strength of the gels were systematically studied by the gel-strength code method and rheological measurements. And the microstructure of the gels was investigated by scanning electron microscope measurements. The results showed that the gelling time of the HPAM-PR system was 13 h at 70 °C. The formed gel could stay stable for 90 days at 140 °C. In addition, the gels showed viscoelastic properties, and the viscosity reached 18,000 mPa·s under a 1.5 s-1 shearing rate due to their three-dimensional cellular network structure. The formation of the gels was attributable to the hydroxyl groups of the PR crosslinking agent, which could undergo the dehydration condensation reaction with amide groups under non-acidic conditions and form intermolecular crosslinking with HPAM molecules. And the organic crosslinker gel system could maintain stability at higher temperatures because covalent bonds formed between molecules.

Multi-interface interaction mechanism of pulp reject-based flocculants for the removal of antibiotics and its combined pollutants

The efficient removal of antibiotics and its combined pollutants is essential for aquatic environment and human health. In this study, a lignin-based organic flocculant named PRL-VAc-DMC was synthesized using pulp reject as the raw material, with vinyl acetate (VAc) and methacryloxyethyltrimethyl ammonium chloride (DMC) as the grafting monomers. A series of modern characterization methods were used to confirm the successful preparation of PRL-VAc-DMC and elucidate its polymerization mechanism. It was found that the Ph-OH group and its contiguous carbon atoms of lignin served as the primary active sites to react with grafting monomers. Flocculation experiments revealed that PRL-VAc-DMC could react with tetracycline (TC) through π-π* interaction, hydrophobic interaction, hydrogen bonding, and electrostatic attraction. With the coexistence of humic acid (HA) and Kaolin, the aromatic ring, hydroxyl, and amide group of TC could react with the benzene ring, hydroxyl group, and carboxyl group of HA, forming TC@HA@Kaolin complexes with Kaolin particles acting as the hydrophilic shell. The increase in particle size, electronegativity, and hydrophily of TC@HA@Kaolin complexes facilitated their interaction with PRL-VAc-DMC through strong interfacial interactions. Consequently, the presence of HA and Kaolin promoted the removal of TC. The synergistic removal mechanism of TC, HA, and Kaolin by PRL-VAc-DMC was systematically analyzed from the perspective of muti-interface interactions. This paper is of great significance for the comprehensive utilization of pulp reject and provides new insights into the flocculation mechanism at the molecular scale.

REVIEW: POTENCY OF AMIDE DERIVATES AS CO-CRYSTAL FORMERS AND ITS IMPACT ON THE PHYSICOCHEMICAL OF ACTIVE PHARMACEUTICAL INGREDIENTS

Enhancing the physicochemical properties of active pharmaceutical ingredients (APIs) has been achieved by utilizing solid modification through the formation of co-crystals. Co-crystal was formed from active pharmaceutical ingredients and co-crystal former, more commonly called coformers. The occurrence of hydrogen bonds in the formation of co-crystals depends on the presence of groups that act as hydrogen bond donors or acceptors in API. Amide-derived coformers are widely used to form hydrogen bonds with API. This review aims to examine the potential of amide derivates as co-crystal-forming materials (coformers), groups in active pharmaceutical ingredients that can form hydrogen bonds with amide derivates and their impact on the physicochemical properties of API. Initial search results yielded 88 articles. Furthermore, the authors then conducted a screening based on exclusion and inclusion criteria, so that a total of 54 articles were obtained as review material. Data analysis in this journal review was carried out using descriptive analysis. Amide derivates have great potential to be used as co-crystal-forming materials due to the presence of amide or carboxamide groups (-CONH2), which can act as donors as well as acceptors of hydrogen bonds. Most of the amide-derived coformers with aliphatic amide groups, aromatic amides, pyridine carboxamides, and sulfonylcarboxamide form heterosynthon bonds with carboxylic groups on API. However, the formation of homosynthon bonds between amide and amide groups can occur, as in the 5-fluorouracil-urea co-crystal. Most of the amide derivates as coformers can change the physicochemical properties of APIs, especially in increasing the solubility and dissolution rate.

Bimetallic Ln-MOF nanofibrous membrane as colorimetric fluorescent test strip for 1, 4-dioxane-glycol mixture ratio sensing

A bimetallic Ln-MOF nanofibrous membrane (NFM) was successfully fabricated by in situ growth of Eu/Tb-MOF crystals onto electrospun polycaprolactam (PA6) nanofibers. For better combining with PA6 nanofibers, the Eu/Tb-MOFs were made into nanocrystals. Characterization with PXRD, FT-IR, EDS and XPS confirmed that the crystal structure of the Eu/Tb-MOFs maintained well on PA6 NFM. The as-prepared Eu/Tb-MOF@PA6 NFM can be used as a colorimetric fluorescent test strip for instant detection of the volume ratio of 1, 4-dioxane in 1, 4-dioxane-glycol mixture. With the increase of 1, 4-dioxane, the test strip presented color changes from green to red, which can be easily distinguished by the naked eye. In view of this, the conversion rate of the condensation reaction of glycol to 1, 4-dioxane will be preliminarily estimated without the help of equipment. More importantly, the test strip exhibited better convenience and reversibility compared with powdered Ln-MOFs because no separation process was needed for test strip before and after recovering. Benefiting from sufficient amide groups in PA6 for anchoring Eu/Tb-MOF particles, the test strip showed satisfactory stability in cycling experiments. This work will provide a new insight into the development of fluorescent test strip based on electrospun MOF NFM for quantitatively monitoring the reaction process.

Interface Dipole Management of D–A‐Type Molecules for Efficient Perovskite Solar Cells

AbstractInterfacial engineering of perovskite films has been the main strategies in improving the efficiency and stability of perovskite solar cells (PSCs). In this study, three new donor‐acceptor (D–A)‐type interfacial dipole (DAID) molecules with hole‐transporting and different anchoring units are designed and employed in PSCs. The formation of interface dipoles by the DAID molecules on the perovskite film can efficiently modulate the energy level alignment, improve charge extraction, and reduce non‐radiative recombination. Among the three DAID molecules, TPA‐BAM with amide group exhibits the best chemical and optoelectrical properties, achieving a champion PCE of 25.29 % with the enhanced open‐circuit voltage of 1.174 V and fill factor of 84.34 %, due to the reduced defect density and improved interfacial hole extraction. Meanwhile, the operational stability of the unencapsulated device has been significantly improved. Our study provides a prospect for rationalized screening of interfacial dipole materials for efficient and stable PSCs.

Interface Dipole Management of D-A-Type Molecules for Efficient Perovskite Solar Cells.

Interfacial engineering of perovskite films has been the main strategies in improving the efficiency and stability of perovskite solar cells (PSCs). In this study, three new donor-acceptor (D-A)-type interfacial dipole (DAID) molecules with hole-transporting and different anchoring units are designed and employed in PSCs. The formation of interface dipoles by the DAID molecules on the perovskite film can efficiently modulate the energy level alignment, improve charge extraction, and reduce non-radiative recombination. Among the three DAID molecules, TPA-BAM with amide group exhibits the best chemical and optoelectrical properties, achieving a champion PCE of 25.29 % with the enhanced open-circuit voltage of 1.174 V and fill factor of 84.34 %, due to the reduced defect density and improved interfacial hole extraction. Meanwhile, the operational stability of the unencapsulated device has been significantly improved. Our study provides a prospect for rationalized screening of interfacial dipole materials for efficient and stable PSCs.

Theoretical studies on the aqueous phase and graphene heterogeneous degradation of acrylamide and acrylonitrile by HO, ClO, and BrO radicals

The newly discovered ClO• and BrO• contribute to pollutant degradation in advanced oxidation processes, while acrylamide (AM) and acrylonitrile (ACN) are always the focus of scientists concerned due to their continuous production and highly toxic effects. Moreover, various particles with a graphene-like structure are the companions of AM/ACN in dry/wet sedimentation or aqueous phase existence, which play an important role in heterogeneous oxidation. Thus, this work focuses on the reaction mechanism and environmental effect of AM/ACN with ClO•/BrO•/HO• in the water environment under the influence of graphene (GP). The results show that although the reactivity sequence of AM and ACN takes the order of with HO• > with BrO• > with ClO•, the easiest channel always occurs at the same C-position of the two reactants. The reaction rate constants (k) of AM with three radicals are 2 times larger than that with ACN, and amide groups have a better ability to activate CC bonds than cyanide groups. The existence of GP can accelerate the target reaction, and the k increased by 9–13 orders of magnitude. The toxicity assessment results show that the toxic effect of most products is lower than that of parent compounds, but the environmental risk of products from ClO•/BrO•-adducts is higher than those from HO•-adducts. The oxidative degradation process based on ClO• and BrO• deserves special attention, and the catalytic effect of GP and its derivatives on the oxidation process is non-negligible.

Bifunctional Ligand Enables Gold-Catalyzed Propargyl C-H Functionalization via Reactive Gold Allenylidene Intermediate.

Gold allenylidene species have been seldom exploited as reactive intermediates in synthetically versatile catalytic reactions. By employing alkynylbenziodoxoles as the substrates and bifunctional WangPhos as the metal ligand, this work demonstrated ready catalytic access to these intermediates of general substitution patterns and their electrophilic reactivities at the γ-carbon center with a diverse range of nucleophiles. The reaction is driven by the reductive decomposition of the benziodoxole moiety and achieves the replacement of a propargylic proton with an N/O/C-based nucleophile, hence realizing reactivity umpolung. Corroborated by Density Functional Theory (DFT) calculations, the reaction mechanism involves a mild propargylic deprotonation. In contrast to prior works employing a tertiary amine functionality, a weakly BrØnsted-basic amide group in WangPhos is surprisingly effective in deprotonation at the propargylic position under a gold-ligand cooperation regime.

Bifunctional Ligand Enables Gold‐Catalyzed Propargyl C−H Functionalization via Reactive Gold Allenylidene Intermediate

AbstractGold allenylidene species have been seldom exploited as reactive intermediates in synthetically versatile catalytic reactions. By employing alkynylbenziodoxoles as the substrates and bifunctional WangPhos as the metal ligand, this work demonstrated ready catalytic access to these intermediates of general substitution patterns and their electrophilic reactivities at the γ‐carbon center with a diverse range of nucleophiles. The reaction is driven by the reductive decomposition of the benziodoxole moiety and achieves the replacement of a propargylic proton with an N/O/C‐based nucleophile, hence realizing reactivity umpolung. Corroborated by Density Functional Theory (DFT) calculations, the reaction mechanism involves a mild propargylic deprotonation. In contrast to prior works employing a tertiary amine functionality, a weakly BrØnsted‐basic amide group in WangPhos is surprisingly effective in deprotonation at the propargylic position under a gold‐ligand cooperation regime.

Synthesis and properties of novel colorless polyimide containing indene and amide groups

AbstractTwo novel diamines 1‐(4‐aminophenyl)‐1,3,3‐trimethyl‐2,3‐dihydro‐1H‐indene‐5‐amine and 4‐amino‐N‐(4‐(5‐(4‐aminobenzamide)‐1,3,3‐trimethyl‐2,3‐dihydro‐1H‐inden‐1‐yl) phenyl) benzamide containing indene and amide groups were successfully designed and synthesized, and a series of colorless polyimides (CPIs) derived from the two diamines with 1,2,4,5‐cyclohexanetetracarboxylic dianhydride in various ratios were copolymerized. The introduction of aliphatic ring structures was conducive to the improvement of optical properties, while the incorporation of amide groups improved thermal and mechanical properties. These CPI films exhibited excellent optical properties (T400 > 80%), high heat resistance (Tg > 300 °C) and mechanical properties with the synergistic action of the two groups. Furthermore, the effect of the content of amide groups on the intermolecular interaction of CPIs was systematically analyzed. This study provides a fancy method for the development of heat‐resistant colorless materials for optical applications.

Coalescence of Porous Coordination Cages into Crystalline and Amorphous Bulk Solids.

Discrete porous coordination cages are attractive as a solution processable material whose porosity is not predicated on a network structure. Here, we leverage the peripheral functionalization of these cage structures to obtain 12 novel, solution processable, porous coordination cages that afford crystalline and amorphous single-phase millimeter-scale monolithic bulk structures (six of each) upon solidification. These structures are based upon prototypal metal-organic polyhedra [Cu24(5-x-isophthalate)24] (where x = NH2, OH), wherein meta-substitution of linker ligands with acyl chloride or isocyanate moieties afforded amide and urethane functional groups, respectively. These porous cage structures were obtainable via direct synthesis between a metal salt and a ligand as well as postsynthetic modification of the cage and formed monoliths following centrifugation and drying of the product. We rationalize their self-assembly as colloidal packing of nanoscale cuboctahedral cages through weak interactions between their hydrophobic alkyl/aromatic surfaces. In general, amorphous solids were obtained via rapid precipitation from the mother liquor upon methanol addition, while crystalline solids could be obtained only following further chloroform and pyridine additions. The structure of the materials is confirmed via gas sorption and spectroscopic methods, while powder X-ray diffraction and transmission electron microscopy are used to determine the nature of these bulk solids.

Melamine-Maleic Acid Polyamide Adduct / Polyacrylonitrile Nanofibers as a Novel Adsorbent for Removal of Methyelene Blue Dye from Aqueous Solutions

Efficient removal of methylene blue (MB) dye from aqueous solutions is crucial for addressing environmental pollution. This study investigates the potential of Melamine-maleic acid polyamide adduct/polyacrylonitrile (ME-MA amide polymer/PAN) nanofibers as a novel adsorbent for MB dye removal. Characterization via scanning electron microscopy (SEM) revealed surface morphology changes, with fiber diameters ranging from 1 to 3 μm. Thermal stability analysis demonstrated enhanced stability for ME-MA/PAN compared to pure PAN fibers. Fourier transform infrared (FT-IR) analysis confirmed the presence of hydroxyl, amide, and thiol groups on the nanoparticle surface, covalently attached to the nanofiber surface. Through electrospinning, ME-MA/PAN composites were synthesized, showing promising capabilities for dye removal. Optimal conditions were observed at pH 12 and a ME-MA PAN dose of 0.02 g. MB removal efficiency increased with higher initial dye concentrations, peaking at 30 mg/L, and higher temperatures up to 40°C. Adsorption isotherm models indicated Langmuir adsorption capacity (Qm) of 111.10 mg g−1 and a separation factor (RL) of 0.297, with Freundlich constants (1/n) and KF values of 0.418 and 22.9, respectively. Kinetic and thermodynamic studies revealed favorable conditions for MB dye removal, validating ME-MA amide polymer/PAN nanofiber composites as environmentally friendly and effective materials for eliminating toxic MB dye from aqueous solutions. This research highlights the potential of ME-MA/PAN nanofibers in addressing dye pollution, suggesting their application in wastewater treatment for sustainable environmental management. Further investigation into regeneration methods and scalability is recommended for practical implementation in real-world scenarios.

Synthesis, characterization and reactivity of a Mn(III)–hydroxido complex as a biomimetic model for lipoxygenase

Manganese hydroxido (Mn–OH) complexes supported by a tripodal N,N′,N″-[nitrilotris(ethane-2,1-diyl)]tris(P,P-diphenylphosphinic amido) ([poat]3−) ligand have been synthesized and characterized by spectroscopic techniques including UV–vis and electron paramagnetic resonance (EPR) spectroscopies. X-ray diffraction (XRD) methods were used to confirm the solid-state molecular structures of {Na2[MnIIpoat(OH)]}2 and {Na[MnIIIpoat(OH)]}2 as clusters that are linked by the electrostatic interactions between the sodium counterions and the oxygen atom of the ligated hydroxido unit and the phosphinic (P=O) amide groups of [poat]3−. Both clusters feature two independent monoanionic fragments in which each contains a trigonal bipyramidal Mn center that is comprised of three equatorial deprotonated amide nitrogen atoms, an apical tertiary amine, and an axial hydroxido ligand. XRD analyses of {Na[MnIIIpoat(OH)]}2 also showed an intramolecular hydrogen bonding interaction between the MnIII–OH unit and P=O group of [poat]3−. Crystalline {Na[MnIIIpoat(OH)]}2 remains as clusters with Na+---O interactions in solution and is unreactive toward external substrates. However, conductivity studies indicated that [MnIIIpoat(OH)]− generated in situ is monomeric and reactivity studies found that it is capable of cleaving C-H bonds, illustrating the importance of solution-phase speciation and its direct effect on chemical reactivity.Synopsis: Manganese–hydroxido complexes were synthesized to study the influence of H-bonds in the secondary coordination sphere and their effects on the oxidative cleavage of substrates containing C-H bonds.

Digestion and absorption characteristics of iron-chelating silver carp scale collagen peptide and insights into their chelation mechanism

Iron deficiency is widespread throughout the world, supplementing sufficient iron or improving the bioavailability of iron is the fundamental strategy to solve the problem of iron scarcity. Herein, we explored a new form of iron supplement, iron chelates of silver carp scales (SCSCP-Fe) were prepared from collagen peptide of silver carp scales (SCSCP) and FeCl2·4H2O, the effects of external environment and simulated gastrointestinal digestive environment on the stability of SCSCP-Fe and the structural changes of peptide iron chelates during digestion were investigated. The results of in vitro iron absorption promotion showed that the iron bioavailability of SCSCP-Fe was higher than that of FeSO4. Two potential high iron chelating peptides DTSGGYDEY (DY) and LQGSNEIEIR (LR) were screened and synthesized from the SCSCP sequence by molecular dynamics and LC-MS/MS techniques. The FTIR results displayed that the binding sites of DY and LR for Fe2+ were the carboxyl group, the amino group, and the nitrogen atom on the amide group on the peptide. ITC results indicated that the chelation reactions of DY and LR with Fe2+ were mainly dominated by electrostatic interactions, forming chelates in stoichiometric ratios of 1:2 and 1:1, respectively. Both DY and LR had a certain ability to promote iron absorption. The transport of DY-Fe chelate may be a combination of the three pathways: PepT1 vector pathway, cell bypass, and endocytosis, while LR-Fe chelate was dominated by bivalent metal ion transporters. This study is expected to provide theoretical reference and technical support for the high-value utilization of silver carp scales and the development of novel iron supplements.

1,2,3-Triazole-Containing Azamacrocycles from Chiral Triazolopeptoids: Synthesis and Solid-State Studies.

Two new chiral 1,2,3-triazole-containing macrocyclic oligoamides (i. e.: triazolopeptoid 4 and 5) were obtained through solid-phase synthesis of linear precursors followed by high dilution macrocyclization reaction. Theoretical (DFT) and spectroscopic (NMR) studies revealed the intricate interplay between the Nα-chiral side chains and their conformational attitudes. BH3-mediated reduction of the tertiary amide groups of known 1-3 and newly synthesized 4 gave novel azamacrocycles 6-9. Detection of borane complexes of azamacrocycles 6 and 9 (i. e.: 10 and 11), corroborated by X-ray diffraction studies, demonstrated the peculiar properties of 1,2,3-triazole-containing macrorings.