Article
Biochemistry & Molecular Biology
Shun-ichi Wada, Akira Shibaike, Junsuke Hayashi, Hidehito Urata
Summary: The conjugate MAP (Aib) -cRGD has been developed for siRNA delivery into cells, with Aib-containing helical peptide requiring 20 residues for the construction of a carrier.
CHEMISTRY & BIODIVERSITY
(2022)
Article
Biochemistry & Molecular Biology
Renate Gessmann, Hans Brueckner, Kyriacos Petratos
Summary: The synthetic peptide Z-Gly-Aib-Gly-Aib-Gly-Aib-OtBu was crystallized in a centrosymmetric space group, with three molecules in the asymmetric unit showing variations in the Z-group conformation. This peptide forms different helical regions and beta-turn types, different from other known Aib-containing peptides which typically adopt 3(10)- or alpha-helical structures.
JOURNAL OF PEPTIDE SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Lizeth Bodero, Karine Guitot, Nathalie Lensen, Olivier Lequin, Thierry Brigaud, Sandrine Ongeri, Gregory Chaume
Summary: Incorporating a chiral residue at one terminus of a peptide chain can control the screw-sense preference of the helical structure. Introducing a trifluoromethyl group can reverse the screw-sense preference of the 3(10)-helix and serve as a reliable F-19 NMR probe to determine the magnitude and sign assignment of the screw-sense preference.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Na Liu, Xinyue Zhou, Li Zhou, Zongquan Wu
Summary: A novel diazoacetate monomer was successfully synthesized, leading to the formation of helical polycarbenes with well-defined molecular weights and low polydispersity. These polycarbenes showed high catalytic ability in asymmetric Michael addition reactions, with increased enantioselectivity and diastereoselectivity compared to traditional catalysts. Additionally, the helical polycarbene catalyst can be easily recovered and reused multiple times without significant loss of its selectivity.
Article
Chemistry, Physical
Dibakar Sarkar, Narayan Chandra Maity, Gourav Shome, Kyriakos Gabriel Varnava, Vijayalekshmi Sarojini, Subramanian Vivekanandan, Nirakar Sahoo, Sourav Kumar, Atin Kumar Mandal, Ranjit Biswas, Anirban Bhunia
Summary: This study investigates the role of specific functional epitopes in the primary structure of hIAPP in regulating amyloidogenesis and subsequent cytotoxicity. The findings suggest that external changes can directly influence the C-terminal fibrillating sequence and indicate a possible collaborative role of this segment in nucleating hIAPP amyloidogenesis in a physiological scenario, making it a potential target for future therapeutic interventions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Ghassan Q. Ali, Ivan Hameed R. Tomi
Summary: Nonsymmetric 1,2,4-oxadiazole derivatives with cholesteryl and alkoxy chain as end moieties exhibit monotropic liquid crystalline behavior. The molecular structures are confirmed by elemental analysis and spectroscopic studies. Differential scanning calorimetry (DSC) studies reveal multiple phase transitions and polarized optical microscopy (POM) investigations confirm the presence of smectic A (SmA) and chiral nematic (N*) phases. The importance of alkyl chain length in mesophase formation is discussed, and a comparison with other reported mesogenic materials with similar molecular structures is provided.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Neurosciences
Atsushi Shimohata, Dilip Rai, Takumi Akagi, Sumiko Usui, Ikuo Ogiwara, Makoto Kaneda
Summary: In this study, the subcellular localization of mGluR6 CTD mutants in 293T cells was investigated using immunocytochemistry, immunoprecipitation, and flow cytometry. The results showed that mGluR6 mutants with 15- and 20-amino acid deletions from the C terminus localized to the ER and were deficient at the cell surface. Introducing an alanine substitution at basic residues within the CTD rescued the surface deficiency of mGluR6 mutants.
MOLECULAR AND CELLULAR NEUROSCIENCE
(2023)
Article
Biochemistry & Molecular Biology
Yeshveer Singh, Ruby Sharma, Manasi Mishra, Praveen Kumar Verma, Ajay Kumar Saxena
Summary: A study presents the structural and biochemical insights into a fungus-specific class III OYE homologue. The enzyme, ArOYE6, exists as a monomer and possesses a (beta/alpha)(8) barrel structure with non-covalently bound FMN. The study also reveals the importance of a novel C-terminus in stabilizing the FMN binding pocket.
Article
Biochemistry & Molecular Biology
Vinothini Santhakumar, Nahren Manuel Mascarenhas
Summary: The C-terminal helix structure of the thermotoga maritima arginine binding protein plays a crucial role in the conformational transition, restraining the protein in its open-state and potentially guiding it back to the open-state upon ligand unbinding.
JOURNAL OF STRUCTURAL BIOLOGY-X
(2022)
Article
Multidisciplinary Sciences
Prasun Kumar, Neil G. Paterson, Jonathan Clayden, Derek N. Woolfson
Summary: The alpha-helix is important in structural biology and protein folding. This study shows that synthetic peptide assemblies can be built from 3(10)-helices, which are less common in natural proteins. The research provides principles and rules for designing in this unexplored region of protein structure.
Review
Chemistry, Multidisciplinary
Olivia F. B. Watts, Jordan Berreur, Beatrice S. L. Collins, Jonathan Clayden
Summary: Atropisomeric compounds are extensively found in natural products and have important applications in asymmetric transition-metal catalysis as ligands. The enantioselective synthesis of atropisomers is a research target due to their biological activity and pharmaceutical relevance. Biocatalytic strategies for the synthesis of atropisomeric compounds include direct asymmetric construction of atropisomeric bonds and asymmetric transformation of molecules with existing axes.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Siyuan Wang, Flavio della Sala, Matthew J. Cliff, George F. S. Whitehead, Inigo J. Vitorica-Yrezabal, Simon J. Webb
Summary: This study developed a new 19F reporter tag and its attachment to peptide foldamers to investigate their conformation in phospholipid bilayers. The results showed that the conformational preferences of the foldamers were the same in organic solvents and phospholipid bilayers, and phospholipid chirality had little influence on the conformation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
David P. Tilly, Jean-Paul Heeb, Simon J. Webb, Jonathan Clayden
Summary: Molecular biology controls complex reaction networks by translating a chemical input into an orthogonal chemical output, but dynamic foldamers have been limited by stereochenical changes that produce spectroscopic signals. In this study, the authors introduce an artificial molecular translation device that converts a chemical input into an unrelated chemical output. This device modulates the reactivity of an imidazole moiety by the presence of chloride ions through the allosteric remote control of imidazole tautomer states.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Luis Martinez-Crespo, Inigo J. Vitorica-Yrezabal, George F. S. Whitehead, Simon J. Webb
Summary: Relaying conformational change over several nanometers is crucial in allosterically regulated proteins. Scientists have successfully replicated this mechanism using nanometer-sized molecules that can reversibly switch between defined shapes in response to signaling molecules. The study demonstrated that a 1.8 nm long rigid rod molecule can serve as a switchable multi-squaramide hydrogen-bond relay, with each relay adopting different orientations based on proton signals and undergoing reversible changes. Additionally, a chemical fuel acted as a dissipative signal, causing the relay to return to its original orientation when consumed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
David P. Tilly, David T. J. Morris, Jonathan Clayden
Summary: In this study, it was discovered that the ethylene-bridged hydrogen-bonded urea oligomer linear chain has reversible anion coordination and cascade conformational changes. The polarity reversals of hydrogen bonds in the oligomer propagate, resulting in a global switch of hydrogen-bond directionality. This induces a change in emission and excitation wavelengths of a fluorophore at the opposite terminus. Consequently, the molecule acts as a chemical sensor with a relayed remote spectroscopic response to varying anion concentrations. The anion-induced polarity switch provides an artificial communication mechanism for conveying information through oligomeric structures.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
David T. J. Morris, Steven M. Wales, Javier Echavarren, Matej Zabka, Giulia Marsico, John W. Ward, Natalie E. Pridmore, Jonathan Clayden
Summary: Cyclic triureas derived from TACN were synthesized and characterized. Dynamic cyclochirality was observed, with the hydrogen-bonded urea groups exchanging enantiomers through bowl inversion and directionality reversal. Structural modifications were found to affect the enantiomerization barrier, resulting in a planar-chiral, atropisomeric bowl-shaped structure with high stereochemical stability solely from its hydrogen-bonding network.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemical Research Methods
Jean-Paul Heeb, Jonathan Clayden, Martin D. Smith, Roly J. Armstrong
Summary: This article describes three experimental methods, namely kinetic analysis, dynamic HPLC, and variable-temperature NMR, for measuring the rate of racemization in atropisomers. Atropisomers are molecules that exhibit stereochemistry from restricted bond rotation and are highly relevant in catalysis, medicine, and materials science. The methods presented in this article provide techniques for evaluating the configurational stability of atropisomeric molecules and can be performed using standard analytical equipment. The article also discusses the selection of a suitable method for determining racemization rates for new molecular structures with unknown properties.
Article
Multidisciplinary Sciences
Ellie Stammers, Chris D. Parsons, Jonathan Clayden, Alastair J. J. Lennox
Summary: In this paper, an electrochemical method is described for the synthesis of biaryls through metal-catalyst-free coupling. The temporary formation and reduction of ureas are utilized to enhance the synthesis yield.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Sarah J. Pike, Richard Telford, Louise Male
Summary: We report a convenient synthetic route for a new photo-responsive ortho-azobenzene/2,6-pyridyldicarboxamide heterofoldamer, which can adopt a stable helical conformation in both solid state and solution. The stimuli-driven structural re-ordering of the supramolecular scaffold from a stable helical conformation to a less well-ordered state under irradiative conditions has been identified and found to be reversible. The robust nature of the responsive, conformational, molecular switching behavior of the foldamer scaffold has been determined using UV/Vis, H-1 NMR, and CD spectroscopy, with minimal loss in efficiency even after multiple cyclic treatments.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Physical
Hussain A. Al Nasser, Luis Martinez-Crespo, Simon J. Webb, Robert A. W. Dryfe
Summary: Thiourea-based receptors’ binding affinity for anions at the aqueous|organic interface was evaluated using electrochemical measurements. Most anions showed a 1:1 stoichiometry for complexation, except for excess Cl- and Br- anions which exhibited higher stoichiometry. High stability constants were observed at the aqueous|1,2-dichlorobenzene (DCB) interface, possibly due to the less competitive environment of the less polar solvent. Protonation of the receptor at the bridgehead tertiary amine was inferred from potential-dependent voltammetric measurements unrelated to anion:receptor complexation.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Multidisciplinary
David T. J. Morris, Jonathan Clayden
Summary: Biological systems and foldamer chemistry both exploit the propagation of conformational change to communicate information on the molecular scale. Switchable screw-sense preference is a communication mechanism that utilizes dynamic helical foldamers to transmit information. This review discusses the functional requirements for communication devices and describes the use of various stimuli to switch the screw sense. It also explores how conformational switching can control chemical events remote from the source of information.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Organic
David P. Tilly, Catherine McColl, Mingda Hu, Inigo J. Vitorica-Yrezabal, Simon J. Webb
Summary: This article describes the study of two short pentapeptides rich in alpha-aminoisobutyric acid (Aib) as enantioselective organocatalysts. The findings show that folding into a 310 helical structure allows the peptides to transmit chiral information and promote the enantioselectivity of the reaction. This demonstrates the important role of achiral residues in catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
David P. Tilly, Matej Zabka, Inigo Vitorica-Yrezabal, Hazel A. Sparkes, Natalie Pridmore, Jonathan Clayden
Summary: This paper investigates the formation mechanism of higher-order structures of ethylene-bridged oligoureas in both crystalline and solution states. The oligoureas self-assemble into supramolecular nanorings or helical chains through hydrogen bonding interactions. The formation of intermolecular hydrogen bonds at the terminus of the oligoureas switches the directionality of the hydrogen bond chain, promoting further assembly. The helices in the crystal state have identical handedness and polarity, and the interactions in solution are consistent with those in the crystals. The switch of hydrogen bond polarity propagates intermolecularly, constituting an example of intermolecular communication within supramolecular polymers.
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)