We demonstrate a new strategy for the construction of supramolecular hemoprotein assemblies. A synthetic heme was selectively introduced onto surface Cys residue cytochrome b562 single mutant (H63C) through thioether bond. After removal native H63C by acid denaturation followed neutralization, externally attached on apoprotein inserted into vacant pocket other apoprotein. Therefore, interprotein heme−heme interaction produces unique submicrometer-sized linear fiber, determined size exclusion...

Virus-like particles (VLPs) have proven to be versatile platforms for chemical and genetic functionalization a variety of purposes in biomedicine, catalysis, materials science. We describe here the simultaneous modification bacteriophage Qβ VLP with metalloporphyrin derivative photodynamic therapy glycan ligand specific targeting cells bearing CD22 receptor. This application benefits from presence function delivery high local concentration singlet oxygen-generating payload.

The physiological roles of endogenous carbon monoxide (CO) have not been fully understood because the difficulty in preparing a loss-of-function phenotype this molecule. Here, we utilized vivo CO receptors, hemoCDs, which are supramolecular 1:1 inclusion complexes meso-tetrakis(4-sulfonatophenyl)porphinatoiron(II) with per-O-methylated β-cyclodextrin dimers. Three types hemoCDs (hemoCD1, hemoCD2, and hemoCD3) that exhibit different CO-affinities tested as CO-depleting agents vivo....

Carbon monoxide (CO) is a gaseous molecule known as the silent killer. It widely believed that an increase in blood carboxyhemoglobin (CO-Hb) best biomarker to define CO intoxication, while fact accumulation tissues most likely direct cause of mortality less investigated. There no reliable method other than gas chromatography accurately determine content tissues. Here we report properties and usage hemoCD1, synthetic supramolecular compound composed iron(II)porphyrin cyclodextrin dimer,...

Carbon monoxide (CO), a gaseous signaling molecule, has shown promise in preventing body weight gain and metabolic dysfunction induced by high fat diet (HFD), but the mechanisms underlying these effects are largely unknown. An essential component response to HFD is gut microbiome, which significantly altered during obesity represents target for developing new therapeutic interventions fight diseases. Here, we show that CO delivered oral administration with CO-releasing molecule (CORM-401)...

Reversible binding of dioxygen occurs in aqueous solution to a myoglobin model composed porphinato iron(II) compound and per-O-methylated β-cyclodextrin dimer with pyridine linker (see picture). The affinity this system is 17.5±1.7 Torr the half-life O2 adduct 30.1 h phosphate buffer at pH 7 25 °C.

The 1:1 inclusion complex of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphinato iron(II) (FeIITPPS) and an O-methylated β-cyclodextrin dimer having a pyridine linker (1) binds dioxygen reversibly in aqueous solution. O2 adduct was very stable (t1/2 = 30.1 h) at pH 7.0 25 °C. ESI-MS NMR spectroscopic measurements molecular mechanics (MM) calculations indicated the sulfonatophenyl groups 5- 15-positions FeIIITPPS or FeIITPPS into two cyclodextrin moieties 1 to form supramolecular (hemoCD1 for...

Qβ virus-like particles encapsulating multiple copies of fluorescent proteins were generated in high yields using a modular system enhanced by specific engineered RNA–protein interactions. The resulting structurally indistinguishable from recombinant alone. encapsidated nearly identical photochemical properties to monomeric analogues, more stable toward thermal degradation, and protected proteolytic cleavage. Residues on the outer capsid surface chemically derivatized acylation azide–alkyne...

Supramolecular protein polymers: When a heme moiety was introduced to the surface of an apo-cytochrome b(562)(H63C) mutant, supramolecular polymers formed through noncovalent heme-heme pocket interactions. The incorporation triad as pivot molecule in polymer further led two-dimensional network structure, which visualized by tapping-mode atomic force microscopy (see picture).

A CO stripper: The O2-bound form of an iron(II) porphyrin cyclodextrin supramolecular complex (hemoCD) infused into a rat vein reacted with internal through ligand exchange, and the CO-bound hemoCD was immediately excreted in urine (see picture). acting as receptor made it possible to quantify endogenous living organism.

A real life saver: supramolecule (met-hemoCD3, see scheme) was prepared by including a water-soluble porphinato iron(III) in capsule of cyclodextrin dimer (Py3OCD), which synthesized only two steps. The structure met-hemoCD3 determined X-ray crystal analysis (see picture). Ferrous hemoCD3 showed functions similar to those hemoglobin/myoglobin and also functioned as an antidote for cyanide poisoning. As service our authors readers, this journal provides supporting information supplied the...

Carbon monoxide (CO) is produced in mammalian cells during heme metabolism and serves as an important signaling messenger. Here we report the bioactive properties of selective CO scavengers, hemoCD1 its derivative R8-hemoCD1, which have ability to detect remove endogenous cells. HemoCD1 a supramolecular hemoprotein-model complex composed 5,10,15,20-tetrakis(4-sulfonatophenyl)porphinatoiron(II) per-O-methylated β-cyclodextrin dimer having pyridine linker. We demonstrate that can be used...

Obesity is characterized by accumulation of adipose tissue and one the most important risk factors in development insulin resistance. Carbon monoxide–releasing (CO-releasing) molecules (CO-RMs) have been reported to improve metabolic profile obese mice, but underlying mechanism remains poorly defined. Here, we show that oral administration CORM-401 mice fed a high-fat diet (HFD) resulted significant reduction body weight gain, accompanied marked improvement glucose homeostasis. We further...

Glaucoma is an optic degenerative neuropathy that driven by a vicious cycle of oxidative stress and mechanical stress. Current clinical treatments aim exclusively at alleviating reducing the intraocular pressure (IOP). With unattended stress, recurrence deterioration are inevitable. Nitric oxide (NO) carbon monoxide (CO) endogenous gaseous signaling molecules for vasodilation anti-inflammation, respectively. Mounting evidence suggests intricate interplay between NO CO to mediate their...

5,10,15,20-Tetrakis(4-sulfonatophenyl)porphinato iron(III) (Fe(III)TPPS) forms a very stable 1:2 complex with heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TMe-β-CD), whose center is located at hydrophobic cleft formed by two face-to-face TMe-β-CD molecules. Various inorganic anions (X-) such as F-, Cl-, Br-, I-, N3-, and SCN- coordinate to Fe(III)TPPS(TMe-β-CD)2 form five-coordinate high-spin Fe(III)TPPS(X)(TMe-β-CD)2, while no coordination occurs ClO4-, H2PO4-, NO3-, HSO4-. Except for none...

Artificial self-assembling systems comprised of proteins have the potential not only for mimicking naturally occurring protein clusters but also creating functionalized supramolecular polymers. Here we report a new type polymer which utilizes original character and reactivity monomer protein. Myoglobin, an oxygen storage hemoprotein, was chosen as unit provided with externally-attached heme on surface drives formation fibrous assembly through successive interprotein interactions between...

The reaction between hydrosulphide and a haemoglobin model compound, composed of Fe(<sc>iii</sc>)-porphyrin cyclodextrin dimer possessing pyridine-linker, was studied.

Circadian rhythms are regulated by transcription-translation feedback loops (TTFL) of clock genes. Previous studies have demonstrated that core transcriptional factors, NPAS2 and CLOCK, in the TTFL can reversibly bind carbon monoxide (CO) vitro. However, little is known about whether endogenous CO, which continuously produced during a heme metabolic process, involved circadian system. Here we show selective removal CO mice considerably disrupts rhythmic expression A highly scavenger,...

Abstract In this study, we designed a new monolayer-forming material, 2, 2′-bis(octadecyloxy)-1, 1′-binaphthyl-6, 6′-dicarboxylic acid (BNOC), which has axial chirality derived from the binaphthyl moiety with two COOH groups. Because of group occupies larger asymmetric space than central chirality, arrangement derivative is expected to show characteristic structure at air–water interface. addition, BNOC carboxyl groups, may form intermolecular hydrogen bonds. We carried out structural...

The reaction between H2O2 and a pyridine-coordinated ferric porphyrin encapsulated by cyclodextrin dimer yielded hydroperoxoferric intermediate, PFeIII−OOH, which rapidly decomposed to oxoferryl (PFeIV═O). Upon with H2O2, PFeIV═O reverted was converted carbon monoxide-coordinated ferrous under CO atmosphere. in the presence of excess behaves as PFeIII−OOH.

A convenient and efficient method for intracellular delivery of a water-soluble anionic porphyrin has been developed by utilizing its supramolecular interaction with per-<italic>O</italic>-methyl-β-cyclodextrin bearing an octaarginine chain as cell-penetrating peptide.

The O₂adduct of an aqueous synthetic heme/copper model system built on a porphyrin/cyclodextrin supramolecular complex has been characterized.

The advent of macrocycle-based supramolecular chemistry can offer powerful strategies for regulating vital bioactivities in living systems and bring about emerging technology biomedical science. Herein, we construct a supra-biomacromolecular nanosystem involving microtubules, cell-permeable porphyrins, antimitotic peptide-decorated permethyl-β-cyclodextrins promoting cell apoptosis cooperative manner. Through specific polypeptide-tubulin recognition, cyclodextrin moieties are capable...

Simultaneous poisoning by carbon monoxide (CO) and hydrogen cyanide is the major cause of mortality in fire gas accidents. Here, we report on invention an injectable antidote against CO (CN – ) mixed poisoning. The solution contains four compounds: iron(III)porphyrin (Fe III TPPS, F), two methyl-β-cyclodextrin (CD) dimers linked pyridine (Py3CD, P) imidazole (Im3CD, I), a reducing agent (Na 2 S O 4 , S). When these compounds are dissolved saline, synthetic heme models including complex F...