scholarly journals Light-gated nano-porous polymersomes from stereoisomer-directed self-assemblies

2020 ◽  
Author(s):  
Hui Chen ◽  
Yujiao Fan ◽  
Xia Yu ◽  
Vincent Semetey ◽  
Sylvain Trépout ◽  
...  
Keyword(s):  
Block Copolymer ◽  
Trans Isomer ◽  
Uv Light ◽  
Drug Carriers ◽  
Natural Systems ◽  
Biomimetic Systems ◽  
Virus Capsids ◽  
Cylindrical Micelles ◽  
Cis Isomer ◽  
Material Exchange

Abstract Capsules with holes in the walls exist in natural systems like virus capsids, and in biomimetic systems like immune-stimulating complexes vaccines and liposomes of phospholipids/surfactants mixtures. Structuring pores into stable membrane and controlling their opening are extremely useful for applications that require nano-pores as channels for material exchange and transportation. Polymersomes, which are stable and robust vesicles made of amphiphilic block copolymer, are good candidates for drug carriers or micro/nanoreactors. Engineering structure-inherent and light-gated nano-porous polymersomes is especially appealing, but still unexplored. Here we present these polymersomes made from a polymer including a tetraphenylethene (TPE) in its center. TPE is an emblematic fluorogen with aggregation-induced emission, which possesses two stereoisomers sensitive to photoisomerization. Trans-isomer of the polymer forms classical vesicles, cis-isomer forms cylindrical micelles, while trans/cis mixtures construct perforated vesicles with nano-pores. Under UV light, the classical polymersomes of trans-isomer can be perforated by its cis-counterpart generated from the photoisomerization.

Photoresponsive Organogel Based on Supramolecular Assembly of Tris(phenylisoxazolyl)benzene

2010 ◽  
Vol 63 (4) ◽  
pp. 640 ◽  
Author(s):  
Takeharu Haino ◽  
Hiroshi Saito
Keyword(s):  
Structural Change ◽  
Solid State ◽  
Trans Isomer ◽  
Self Assembly ◽  
Uv Light ◽  
Supramolecular Assembly ◽  
The Self ◽  
Solvent Molecules ◽  
Supramolecular Networks ◽  
Cis Isomer

Azobenzene-substituted tris(phenylisoxazolyl)benzene 1 was developed as a photoresponsive gelator. A detailed study of the self-assembly of the trans- and cis-isomers in solution revealed that the planar trans-isomer assembled to form molecular stacks along its C 3 axis, whereas the cis-isomer did not owing to steric requirements. Based on diffusion ordered spectroscopy experiments, the size of the aggregates formed from the trans-isomer were roughly four times as large as those of the cis-isomer. The photoinduced gel-to-sol transition was achieved by irradiation with UV light at 360 nm. Solid-state morphologies of the trans- and cis-isomers were quite contrastive; the trans-isomer created fibrous supramolecular networks with a lot of voids in which solvent molecules could be immobilized, whereas the cis-isomer never created such fibrous morphologies. The trans–cis structural change of the azobenzene moieties obviously regulates the gelation ability of 1.

scholarly journals Reaction of cis- and trans-Dichlorotetra(Dimethylsulfoxide)Ruthenium(II) With the Antiviral Drug Acyclovir

2000 ◽  
Vol 7 (6) ◽  
pp. 325-334 ◽  
Author(s):  
Aglaia Koutsodimou ◽  
Giovanni Natile
Keyword(s):  
Trans Isomer ◽  
Early Stage ◽  
Antiviral Drug ◽  
Metallic Substrate ◽  
Purine Base ◽  
Coordination Environment ◽  
Molar Ratios ◽  
Discrete Amount ◽  
Cis And Trans ◽  
Cis Isomer

NMR was used to investigate the reaction of cis- and trans-[RuCl2(DMSO)4] with the antiviral drug acyclovir, a guanine derivative containing the acyclic (2-hydroxo) ethoxymethyl pendant linked to N(9). Studies were performed in aqueous solutions at ambient temperature and at 37 °C, and at various molar ratios. Both isomers yielded two compounds, a monoadduct and a bisadduct, the relative yields being dependent upon the metal to ligand concentration ratios. The products derived from the two Ru isomers displayed identical NMR spectra, suggesting that they have the same coordination environment, however the rate of formation of the monoadduct was higher in the case of the trans isomer than in the case of the cis isomer, while the rate of conversion of the monoadduct into the bisadduct appeared to be similar in both cases. As a consequence in the case of the trans isomer there is accumulation of monoadduct in the early stage of the reaction, whose concentration afterwards decreases with the progress of the reaction. As for platinum, also for ruthenium the preferred binding site is N(7) of the purine base, however, in the case of ruthenium a discrete amount of bisadduct is formed even in the presence of an excess of metallic substrate with respect to the acyclovir ligand; under similar conditions a platinum substrate would have given, nearly exclusively, the monoadduct.

[1H,15N] N.M.R. Kinetic Studies of Reactions of cis- and trans-[PtCl2(15NH3)(c-C6H1115NH2)] with Guanosine 5'-Monophosphate

1999 ◽  
Vol 52 (3) ◽  
pp. 173 ◽  
Author(s):  
Sarah J. Barton ◽  
Kevin J. Barnham ◽  
Abraha Habtemariam ◽  
Urban Frey ◽  
Rodney E. Sue ◽  
...  
Keyword(s):  
Trans Isomer ◽  
Active Metabolite ◽  
Kinetic Studies ◽  
Trans Influence ◽  
Trans Complex ◽  
Kinetics Of Reaction ◽  
Cis And Trans ◽  
Kinetics Of ◽  
Cis Isomer ◽  
Amine Ligand

cis-[PtCl2(15NH3)(c-C6H11NH2)] is an active metabolite of the oral platinum(IV) anticancer drug cis,trans,cis-[PtCl2(CH3CO2)2(NH2)(c-C6H11NH2)]. Since it is likely that guanine bases on DNA are targets for this drug, we have analysed the kinetics of reaction of this platinum(II) metabolite with guanosine 5′-monophosphate (5′-GMP) at 310 K, pH 7, using [1H, 15N] n.m.r. methods. Reactions of the trans isomer are reported for comparison. The reactions proceed via aquated intermediates, and, for the cis isomer, the rates of aquation and substitution of H2O by 5′-GMP are 2-5 times faster trans to the amine ligand (c-C6H11NH2) compared to trans to NH3 for both the first and second steps. For the trans complex, the first aquation step is c. 3 times faster than for the cis complex, as expected from the higher trans influence of Cl¯, whereas the rate of the second aquation step (trans to N7 of 5′-GMP) is comparable to that trans to NH3. These findings have implications for the courses of reactions with DNA.

UV Light Stability of α-Cyclodextrin/Resveratrol Host - Guest Complexes and Isomer Stability at Varying pH

2009 ◽  
Vol 62 (8) ◽  
pp. 921 ◽  
Author(s):  
Kerrilee E. Allan ◽  
Claire E. Lenehan ◽  
Amanda V. Ellis
Keyword(s):  
Inclusion Complex ◽  
Uv Light ◽  
Sodium Dodecyl ◽  
Molar Absorptivity ◽  
Photo Degradation ◽  
Light Stability ◽  
Uv Visible ◽  
The Stability ◽  
Ph Range ◽  
Cis Isomer

trans-Resveratrol is an antioxidant that readily isomerizes to the cis isomer under UV irradiation. Here we report on the UV-Visible analysis of the stability of both trans- and cis-resveratrol isomers in the presence of UV light over a pH range of 2.0–9.0 in a phosphate-borate buffer that contains sodium dodecyl sulphate and acetonitrile. The molar absorptivity of the trans-resveratrol solution absorbing at 320 nm (3.88 eV) and 305 nm (4.07 eV) was 33000 and 34000 M–1 cm–1, respectively. Results indicate that trans-resveratrol has a slower isomerization within a pH range of 5.0–8.0. A pH > 8.0 results in almost immediate isomerization of the sample, whereas at pH 2.0 a photo-degradation product appears at 260 nm (4.77 eV). This was not apparent at pH 8.0. By including trans-resveratrol into a trans-resveratrol/α-cyclodextrin host–guest inclusion complex in pH 8.0 buffer isomerization was greatly reduced, with enhanced trans-resveratrol photostability.

Y-shaped block copolymer (methoxy-poly(ethylene glycol))2-b-poly(l-glutamic acid): preparation, self-assembly, and use as drug carriers

RSC Advances ◽  
2014 ◽  
Vol 4 (78) ◽  
pp. 41588-41596 ◽  
Author(s):  
Lixin Yang ◽  
Xiuli Hu ◽  
Weiqi Wang ◽  
Shi Liu ◽  
Tingting Sun ◽  
...  
Keyword(s):  
Block Copolymer ◽  
Ethylene Glycol ◽  
Glutamic Acid ◽  
Solid Tumors ◽  
Self Assembly ◽  
Drug Carriers ◽  
Poly Ethylene Glycol ◽  
Poly Ethylene ◽  
Polymer Drugs

The nano polymer drugs based on Y-shaped block copolymer mPEG2-PGA show a great potential on the treatment for solid tumors.

Ketal containing amphiphilic block copolymer micelles as pH-sensitive drug carriers

2013 ◽  
Vol 448 (1) ◽  
pp. 259-266 ◽  
Author(s):  
Iljae Lee ◽  
Minhyung Park ◽  
Yerang Kim ◽  
On Hwang ◽  
Gilson Khang ◽  
...  
Keyword(s):  
Block Copolymer ◽  
Drug Carriers ◽  
Ph Sensitive ◽  
Amphiphilic Block Copolymer ◽  
Block Copolymer Micelles ◽  
Copolymer Micelles

Sur la réduction de polyméthyldihydro-2,3 phénalènones-1 par l'hydrure de lithium et d'aluminium

1974 ◽  
Vol 52 (17) ◽  
pp. 3106-3112 ◽  
Author(s):  
E. Costakis ◽  
P. Canonne ◽  
R. St-Jean
Keyword(s):  
Trans Isomer ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Considerable Extent ◽  
Lithium Aluminum ◽  
Trans Isomers ◽  
Cis And Trans Isomers ◽  
Cis And Trans ◽  
Cis Isomer ◽  
Steric Constraints

The reduction of some polymethyl-2,3-dihydro phenalen-1-ones by lithium aluminum hydride yields a mixture of cis and trans isomers; the percentage of each isomer depends to a considerable extent on its structure. Indeed, for some, the trans isomer predominates while for others the cis isomer is obtained in up to 88% yields. Moreover, in the particular case in which the trans isomer is formed in low yields, its preferred conformation is trans diaxial.The steric constraints which render certain transition states unfavourable during the attack of the hydride are discussed with the aid of spectroscopic data on the alcohols obtained. [Journal translation]

The importance of conformation in the reactivity of radical cations. Changing configuration at saturated carbon centres

1992 ◽  
Vol 70 (1) ◽  
pp. 272-279 ◽  
Author(s):  
Allyson L. Perrott ◽  
Donald R. Arnold
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Molecular Mechanics ◽  
Radical Cation ◽  
Trans Isomer ◽  
Radical Cations ◽  
Singlet Excited State ◽  
Photostationary State ◽  
Configurational Isomerization ◽  
Cis Isomer

Irradiation of an acetonitrile solution of cis 1-methyl-2-phenylcyclopentane (1bcis); 1,4-dicyanobenzene (2), an electron-accepting photosensitizer; and 2,4,6-collidine (3), a nonnucleophilic base, leads to configurational isomerization of the cyclopentane; the photostationary state lies > 99% in favour of the trans isomer. The mechanism proposed for this reaction involves formation of the radical cation of 1bcis by photoinduced electron transfer to the singlet excited state of 2, deprotonation of the radical cation assisted by the base 3, reduction of the resulting benzylic radical by the radical anion [Formula: see text], and reprotonation of the benzylic anion to give both the cis and the trans isomers of 1b. The photostationary state is controlled by the relative rates of deprotonation of the radical cations of 1bcis and trans; these rates are dependent upon the extent of overlap of the SOMO of the radical cation, which is largely associated with the phenyl ring, and the benzylic carbon–hydrogen bond. Molecular mechanics calculations (MM3 and MMP2) are used to calculate the preferred conformations of the isomers. The required orbital overlap is 31% effective with the global minimum conformation of the cis isomer and essentially ineffective for the low-lying conformations of the trans isomer. This proposed mechanism is supported by Stem–Volmer quenching studies, which indicate that both isomers quench the singlet excited state of 2 at the diffusion-controlled rate, and by deuterium incorporation studies. When irradiation of the cis isomer is carried out in acetonitrile–methanol-O-d as solvent, isomerization is accompanied by deuterium exchange at the benzylic position; the trans isomer is stable under these conditions. Keywords: photosensitized electron transfer, radical cation, deprotonation, configurational isomerization, conformation, molecular mechanics (MM3).

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