The role of amide (n,π∗) transitions in polypeptide clusteroluminescence

Zhang, Zhiming; Yan, Wei; Dang, Dongfeng; Zhang, Haoke; Sun, Jing; Tang, Ben Zhong

doi:10.1016/j.xcrp.2021.100716

Cited by 33 publications

(52 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In Figure 5A, our group has achieved the pure compound 3 via vacuum distillation, it is a very simple structure that only possesses an amide group. 30 As expected, PL characterization on 3 shows a CL emission with λ em at 435 nm whose intensity is enhanced with the increase of solution concentration. As mentioned above, the nitrogen atom in the amide group may also proceed with oxidation and generate such blue emission.…”

Section: In Carbonyl-based Small Moleculessupporting

confidence: 76%

“…Recently, our group reported the CL from poly(Lglutamic acid) (PLGA) and its derivatives whose maximum emission locates around 440 nm. 30 Further experimental and theoretical studies unraveled the important role of (n, π*) transition of amide groups in the CL. Based on this work, we have summarized the CL properties in other systems, such as natural protein, poly(amido amine), polyester, polyketone and their small molecules, then discovered that the blue emission around 440 nm widely exists in these CLgens.…”

Section: Introductionmentioning

confidence: 98%

See 1 more Smart Citation

The mysterious blue emission around 440 nm in carbonyl‐based aliphatic clusteroluminogens

Zhang

et al. 2022

Journal of Polymer Science

Self Cite

View full text Add to dashboard Cite

Nonconjugated and nonaromatic heteroatoms-based structures are discovered with visible emission at clustering state, namely clusteroluminogens (CLgens).Such kind of luminescence is termed clusteroluminescence (CL) which could not be explained by the traditional molecular photophysical theories constructed upon through-bond conjugation, so investigation on CL has great theoretical significance. In this perspective, we summarize a general feature for C═O bond-based CLgens that a magic blue emission around 440 nm widely exists in different systems such as natural protein, polyamide, polyester, and polyketone. Comprehensive analysis of the reported works suggests that the (n, π*) transition of carbonyl group most likely generates the 440 nm CL. This perspective aims to draw researchers' attention to the common features and general photophysical theories of CL, and shine new light on aggregate photophysics.

show abstract

Section: In Carbonyl-based Small Moleculessupporting

confidence: 76%

Section: Introductionmentioning

confidence: 98%

The mysterious blue emission around 440 nm in carbonyl‐based aliphatic clusteroluminogens

Zhang

et al. 2022

Journal of Polymer Science

Self Cite

View full text Add to dashboard Cite

show abstract

“…The maximum PL peak is at 460 nm which is the typical n−π* transition peak of isolated C�O groups according to our previous results. 46,47 Meanwhile, the PL spectra of P1∼P6 both in DCM and solid state (Figures 2B and S69−S70) show a clear excitation-dependent emission (EDE) effect with the transformation from dominant shortwavelength emission (∼460 nm) to negligible long-wavelength emission (∼530 nm). Concentration-dependent PL spectra and excitation-spectra of P2 in DCM were measured and show a similar clusterization-triggered emission (CTE) effect that PL intensity is enhanced with concentration (c) increasing from 10 −5 M to 10 −1 M (Figures 2C and S71).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Aliphatic Polyesters with White-Light Clusteroluminescence

et al. 2022

Self Cite

View full text Add to dashboard Cite

Single-molecule white-light emission (SMWLE) has many advantages in practical applications; however, the fabrication of SMWLE from nonconjugated luminescent polymers, namely, clusteroluminogens (CLgens), is still a big challenge. Herein, the first example of linear nonconjugated polyesters with SMWLE is reported. Twenty-four kinds of nonconjugated aliphatic polyesters with tunable clusteroluminescence (CL) colors and efficiency were synthesized by the copolymerization of six epoxides and four anhydrides. Experimental and calculation results prove that, at the primary structure level, the balance of structural flexibility and rigidity via adjusting the side-chain length significantly enhances the efficiency of CL without wavelength change. However, altering the chemical structures of the monomer from succinic anhydride to trans-maleic anhydride (MA), cis-MA, and citraconic anhydride (CA), secondary structures of these polyesters change from helix to straight and folding sheet accompanied by gradually red-shifted CL from 460 to 570 nm due to the increase in through-space n–π* interactions, as demonstrated by the computational and experimental results. Then, pure SMWLE with CIE coordination (0.30, 0.32) based on overlapped short-wavelength and long-wavelength CL is achieved in CA-based polyesters. This work not only provides further insights into the emission mechanism of CL but also provides a new strategy to manipulate the properties of CL by regulating the hierarchical structures of CLgens.

show abstract

“…Meanwhile, the absorbance peak at ∼270 nm and PL peak at ∼440 nm also ascend with the concentration (Figures b,c and S3a,b). These facts suggest that π–π* and n−π* interactions between the heteroatoms on the copolymers are enhanced with higher density of polymer–polymer H-bonds at higher concentration. , We also investigated the effect of nonsolvent on the fluorescence of polymer solutions (Figure S5). With the addition of dibutyl ether (DBE), the nonsolvent, into the DMF solution of the copolymer, the fluorescence intensity of the polymer mixed solution first increased until the volume fraction of DBE reached 25% and then decreased suddenly.…”

Section: Results and Discussionmentioning

confidence: 99%

Hydrogen-Bonding-Induced Clusteroluminescence and UCST-Type Thermoresponsiveness of Nonconjugated Copolymers

Liu

Han

et al. 2022

Macromolecules

View full text Add to dashboard Cite

Stimuli-responsive light-emitting polymers (SRLEPs) have many promising applications. However, the synthesis of SRLEPs from nonconjugated and water-soluble monomers remains a challenge. Herein, for the first time, nonconjugated luminescent polymers with an upper critical solution temperature (UCST) in aqueous solution are reported. The polymer is synthesized through copolymerization of a strong hydrogen-donating monomer, acrylic acid (AAc), and a strong hydrogen-accepting monomer, N-vinylcaprolactam (NVCL). The polymer–polymer hydrogen-bonding rigidifies the chain conformation and enhances the clustering of the heteroatoms and carbonyl groups, resulting in an improved clusteroluminescence. Meanwhile, the polymer–polymer hydrogen bonding also brings in dynamic chain association that can be switched with temperature, yielding a UCST-type thermoresponsiveness in aqueous solution. This work demonstrates a novel and facile method of designing SRLEPs through tailoring the hydrogen bonds in the polymer. The properties of clusteroluminescence and thermoresponsiveness of the AAc–NVCL copolymers may render themselves with applications as temperature-sensitive biosensing.

show abstract

The role of amide (n,π∗) transitions in polypeptide clusteroluminescence

Cited by 33 publications

References 47 publications

The mysterious blue emission around 440 nm in carbonyl‐based aliphatic clusteroluminogens

The mysterious blue emission around 440 nm in carbonyl‐based aliphatic clusteroluminogens

Aliphatic Polyesters with White-Light Clusteroluminescence

Hydrogen-Bonding-Induced Clusteroluminescence and UCST-Type Thermoresponsiveness of Nonconjugated Copolymers

Contact Info

Product

Resources

About