Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 129
Filtrar
1.
Chem Soc Rev ; 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38747082

RESUMO

Delayed luminescence (DF), including phosphorescence and thermally activated delayed fluorescence (TADF), and circularly polarized luminescence (CPL) exhibit common and broad application prospects in optoelectronic displays, biological imaging, and encryption. Thus, the combination of delayed luminescence and circularly polarized luminescence is attracting increasing attention. The encapsulation of guest emitters in various host matrices to form host-guest systems has been demonstrated to be an appealing strategy to further enhance and/or modulate their delayed luminescence and circularly polarized luminescence. Compared with conventional liquid crystals, polymers, and supramolecular matrices, porous crystalline frameworks (PCFs) including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), zeolites and hydrogen-bonded organic frameworks (HOFs) can not only overcome shortcomings such as flexibility and disorder but also achieve the ordered encapsulation of guests and long-term stability of chiral structures, providing new promising host platforms for the development of DF and CPL. In this review, we provide a comprehensive and critical summary of the recent progress in host-guest photochemistry via the encapsulation engineering of guest emitters in PCFs, particularly focusing on delayed luminescence and circularly polarized luminescence. Initially, the general principle of phosphorescence, TADF and CPL, the combination of DF and CPL, and energy transfer processes between host and guests are introduced. Subsequently, we comprehensively discuss the critical factors affecting the encapsulation engineering of guest emitters in PCFs, such as pore structures, the confinement effect, charge and energy transfer between the host and guest, conformational dynamics, and aggregation model of guest emitters. Thereafter, we summarize the effective methods for the preparation of host-guest systems, especially single-crystal-to-single-crystal (SC-SC) transformation and epitaxial growth, which are distinct from conventional methods based on amorphous materials. Then, the recent advancements in host-guest systems based on PCFs for delayed luminescence and circularly polarized luminescence are highlighted. Finally, we present our personal insights into the challenges and future opportunities in this promising field.

2.
Angew Chem Int Ed Engl ; : e202406552, 2024 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-38766881

RESUMO

Triply interlocked [2]catenane complexes featuring two identical, mechanically interlocked units are extraordinarily rare chemical compounds, whose properties and applications remain open to detailed studies. Herein, we introduce the rational design of a new ligand precursor, L1, suitable for the synthesis of six triply interlocked [2]catenanes by coordination-driven self-assembly. The interlocked compounds can be reversibly converted into the corresponding simple triangular prism metallacage by addition of H2O or DMF solvents to their CH3OH solutions, thereby demonstrating the importance of π···π stacking and hydrogen bonding interactions in the formation of triply interlocked [2]catenanes. Moreover, extensive studies have been conducted to assess the remarkable photothermal conversion performance. Complex 6a, exhibiting outstanding photothermal conversion performance (conversion efficiency in solution : 31.82%), is used to prepare novel photoresponsive elastomer in combination with thermally activated liquid crystal elastomer. The resultant material displays robust response to near-infrared (NIR) laser and the capability of completely reforming the shape and reversible actuation, paving the way for the application of half-sandwich organometallic units in photo-responsive smart materials.

3.
RSC Adv ; 14(7): 4503-4508, 2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-38312733

RESUMO

Organic cocrystal engineering provides a promising route to promote the near-infrared (NIR) light harvesting and photothermal conversion (PTC) abilities of small organic molecules through the rich noncovalent bond interactions of D/A units. Besides, the single-bond rotatable groups known as "rotors" are considered to be conducive to the nonradiative transitions of the excited states of organic molecules. Herein, we propose a single-/double-bond dual-rotor strategy to construct D-A cocrystals for NIR PTC application. The results reveal that the cocrystal exhibits an ultra-broadband absorption from 300 nm to 2000 nm profiting from the strong π-π stacking and charge transfer interactions, and the weakened p-π interaction. More importantly, the PTC efficiency of cocrystals at 1064 nm in the NIR-II region can be largely enhanced by modulating the number of rotor groups and the F-substituents of D/A units. As is revealed by fs-TA spectroscopy, the superior NIR PTC performance can be attributed to the nonradiative decays of excited states induced by the free rotation of the single-bond rotor (-CH3) from the donors and the inactive double-bond rotor ([double bond, length as m-dash]C(C[triple bond, length as m-dash]N)2) being in the active form of [-C(C[triple bond, length as m-dash]N)2] in the excited states from the acceptors. This prototype displays a promising route to extend the functionalization of small organic molecules based on organic cocrystal engineering.

4.
Angew Chem Int Ed Engl ; 63(10): e202318628, 2024 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-38225206

RESUMO

An anion-counterion strategy is proposed to construct organic mono-radical charge-transfer cocrystals for near-infrared photothermal conversion and solar-driven water evaporation. Ionic compounds with halogen anions as the counterions serve as electron donors, providing the necessary electrons for efficient charge transfer with unchanged skeleton atoms and structures as well as the broad red-shifted absorption (200-2000 nm) and unprecedented photothermal conversion efficiency (~90.5 %@808 nm) for the cocrystals. Based on these cocrystals, an excellent solar-driven interfacial water evaporation rate up to 6.1±1.1 kg ⋅ m-2 ⋅ h-1 under 1 sun is recorded due to the comprehensive evaporation effect from the cocrystal loading in polyurethane foams and chimney addition, such performance is superior to the reported results on charge-transfer cocrystals or other materials for solar-driven interfacial evaporation. This prototype exhibits the great potential of cocrystals prepared by the one-step mechanochemistry method in practical large-scale seawater desalination applications.

5.
Int J Legal Med ; 138(1): 197-206, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37804331

RESUMO

Given that combination with multiple biomarkers may well raise the predictive value of wound age, it appears critically essential to identify new features under the limited cost. For this purpose, the present study explored whether the gene expression ratios provide unique time information as an additional indicator for wound age estimation not requiring the detection of new biomarkers and allowing full use of the available data. The expression levels of four wound-healing genes (Arid5a, Ier3, Stom, and Lcp1) were detected by real-time polymerase chain reaction, and a total of six expression ratios were calculated among these four genes. The results showed that the expression levels of four genes and six ratios of expression changed time-dependent during wound repair. The six expression ratios provided additional temporal information, distinct from the four genes analyzed separately by principal component analysis. The overall performance metrics for cross-validation and external validation of four typical prediction models were improved when six ratios of expression were added as additional input variables. Overall, expression ratios among genes provide temporal information and have excellent potential as predictive markers for wound age estimation. Combining the expression levels of genes with ratio-expression of genes may allow for more accurate estimates of the time of injury.


Assuntos
Contusões , Ratos , Animais , Humanos , Ratos Sprague-Dawley , Contusões/genética , Contusões/metabolismo , Músculo Esquelético/metabolismo , Cicatrização/genética , Biomarcadores/metabolismo
6.
J Phys Chem Lett ; 15(1): 68-75, 2024 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-38131660

RESUMO

The specific stacking mode of D/A blocks is often considered to largely determine the physicochemical properties of cocrystals. However, this rule may fail when encountering a large degree of (integer or near-integer) charge transfer situations. Herein, we explore the extensive correlations between the possible smallest structural units, stacking modes, and near-infrared photothermal conversion (NIR-PTC) properties of F4TCNQ-based cocrystals with typical features of integer-charge-transfer. Surprisingly, these cocrystals with distinct stacking modes display analogous D-A interactions, broad red-shift absorption, ultrafast (1-3 ps) relaxation dynamics of excited states, and excellent NIR-PTC properties. This supports that the resulting "D+A-" ion pairs from integer-charge-transfer may serve as the primary structural units beneath the secondary stacking modes to dominate the property of cocrystals. The stacking modes play an important but only secondary role. This work provides new insights into the structure-dynamics-property correlations and modular design of organic cocrystals for PTC and other applications.

7.
Zhongguo Dang Dai Er Ke Za Zhi ; 25(12): 1211-1218, 2023 Dec 15.
Artigo em Chinês | MEDLINE | ID: mdl-38112137

RESUMO

OBJECTIVES: Based on peripheral blood lymphocyte subsets and common laboratory test indexes, this study aimed to construct a predictive scoring system for intravenous immunoglobulin (IVIG)-resistant Kawasaki disease (KD). METHODS: Children hospitalized in Tianjin Children's Hospital from January 2021 to March 2023 were included in the study (185 cases of IVIG-sensitive KD and 41 cases of IVIG -resistant KD). Forty-six healthy children matched for age and gender were selected as controls. The relative percentage and absolute counts of peripheral lymphocyte subsets were measured by flow cytometry. Multivariate logistic regression was used to identify the predictive factors for IVIG-resistant KD and to construct a predictive scoring system for predicting IVIG-resistant KD. RESULTS: The multivariate logistic regression analysis showed that CD4+ T cell absolute count, natural killer cell absolute count, serum sodium level, globulin level, and total bilirubin level were identified as predictive factors for IVIG-resistant KD (P<0.05). The predictive scoring system based on these factors achieved a sensitivity of 70.7% and a specificity of 83.8% in predicting IVIG-resistant KD. CONCLUSIONS: Peripheral blood lymphocyte subsets can serve as predictive indicators for IVIG-resistant KD in children. The introduction of this indicator and the establishment of a scoring system based on it can provide a higher accuracy in predicting IVIG-resistant KD in children.


Assuntos
Imunoglobulinas Intravenosas , Síndrome de Linfonodos Mucocutâneos , Criança , Humanos , Lactente , Imunoglobulinas Intravenosas/uso terapêutico , Síndrome de Linfonodos Mucocutâneos/tratamento farmacológico , Contagem de Linfócitos , Subpopulações de Linfócitos , Estudos Retrospectivos
8.
J Phys Chem Lett ; 14(51): 11580-11586, 2023 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-38100086

RESUMO

Blebbistatin (Bleb) derivatives are a visible light photocage platform. During the photocleavage process, intramolecular charge transfer (ICT) and cationic intermediates play a decisive role. However, slow photolysis rate and low photolysis quantum yield are the main problems for Bleb's derivatives. Herein, by introducing a substituted OCH3 group at the para-position of the D ring, Bleb and Bleb derivatives with various leaving groups were synthesized and studied, and the photolysis performance was unveiled by steady-state spectra, photolysis rate experiments, photolysis quantum yield, and density functional theory calculations. Substituted OCH3 derivatives of Bleb may enhance the photolysis rate and increase the photolysis quantum yield because the electron-donating group can promote the ICT process and stabilize the cationic intermediate during the photolytic reaction. More generally, the insights gained from this structure-reactivity relationship may provide theoretical guidance and aid in the development of new highly efficient photoreactions.

9.
Polymers (Basel) ; 15(21)2023 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-37959928

RESUMO

In this work, an effective flame retardant consisting of nanoscale zinc oxide doped on the surface of hexagonal lamellar magnesium hydrate (ZO@MH) has been successfully synthesized via a hydrothermal process. Approximately 3-methacryloxypropyltrimethoxysilane (KH-570) is chosen as a modifier of ZO@MH for the purpose of enhancing the interfacial interaction between ZO@MH and the polypropylene (PP) matrix and reducing the agglomeration of ZO@MH. Afterwards, ZO@MH and KH-570 modified ZO@MH (KZO@MH) filled PP (PP/ZO@MH and PP/KZO@MH) composites are respectively prepared via the melt blending method. The flame retardant and smoke suppression properties of PP/ZO@MH and PP/KZO@MH composites are estimated by a cone calorimetry test (CCT). The peak value of the heat release rate of the PP/40KZO@MH composite is 327.0 kW/m2, which is 6.1% and 31.2% lower than that of the PP/40ZO@MH and PP/40MH composites, respectively. The lowest peak values of CO and CO2 production, 0.008 and 0.62 g/s, also appeared in the PP/40KZO@MH composite, which are 11.1% and 10.1% lower than those of the PP/40ZO@MH composite. Analysis of char residues indicates that nanoscale ZO and modification of KH-570 improve the amount and quality of char residues, which should be the main reason for the good flame retardant and smoke suppression properties of KZO@MH. Impact strength and nominal strain at break results show that the PP matrix is toughened by ZO@MH rather than KZO@MH. Tensile properties and the quantitative interfacial interaction calculated by the Turcsányi equation both prove the reinforcement of KZO@MH on the PP matrix.

10.
Molecules ; 28(19)2023 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-37836669

RESUMO

Due to their fascinating topological structures and application prospects, coordination supramolecular complexes have continuously been studied by scientists. However, the controlled construction and property study of organometallic handcuffs remains a significant and challenging research subject in the area of supramolecular chemistry. Hence, a series of tetranuclear organometallic and heterometallic handcuffs bearing different size and metal types were rationally designed and successfully synthesized by utilizing a quadridentate pyridyl ligand (tetra-(3-pyridylphenyl)ethylene) based on three Cp*Rh (Cp* = η5-C5Me5) fragments bearing specific longitudinal dimensions and conjugated planes. These results were determined with single-crystal X-ray diffraction analysis technology, ESI-MS NMR spectroscopy, etc. Importantly, the photoquenching effect of Cp* groups and the discrepancy of intermolecular π-π stacking interactions between building block and half-sandwich fragments promote markedly different photothermal conversion results. These results will further push the synthesis of topological structures and the development of photothermal conversion materials.

11.
Polymers (Basel) ; 15(20)2023 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-37896358

RESUMO

Maleic anhydride-modified homopolymerized polypropylene (PP-g-MAH) and maleic anhydride-modified polyolefin elastomer (POE-g-MAH) were used as bulking agents to improve the poor processing and mechanical properties of highly filled composites due to high filler content. In this study, a series of linear low-density polyethylene (LLDPE)/magnesium hydroxide (MH) composites were prepared by the melt blending method, and the effects of the compatibilizer on the mechanical properties, flame retardancy, and rheological behavior of the composites were investigated. The addition of the compatibilizer decreased the limiting oxygen index (LOI) values of the composites, but they were all greater than 30.00%, which belonged to the flame retardant grade. Mechanical property tests showed that the addition of the compatibilizer significantly increased the tensile and impact strengths of the LLDPE/60MH (MH addition of 60 wt%) composites. Specifically, the addition of 5 wt% POE-g-MAH increased 154.07% and 415.47% compared to the LLDPE/60MH composites, respectively. The rotational rheology test showed that the addition of the compatibilizer could effectively improve the processing flow properties of the composites. However, due to the hydrocarbon structure of the compatibilizer, its flame retardant properties were adversely affected. This study provides a strategy that can improve the processing and mechanical properties of highly filled composites.

12.
J Chem Phys ; 159(14)2023 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-37818997

RESUMO

Photofunctional materials based on donor-acceptor molecules have drawn intense attention due to their unique optical properties. Importantly, Systematic investigation of substitution effects on excited-state charge transfer dynamics of donor-acceptor molecules is a powerful approach for identifying application-relevant design principles. Here, by coupling phenothiazine (PTZ) at the ortho-, meta-, and para-positions of the benzene ring of benzophenone (BP), three regioisomeric BP-PTZ dyads were designed to understand the relationship between substituted positions and excited-state evolution channels. Ultrafast transient absorption is used to detect and trace the transient species and related evolution channels of BP-PTZ dyads at excited state. In a non-polar solvent, BP-o-PTZ undergoes the through-space charge transfer process to produce a singlet charge-transfer (1CT) state, which subsequently proceeds the intersystem crossing process and transforms into a triplet charge-transfer (3CT) state; BP-m-PTZ experiences intramolecular charge transfer (ICT) process to generate the 1CT state, which subsequently transforms into the 3CT state by the intersystem crossing (ISC) and finally converts into the local-excited triplet (3LE) state; as for BP-p-PTZ, only 3LE states can be detected after the ISC process from the 1CT state. On the other hand, the twisted ICT states are generated via twisted motion between the donor and acceptor for all BP-PTZ dyads or planarization of the PTZ unit in high polar solvents. The excited-state theoretical calculations unveil that the features of ICT and intramolecular interaction between the three dyads play a decisive role in determining the through-bond charge transfer and through-space charge transfer processes. Also, these results demonstrate that the excited-state evolution channels of PTZ derivatives could be modified by tuning the substituted positions of the donor-acceptor dyads. This study provides a deep perspective for the substitute-position effect on donor-acceptor-type PTZ derivatives.

13.
J Phys Chem A ; 127(45): 9473-9482, 2023 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-37824456

RESUMO

The detailed mechanism for NHC-Cu(I)-catalyzed intermolecular nucleophilic substitution of the C-H bonds at aniline (2-methyl-N-methoxyaniline) was studied via DFT methods to reveal the essence of the selectivity. Calculations revealed that the meta C-H functionalization proceeds via two nucleophilic attacks on the aromatic ring rather than a one-step meta C-H substitution to give the experimentally observed major product. The reaction is initiated by activation of the substrate via oxidative addition with an NHC-Cu(I) catalyst, through which an umpolung occurs at the ring. From the activated intermediate, methoxyl group transfer to benzyl forms a resting state, while a nucleophile can attack the ortho position of benzyl to form a more stable intermediate. The nucleophile group can then transfer to the meta position by a 1,2-Wagner-Meerwein rearrangement to form the final product through a proton shuttle. In contrast, other transfer processes affording ortho- or para-substituted products encounter higher activation barriers. This work investigates the relationship of product selectivity with the umpolung of the aromatic ring, as well as the priority of a nucleophilic attack at the ortho position of the aromatic, 1,2-Wagner-Meerwein rearrangement from the ortho-substituted intermediate, and proton shuttle from the meta-substituted intermediate.

14.
Front Immunol ; 14: 1269665, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37828994

RESUMO

Objective: Analysis of SARS-CoV-2 IgG antibody and neutralizing antibody levels following SARS-CoV-2 infection in children aged 3-11 years, comparing those who had received the inactivated SARS-CoV-2 vaccine to those who were unvaccinated prior to infection, provides evidence for public health centers in formulating vaccination strategies and control policies. Methods: A study was conducted on children who visited the Children's Hospital, Capital Institute of Pediatrics from January 10, 2023 to March 31, 2023 (Beijing, China). Participants or their guardians completed a survey questionnaire providing information about their SARS-CoV-2 infection history and vaccination status. Serum samples were collected for testing of SARS-CoV-2 immunoglobulin G (IgG) and neutralizing antibodies (Nabs), which were performed using chemiluminescence immunoassay. Results: The study included 1,504 children aged 3-11 years with previous SARS-CoV-2 infection history. Among the 333 unvaccinated children, the serum SARS-CoV-2 IgG antibody level was median 2.30 (IQR, 1.27-3.99). However, children received one dose (78 cases) and two doses (1093 cases) of the inactivated vaccine prior to infection showed significantly higher SARS-CoV-2 IgG antibody levels, with values of median 10.11 (IQR, 8.66-10.93) and median 10.58 (IQR, 9.79-11.07), respectively. As to the unvaccinated children, 70.3% (234/333) were negative for SARS-CoV-2 Nabs, which were less than 6.00AU/ml. The remaining 29.7% (99/333) showed relatively low levels of Nabs, ranging from 6.00 to 50.00AU/ml. In contrast, for children who had received two doses of vaccine prior to infection, an overwhelming 99.3% (1086/1093) exhibited high levels of Nas in the range of 100.00-120.00 AU/ml. Remarkably, these elevated Nab levels persisted for at least a period of 3 months post-infection in children who had received two doses of inactivated SARS-CoV-2 vaccine prior to infection, regardless of age or sex and vaccine manufacturer. Conclusion: The administration of two doses of inactivated SARS-CoV-2 vaccine prior to infection has been shown to significantly enhance humoral immunity following SARS-CoV-2 infection in pediatric populations, producing adequate Nabs that persist at elevated levels for up to 3 months post-infection. For unvaccinated children who displayed weak humoral immunity following a primary natural infection, timely vaccination is recommended to bolster their immunization protection. The findings underscore the importance of vaccination in strengthening immune responses and protecting pediatric populations against SARS-CoV-2 infection.


Assuntos
Antígenos de Grupos Sanguíneos , COVID-19 , Humanos , Criança , Pequim , Imunidade Humoral , Vacinas contra COVID-19 , SARS-CoV-2 , COVID-19/prevenção & controle , Vacinação , Anticorpos Neutralizantes , Anticorpos Antivirais , Imunoglobulina G
15.
Angew Chem Int Ed Engl ; 62(43): e202312698, 2023 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-37682089

RESUMO

The first coordination-saturated buckyball with a C60 molecule totally encased in an icosidodecahedral Cu30 in a (µ30 -(η2 )30 )-fashion, namely C60 @Cu30 @Cl36 N12 , has been successfully realized by a C60 -templated assembly. The 48 outmost coordinating atoms (36Cl+12N) comprise a new simple polyhedron that is described by a ccf topology. Charge transfer from (CuI , Cl) to C60 explains the expansion of the light absorption up to 700 nm, and accounts for an ultrafast photophysical process that underpins its high photothermal conversion efficiency. This work makes a giant step forward in exohedral metallofullerene (ExMF) chemistry.

16.
ACS Appl Mater Interfaces ; 15(31): 37371-37380, 2023 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-37515570

RESUMO

Morphology instability holds the major responsibility for efficiency degradation of organic solar cells (OSCs). However, how to develop polymer donors simultaneously with high efficiency and excellent morphology stability remains challenging. Herein, we reported naphtho[2,1-b:3,4-b']dithiophene-5,6-imide (NDTI)-based new polymers PNDT1 and PNDT2. The alkyl chain engineering leads to high crystallinity, high hole mobility (>10-3 cm2 V-1 S-1), and nanofibrous film morphology, which enable PNDT2 to exhibit an efficiency of 18.13% and a remarkable FF value of 0.80. Moreover, the NDTIs have short π-π stacking and abundant short interactions, and their polymers exhibit superior morphological stability. Therefore, the PNDT2-based OSCs exhibit much better device stability than that of PNDT1, PAB-α, and benchmark polymers PM6 and D18. This work suggests the great importance of the large conjugated backbone of the monomer and alkyl chain engineering to develop high-performance and morphology-stable polymers for OSCs.

17.
J Phys Chem Lett ; 14(30): 6927-6934, 2023 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-37498211

RESUMO

Notably, the intermolecular charge transfer between pyrene (Py) and benzophonenes (BPs) can significantly enhance the quantum yield of the triplet state of Py, which will convert Py from a fluorescence molecule to a phosphorescence molecule. The intermolecular charge transfer is confirmed by steady-state and time-resolved spectroscopy and theoretical study. Based on these foundations, Py is doped into BPs systems and a large Stokes-shift organic room temperature phosphorescence (ORTP) is observed. By using different benzophenone derivatives, a series of host-guest ORTP materials with different luminescent properties adjusted by intermolecular charge transfer features are developed. Fortunately, these host-guest ORTP systems from benzophenone derivatives and pyrene are readily fabricated, and the red gradient color lasting as long as 3 s is observed after removing UV excitation. This host-guest charge transfer strategy plays an important role in the mechanism of the luminous type shift. Our strategy paves the way to design ORTP materials conveniently and apply these materials in encryption and temperature alarm device.

18.
ChemSusChem ; 16(14): e202300919, 2023 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-37431190

RESUMO

Invited for this month's cover is the group of Shun-Li Chen and Ming-De Li at the Shantou University. The image shows that one electron can be transferred easily from donor to acceptor unit to obtain integer-charge-transfer cocrystals for realizing high-efficient solar-harvesting and photothermal conversion. The Research Article itself is available at 10.1002/cssc.202300644.

19.
J Am Chem Soc ; 145(32): 18036-18047, 2023 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-37459092

RESUMO

A variety of organometallic supramolecular architectures have been constructed over the past decades and their properties were also explored via different strategies. However, the synthesis of metalla-Russian doll is still a fascinating challenge. Herein, a series of new coordination supramolecular complexes, including a metalla-Russian doll, metalla[2]catenanes, and metallarectangles, were synthesized by using meticulously selected Cp*Rh (Cp* = η5-C5Me5) building units (E1, E2, and E3) and three rigid anthracylpyridine ligands (L1, L2, and L3) via a self-assembly strategy. While the combination of the short ligand L1 and E1 or E2 generated two metallarectangles, the longer ligand L2 containing an alkynyl group resulted in two new [2]catenanes, most likely due to which the strong electron-donating effect of alkynyl groups causes self-accumulation. Interestingly, an unusual Russian doll assembly was obtained through the reaction of L3 and E3 based on sextuple π···π stacking interactions. Furthermore, the dynamic structural conversion between [2]catenanes and the corresponding metallarectangles could be observed through concentration-, solvent-, and guest-induced effects. The [2]catenane complexes 4b displayed efficient photothermal conversion efficiency in solution (20.2%), in comparison with other organometallic macrocycles. We believe that π···π stacking interactions generate active nonradiative pathways and promote radiative photodeactivation pathways. This study proves the versatility of half-sandwich building units, not only to build complicated supramolecular topologies but also in effective functional materials for various appealing applications.

20.
Polymers (Basel) ; 15(11)2023 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-37299373

RESUMO

The poor processing and rheological properties of highly filled composites caused by the high loading of fillers can be improved with the use of maleic anhydride grafted polyethylene wax (PEWM) as compatibilizer and lubricant. In this study, two PEWMs with different molecular weights were synthesized by melt grafting, and their compositions and grafting degrees were characterized by Fourier transform infrared (FTIR) spectroscopy and acid-base titration. Subsequently, magnesium hydroxide (MH)/linear low-density polyethylene (LLDPE) composites with 60 wt% of MH were prepared using polyethylene wax (PEW) and PEWM, respectively. The equilibrium torque and melt flow index tests indicate that the processability and fluidity of MH/MAPP/LLDPE composites are significantly improved with the addition of PEWM. The addition of PEWM with a lower molecular weight leads to a substantial reduction in viscosity. The mechanical properties are also increased. The limiting oxygen index (LOI) test and cone calorimeter test (CCT) show that both PEW and PEWM have adverse effects on flame retardancy. This study provides a strategy to simultaneously improve the processability and mechanical properties of highly filled composites.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...