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Key progresses of MOE key laboratory of macromolecular synthesis and functionalization in 2022

Chinese Chemical Letters 2024年第3期35卷 114-126页

作者： Xumeng Deng Kaihao Chen Kai Pang Xiaoting Liu Minsong Gao Jie Ren Guanwen Yang Guangpeng Wu Chengjian Zhang Xufeng Ni Peng Zhang Jian Ji Jianzhao Liu Zhengwei Mao Ziliang Wu Zhen Xu Haoke Zhang Hanying Li MOE Key Laboratory of Macromolecular Synthesis and Functionalization International Research Center for X PolymersDepartment of Polymer Science and EngineeringZhejiang UniversityHangzhou 310027China

In 2022,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important ***,a series of well-defined dinuclear organoboron catalysts were developed to precisely control the enchainment of ether and carbonate segments during the copolymerization of CO_(2)and ***,polyester had been synthesized through cationic copolymerization of cyclic ***,ring-opening polymerization of carbon dioxide based valerolactone had been achieved,revealing the prospect of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one(EVL)in utilizing CO_(2)and synthesizing functional ***,machine learning methods have been applied to biomaterial research,enabling high-throughput screening of functional biomaterial surfaces for implantable devices,and searching for potent antimicrobial peptides in whole combinatorial peptide ***,methods of characterization of biomacromolecule RNA transcription and manipulation of nucleoside modification were ***,artificial enzymes-armed Bifidobacterium Longum probiotics were established to tune down gut ***,three-dimensional(3D)printing technologies were used to engineer tough supramolecular ***,hydroplastic foaming graphene frameworks for acoustic and conductive polymer composites were provided for ***,aggregate photophysics about the nature of through-space interactions(TSIs)and manipulating their strength in small molecules with non-conjugated structure had been ***,the forming mechanism of a newfound nested texture in poly(L-lactic acid)(PLLA)spherulitic films had been ***,the isotropically dyeing mechanism of KDP single crystals grown from hydrogels have been *** related works are reviewed in this paper.

关键词： Polymer Catalyst Biomaterial research mRNA Hydrogel Graphene Crystal

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Tailoring sulfur-doped and nitrogen-defective carbon nitride nanosheets for efficient photo-controlled radical polymerizations

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Science China Chemistry 2024年第7期67卷 2325-2334页

作者： Xue Li Meng Kai Xu Yuan Huang Tao Cai Key Laboratory of Biomedical polymers of Ministry of Education College of Chemistry and Molecular SciencesWuhan UniversityWuhan 430072China Wuhan University Shenzhen research Institute Shenzhen 518057China

Despite the challenges that remain,the synergistic adjustment of various microstructures and photochemical parameters of graphitic carbon nitride(g-C_(3)N_(4))in photocatalytic reactions holds promises for improving catalytic efficiency and reducing energy ***,sulfur-doped and nitrogen-defective g-C_(3)N_(4)(n-SC_(3)N_(x))nanosheets were designed and elaborately *** resultant n-SC_(3)N_(x)possessed a precisely defined 2D layer structure with extensive porosity and incremental specific surface *** photoinduced electron transfer-reversible addition-fragmentation chain transfer(PET-RAFT)polymerization of vinyl monomers with low dispersity,excellent temporal control and high chain-end fidelity was achieved under mild blue light irradiation in a nondegassed *** to their ultrathin nanostructures with nitrogen defects and sulfur dopants,n-SC_(3)N_(x)was capable of catalyzing RAFT polymerization in aqueous solutions at significantly accelerated rates,which were nearly 8 times faster compared to bulk g-C_(3)N_(4).The ease of separation and efficient reusability in subsequent polymerizations was enabled by the heterogeneous nature of n-SC_(3)N_(x).The appeal of this approach was illustrated by the fact that utilizing a reusable and metal-free photocatalyst in aqueous environments allowed for the synthesis of polymers with molecular weight up to 300 kg mol^(-1) and a dispersity of 1.32.

关键词： graphitic carbon nitride nitrogen defects sulfur dopants PET-RAFT polymerization recyclability

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Significantly Enhanced Melt Memory Effect of Metallocene-made Isotactic Polypropylene Containing Talc

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Chinese Journal of Polymer Science 2024年第2期42卷 213-222,I0008页

作者： Hong-Wen Sun Fu-Shan Wang Yan Gao Fu-Qing Wei Jia-Chun Feng State Key Laboratory of Molecular Engineering of polymers Department of Macromolecular ScienceFudan UniversityShanghai200433China Lanzhou Petrochemical Corporation of PetroChina Lanzhou730060China Lanzhou Petrochemical research Center Petrochemical Research Institute of PetroChinaLanzhou730060China

The melt memory effect is a widely observed phenomenon in semi-crystalline polymers. In practical applications, various additives are usually introduced into polymers, which may affect their melt memory behavior. In this work, the effect of talc on the melt memory effect of metallocene-made isotactic polypropylene(M-PP) was investigated in detail by using the differential scanning calorimetry. The results indicated that the introduction of talc significantly strengthened the melt memory effect of M-PP. Specifically, the upper limit temperature of Domain II increased from 161 ℃ to 174 ℃, resulting in a substantial widening of the temperature range of Domain IIa from 1 ℃ to 14 ℃. Analysis of the crystal orientation of the M-PP containing talc cooled from various Ts suggested that the remarkably enhanced melt memory effect could be ascribed to the stabilization of oriented nuclei facilitated by talc. This stabilizing effect was likely attributable to the prefreezing effect or the sorption interaction between talc and the M-PP chains.

关键词： Metallocene-made isotactic polypropylene Talc Melt memory effect Crystal orientation

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Interparticle energy transfer between NaNdF_(4) and NaYbF_(4) in self-assembled nanostructures

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Journal of Rare Earths 2024年第6期42卷 1029-1035,I0001页

作者： Xinyu Chen Haoze Yang Yuyang Gu Chenqing Wen Yishuo Sun Jiaming Ke Wei Feng Department of Chemistry and State Key Laboratory of Molecular Engineering of polymers Fudan University Shanghai200433China

Forster resonance energy transfer(FRET)is a widely used spectroscopic *** development of donor-acceptor combinations is essential to advance this *** make the energy transfer efficiency independent of the external environment,we explored the potential of constructing donor—acceptor combinations with lanthanide ion-doped nanoparticles(LNPs),in which the 4f electrons of the lanthanide ions are shielded by the 5s and 6p ***-radiative energy transfer between LNPs was demonstrated in self-assembled nanostructures and core-shell structure of LNPs was used to control the distance between donor and acceptor in self-assembled *** emission intensity ratio of donor and acceptor illustrates that the energy transfer efficiency decreases significantly with increasing distance and the effective energy transfer distance is 8.5 nm,showing the potential of using LNPs as donor-acceptor pairs in the construction of distance-dependent energy transfer system.

关键词： Lanthanide nanoparticles Self-assembly Energy transfer Distance Epitaxialgrowth Rare earths

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Polarization-driven multifunctional organohydrogels with strain sensitivity toward electromagnetic wave absorption

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Nano research 2024年第6期17卷 5688-5697页

作者： Yunfei Zhang Lei Zhang Bingqian Zhou Yishan Gao Baoliang Zhang School of Chemistry and Chemical Engineering Northwestern Polytechnical UniversityXi’an 710072China Shaanxi Engineering and research Center for Functional polymers on Adsorption and Separation Sunresins New Materials Co.Ltd.Xi’an 710072China

Rapid advancements in flexible electronics and military applications necessitate high-performance electromagnetic wave(EMW)*** huge breakthroughs in achieving high-attenuation microwave absorption,conventional EMW absorbing materials have single function and ambiguous absorption ***,numerous gel-type absorbers are fabricated by introducing“regulators”into poly(acrylamide-co-acrylic acid)(P(AM-co-AA))networks through radical polymerization in a glycerol-water mixed *** dielectric constant and EMW absorption performance of the gels are precisely predicted by adjusting monomer concentration,the ratio of glycerol/water,and the content of the ***,A_(6)G_(20)T_(20)-2 exhibits promising absorption performance with a minimum reflection loss(RL_(min))of-33.8 dB at 12.4 *** effective absorption bandwidth(EAB)covers the entire X-band(8.2-12.4 GHz)at a thickness of 2.7 mm.A_(6)G_(20)T_(20)-2 also has sensitive deformation responses and excellent tensile strength,adhesiveness,self-healing and anti-freezing ***,this work not only provides insight into the polarization loss mechanism of the gels as the result of high correlation between EMW absorbing properties and molecular polarization,but also offers an important reference for developing functional protective materials because of the rich functionalities and efficient protective capabilities of the gels.

关键词： organohydrogels molecular polarization microwave absorption strain sensor

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Automated Identification of Ordered Phases for Simulation Studies of Block Copolymers

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Chinese Journal of Polymer Science 2024年第5期42卷 683-692,I0011页

作者： Yu-Chen Zhang Wei-Ling Huang Yi-Xin Liu State Key Laboratory of Molecule Engineering of polymers Department of Macromolecular ScienceFudan UniversityShanghai200433China

In unit cell simulations,identification of ordered phases in block copolymers(BCPs)is a tedious and time-consuming task,impeding the advancement of more streamlined and potentially automated research *** this study,we propose a scattering-based automated identification strategy(SAIS)for characterization and identification of ordered phases of BCPs based on their computed scattering *** approach leverages the scattering theory of perfect crystals to efficiently compute the scattering patterns of periodic morphologies in a unit *** the first stage of the SAIS,phases are identified by comparing reflection conditions at a sequence of Miller *** confirm or refine the identification results of the first stage,the second stage of the SAIS introduces a tailored residual between the test phase and each of the known candidate ***,our strategy incorporates a variance-like criterion to distinguish background species,enabling its extension to multi-species BCP *** has been demonstrated that our strategy achieves exceptional accuracy and robustness while requiring minimal computational ***,the approach allows for real-time expansion and improvement to the candidate phase library,facilitating the development of automated research workflows for designing specific ordered structures and discovering new ordered phases in BCPs.

关键词： Block copolymer Phase identification Scattering function

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Mechanisms of inclusion-induced pitting of stainless steels:A review

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Journal of Materials Science & Technology 2024年第1期168卷 143-156页

作者： Yangting Sun Xin Tan Rulei Lan Guoyong Ran Jin Li Yiming Jiang Department of Materials Science State Key Laboratory of Molecular Engineering of PolymersFudan UniversityShanghai 200438China

Pitting is a common type of localized corrosion in passive alloys that can cause rapid failure of material or *** the case of stainless steels,non-metallic inclusions have been identified as the most susceptible sites for pitting,and have therefore garnered significant *** review critically ex-amines the issue of how inclusions induce pitting,with a particular focus on three mechanisms:sponta-neous dissolution of inclusions,active dissolution of Cr-depleted regions,and propagation of microcracks at the inclusion-matrix *** researchers have made significant strides in understanding these mechanisms over the past few decades,many gaps and controversies *** such as the ini-tial driving force of inclusion dissolution and factors affecting Cr-depleted regions require further ***,some old concepts and methods need to be revised to arrive at more credible *** review aims to delve deeply into these important issues and provide inspiration for future research.

关键词： Pitting Inclusion Stainless steel Localized corrosion MnS

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Effects of serum proteins on corrosion rates and product bioabsorbability of biodegradable metals

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Regenerative Biomaterials 2024年第1期3卷 132-148页

作者： Hongjie Zhang Xin Li Zehua Qu Wanqian Zhang Qunsong Wang Dinglingge Cao Yaoben Wang Xin Wang Yang Wang Lin Yu Jiandong Ding State Key Laboratory of Molecular Engineering of polymers Department of Macromolecular ScienceFudan UniversityShanghai 200438China

Corrodible metals are the newest kind of biodegradable materials and raise a new problem of the corrosion ***,the removal of the precipitated products has been unclear and even largely ignored in ***,we find that albumin,an abundant macromolecule in serum,enhances the solubility of corrosion products of iron in blood mimetic Hank’s solution *** is universal for other main biodegradable metals such as magnesium,zinc and polyester-coated *** also influences corrosion rates in diverse trends in Hank’s solution and normal *** on quantitative study theoretically and experimentally,both the effects on corrosion rates and soluble fractions are interpreted by a unified mechanism,and the key factor leading to different corrosion behaviors in corrosion media is the interference of albumin to the Ca/P passivation layer on the metal *** work has illustrated that the interactions between metals and media macromolecules should be taken into consideration in the design of the next-generation metal-based biodegradable medical devices in the formulism of precision *** improved Hank’s solution in the presence of albumin and with a higher content of initial calcium salt is suggested to access biodegradable metals potentially for cardiovascular medical devices,where the content of calcium salt is calculated after consideration of chelating of calcium ions by albumin,resulting in the physiological concentration of free calcium ions.

关键词： biodegradable metal macromolecule albumin corrosion bioabsorbability iron polylactide magnesium zinc

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Stereocomplexation and Mechanical Properties of Polylactide-bpoly(propylene glycol)-b-polylactide Blend Films: Effects of Polylactide Block Length and Blend Ratio

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Chinese Journal of Polymer Science 2017年第11期35卷 1391-1401页

作者： Dutchanee Pholharn Onanong Cheerarot Yodthong Baimark biodegradable polymers research unit Department of Chemistry and Center of Excellence for Innovation in ChemistryFaculty of Science Mahasarakham University

In the present work, poly（propylene glycol）（PPG） was block copolymerized to form polylactide-poly（propylene glycol）-polylactide （PL-PPG-PL） triblock copolymers for preparing flexible stereocomplex PL （scPL） blend films. The scPL blend films were prepared by solution blending of poly（L-lactide）-PPG-poly（L-lactide）（PLL-PPG-PLL） and poly（D-lactide）- PPG-poly（D-lactide）（PDL-PPG-PDL） triblock copolymers before film casting. The influences of PL end-block lengths （2 ×10^4 and 4×10^4 g/tool） and blend ratios （75/25, 50/50 and 25/75 W/W） on the stereocomplexation and mechanical properties of the blend films were evaluated. From DSC and WAXD results, the 50/50 blend films had complete stereocomplexation. Phase separation between the scPL and PPG phases was not observed from their SEM images. The tensile stress and elongation at break increased with the sterecomplex crystallinities and PL end-block lengths. The PPG middle-blocks enhanced elongation at break of the scPL films. The results showed that the PL-PPG-PL triblock structures did not affect stereocomplexation of the PLL/PDL block blending. In conclusion, the phase compatibility and flexibility of the scPL films were improved by PPG block copolymerization.

关键词： Stereocomplex Polylactide Poly(propylene glycol) Block copolymers Mechanical properties

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A Sustainable Dual Cross‑Linked Cellulose Hydrogel Electrolyte for High‑Performance Zinc‑Metal Batteries

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Nano-Micro Letters 2024年第6期16卷 63-75页

作者： Haodong Zhang Xiaotang Gan Yuyang Yan Jinping Zhou Hubei Engineering Center of Natural polymers‑Based Medical Materials Key Laboratory of Biomedical Polymers of Ministry of EducationCollege of Chemistry and Molecular SciencesWuhan UniversityWuhan 430072People’s Republic of China Zhongnan Hospital of Wuhan University Institute of Hepatobiliary Diseases of Wuhan UniversityTransplant Center of Wuhan UniversityWuhan 430072People’s Republic of China

Aqueous rechargeable Zn-metal batteries(ARZBs)are considered one of the most promising candidates for grid-scale energy ***,their widespread commercial application is largely plagued by three major challenges:The uncontrollable Zn dendrites,notorious parasitic side reactions,and sluggish Zn^(2+) ion *** address these issues,we design a sustainable dual crosslinked cellulose hydrogel electrolyte,which has excellent mechanical strength to inhibit dendrite formation,high Zn^(2+) ions binding capacity to suppress side reaction,and abundant porous structure to facilitate Zn^(2+) ions ***,the Zn||Zn cell with the hydrogel electrolyte can cycle stably for more than 400 h under a high current density of 10 mA cm^(−2).Moreover,the hydrogel electrolyte also enables the Zn||polyaniline cell to achieve high-rate and long-term cycling performance(>2000 cycles at 2000 mA g^(−1)).Remarkably,the hydrogel electrolyte is easily accessible and biodegradable,making the ARZBs attractive in terms of scalability and sustainability.

关键词： Cellulose Dual cross-linked Aqueous rechargeable Zn-metal batteries Hydrogel electrolyte

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