The modern lifestyle necessitates significant energy consumption,which con-tinues to increase as human development progresses.Solar energy presents an attractive alternative resource that can meet the global demand for energy in light of the limited availability of fossil fuels.In nature,photosynthetic organelles utilize solar energy to convert inorganic matter into organic matter through photosynthesis.Solar energy can be converted into chemical energy through a natural process,and humans can replicate this technology through artificial photosynthesis.Artificial photosynthesis is an emerging discipline that imitates the mechanism of photosynthesis found in living organisms.Significant ad-vancements have been made in this field,and this review specifically focuses on the self-assembly process of supramolecular nanomaterials through non-covalent bonding.The self-assembly process of photosensitizer molecules combined with catalysts and substrates for photocatalytic reactions is of particular interest.This review presents three categories of photocatalytic reactions,followed by a brief discussion of the prospects and challenges within this field.
Xin-Gang TanPonmani JeyakkumarYi-Xuan ZhangLin-Wang ChuYu-Ru HaoSheng-Ke LiKai-Ya WangXiao-Yu Hu
In the application of polymer gels to profile control and water shutoff,the gelation time will directly determine whether the gel can"go further"in the formation,but the most of the methods for delaying gel gelation time are complicated or have low responsiveness.There is an urgent need for an effective method for delaying gel gelation time with intelligent response.Inspired by the slow-release effect of drug capsules,this paper uses the self-assembly effect of gas-phase hydrophobic SiO_(2) in aqueous solution as a capsule to prepare an intelligent responsive self-assembled micro-nanocapsules.The capsule slowly releases the cross-linking agent under the stimulation of external conditions such as temperature and pH value,thus delaying gel gelation time.When the pH value is 2 and the concentration of gas-phase hydrophobic SiO_(2) particles is 10%,the gelation time of the capsule gel system at 30,60,90,and 120℃is12.5,13.2,15.2,and 21.1 times longer than that of the gel system without containing capsule,respectively.Compared with other methods,the yield stress of the gel without containing capsules was 78 Pa,and the yield stress after the addition of capsules was 322 Pa.The intelligent responsive self-assembled micronanocapsules prepared by gas-phase hydrophobic silica nanoparticles can not only delay the gel gelation time,but also increase the gel strength.The slow release of cross-linking agent from capsule provides an effective method for prolongating the gelation time of polymer gels.
Soft hydrogels are excellent candidate materials for repairing various tissue defects,yet the mechanical strength,anti-swelling properties,and biocompatibility of many soft hydrogels need to be improved.Herein,inspired by the nanostructure of collagen fibrils,we developed a strategy toward achieving a soft but tough,anti-swelling nanofibrillar hydrogel by combining the self-assembly and chemical crosslinking of nanoparticles.Specifically,the collagen fibril-like injectable hydrogel was subtly designed and fabricated by self-assembling methylacrylyl hydroxypropyl chitosan(HM)with laponite(LAP)to form nanoparticles,followed by the inter-nanoparticle bonding through photo-crosslinking.The assembly mechanism of nanoparticles was elucidated by both experimental and simulation techniques.Due to the unique structure of the crosslinked nanoparticles,the nanocomposite hydrogels exhibited low stiffness(G’<2 kPa),high compressive strength(709 kPa),and anti-swelling(swelling ratio of 1.07 in PBS)properties.Additionally,by harnessing the photo-crosslinking ability of the nanoparticles,the nanocomposite hydrogels were processed as microgels,which can be three-dimensionally(3D)printed into complex shapes.Furthermore,we demonstrated that these nanocomposite hydrogels are highly biocompatible,biodegradability,and can effectively promote fibroblast migration and accelerate blood vessel formation during wound healing.This work presents a promising approach to develop biomimetic,nanofibrillar soft hydrogels for regenerative medicine applications.
Shanshan LiXiaoyun LiYidi XuChaoran FanZhong Alan LiLu ZhengBichong LuoZhi-Peng LiBaofeng LinZhen-Gang ZhaHuan-Tian ZhangXiaoying Wang
Extensive efforts have been made to pursue a low-friction state with promising applications in many fields,such as mechanical and biomedical engineering.Among which,the load capacity of the low-friction state has been considered to be crucial for industrial applications.Here,we report a low friction under ultrahigh contact pressure by building a novel self-assembled fluorinated azobenzene layer on an atomically smooth highly-oriented pyrolytic graphite(HOPG)surface.Sliding friction coefficients could be as low as 0.0005 or even lower under a contact pressure of up to 4 GPa.It demonstrates that the low friction under ultrahigh contact pressure is attributed to molecular fluorination.The fluorination leads to effective and robust lubrication between the tip and the self-assembled layer and enhances tighter rigidity which can reduce the stress concentration in the substrate,which was verified by density functional theory(DFT)and molecular dynamics(MD)simulation.This work provides a new approach to avoid the failure of ultralow friction coefficient under relatively high contact pressure,which has promising potential application value in the future.
Dandan XUEZhi XULinyuan GUOWendi LUOLiran MAYu TIANMing MAQingdao ZENGKe DENGWenjing ZHANGYichun XIAShizhu WENJianbin LUO
Inverted perovskite solar cells have gained prominence in industrial advancement due to their easy fabrication,low hysteresis effects,and high stability.Despite these advantages,their efficiency is currently limited by excessive defects and poor carrier transport at the perovskite-electrode interface,particularly at the buried interface between the perovskite and transparent conductive oxide(TCO).Recent efforts in the perovskite community have focused on designing novel self-assembled molecules(SAMs)to improve the quality of the buried interface.However,a notable gap remains in understanding the regulation of atomic-scale interfacial properties of SAMs between the perovskite and TCO interfaces.This understanding is crucial,particularly in terms of identifying chemically active anchoring groups.In this study,we used the star SAM([2-(9H-carbazol-9-yl)ethyl]phosphonic acid)as the base structure to investigate the defect passivation effects of eight common anchoring groups at the perovskite-TCO interface.Our findings indicate that the phosphonic and boric acid groups exhibit notable advantages.These groups fulfill three key criteria:they provide the greatest potential for defect passivation,exhibit stable adsorption with defects,and exert significant regulatory effects on interface dipoles.Ionized anchoring groups exhibit enhanced passivation capabilities for defect energy levels due to their superior Lewis base properties,which effectively neutralize local charges near defects.Among various defect types,iodine vacancies are the easiest to passivate,whereas iodine-substituted lead defects are the most challenging to passivate.Our study provides comprehensive theoretical insights and inspiration for the design of anchoring groups in SAMs,contributing to the ongoing development of more efficient inverted perovskite solar cells.
Immune checkpoint inhibitors(ICIs)therapy targeting programmed cell death ligand 1(PD-L1)and programmed death protein 1(PD-1)had exhibited significant clinical benefits for cancer treatment such as triple negative breast cancer(TNBC).However,the relatively low anti-tumor immune response rate and ICIs drug resistance highlight the necessity of developing ICIs combination therapy strategies to improve the anti-tumor effect of immunotherapy.Herein,the immunomodulator epigallocatechin gallate palmitate(PEGCG)and the immunoadjuvant metformin(MET)self-assembled into tumor-targeted micelles via hydrogen bond and electrostatic interaction,which encapsulated the therapeutic agents doxorubicin(DOX)-loaded PEGCG-MET micelles(PMD)and combined with ICIs(anti-PD-1 antibody)as therapeutic strategy to reduce the endogenous expression of PD-L1 and improve the tumor immunosuppressive microenvironment.The results presented that PMD integrated chemotherapy and immunotherapy to enhance antitumor efficacy in vitro and in vivo,compared with DOX or anti-PD-1 antibody for the therapy of TNBC.PMD micelles might be a potential candidate,which could remedy the shortcomings of antibody-based ICIs and provide synergistic effect to enhance the antitumor effects of ICIs in tumor therapy.
Proteolysis targeting chimeras (PROTACs) have recently emerged as promising therapeutic agents for cancer therapy. However, their clinical application is considerably hindered by the poor membrane permeability and insufficient tumor distribution of PROTACs. Here we proposed a nanoengineered targeting strategy to construct a self-assembled affibody-PROTAC conjugate nanomedicine (APCN) for tumor-specific delivery of PROTACs. As proof of concept, a hydrophobic PROTAC MZ1 (a bromodomain-containing protein 4 degrader) was selected to couple with a hydrophilic affibody ZHER2:342 (an affinity protein of human epidermal growth factor receptor 2, HER2) via a smart linker containing disulfide bond to form an amphiphilic ZHER2:342-MZ1 conjugate. It spontaneously self-assembled into nanoparticles (ZHER2:342-MZ1 APCN) in water. Upon the excellent targeting property of ZHER2:342 and HER2 receptor-mediated endocytosis, ZHER2:342-MZ1 APCN was accumulated in tumor sites and internalized by cancer cells effectively in vitro. Under the intracellular high level of glutathione (GSH), ZHER2:342-MZ1 APCN released MZ1 to specifically degrade bromodomain-containing protein 4 (BRD4) and subsequently induced BRD4 deficiency-mediated apoptosis of cancer cells. By the tail-vein injection, ZHER2:342-MZ1 APCN showed the outstanding tumor-specific targeting ability, drug accumulation capacity, enhanced BRD4 degradation and antitumor efficacy in vivo for an HER2-positive SKOV-3 tumor model. Such an affibody mediated nanoengineered strategy would facilitate the application of PROTACs for targeted cancer therapy.
Qingrong LiXiaoyuan YangMengqiao ZhaoXuelin XiaWenhui GaoWei HuangXiaoxia XiaDeyue Yan
The emergence of antibiotic-resistant bacteria has become a major threat to global public health and has prompted the discovery of antibiotic alternatives.Natural antimicrobial peptides(AMPs)confer a unique non-specific membrane rupture mechanism,showing great potential in killing drug-resistant bacteria.However,natural AMPs have certain weaknesses,including stability and toxicity issues,which seriously hinder their in vivo applications.Synthetic AMPs possess similar characteristics to natural AMPs,including positive charges,amphiphilicity,and the ability to fold into diverse secondary structures.These properties are essential for AMPs penetration into membranes,allowing them to exhibit antimicrobial effects.Moreover,supramolecular self-assembly,facilitated by hydrophobic interaction,hydrogen bonding,π-πstacking,and electrostatic interaction,can generate nanoparticles,nanotubes,nanofibers,and hydrogels with well-defined nanoarchitectures.Utilizing peptide self-assembly to form various nanoarchitectures is an effective approach for generating antibacterial nanomaterials,offering potential advantages such as enhanced antibacterial properties,improved stability,and reduced cytotoxicity.This review highlights recent advancements in tailoring supramolecular AMPs to create diverse nano-architectures for combating infectious diseases.
Chiral supramolecular assembly of π-conjugated luminophores provides a promising avenue for enhancing circularly polarized luminescence.In this study,we shed light on the impact of π-conjugation length on circularly polarized luminescent performance of the resulting supramolecular assemblies,by designing a tetra-cyanostilbene monomeric compound alongside two dicyanostilbene control compounds.These cyanostilbene-based compounds possess the ability to form chiral supramolecular polymers in toluene,driven by a synergistic combination of intermolecular hydrogen bonding and π-stacking interactions.The extended π π-aromatic skeleton brings bathochromic-shifted fluorescence and enhanced intermolecular stacking capability for the tetra-cyanostilbene compound.Consequently,chiral supramolecular assemblies formed by the tetra-cyanostilbene compound demonstrate a remarkable two-fold increase in g_(lum) values relative to the assemblies formed by the dicyanostilbene compounds.Overall,this study provides valuable insights into the relationship between-conjugation length and the circularly polarized luminescent performance of π-conjugatedsupramolecularassemblies.
Tongjin LvSong WuYu JinJianfei MaSixun JiangYuncong XueFeng Wang
