Active and passive modulation of solar light transmittance in a uniquely multifunctional dual-band single molecule for smart window applications

Functional materials may change color by heat and electricity separately or simultaneously in smart windows.These materials have not only demonstrated remarkable potential in the modulation of solar radiation but are also leading to the development of indoor environments that are more comfortable and conducive to improving individuals'quality of life.Unfortunately,dual-responsive materials have not received ample research attention due to economic and technological challenges.As a consequence,the broader utilization of smart windows faces hindrances.To address this new generational multistimulus responsive chromic materials,our group has adopted a developmental strategy to create a poly(NIPAM)n-HV as a switchable material by anchoring active viologen(HV)onto a phase-changing poly(NIPAM)n-based smart material for better utility and activity.These constructed smart windows facilitate individualistic reversible switching,from a highly transparent state to an opaque state(thermochromic)and a red state(electrochromic),as well as facilitate a simultaneous dual-stimuli response reversible switching from a clear transparent state to a fully opaque(thermochromic)and orange(electrochromic)states.Absolute privacy can be attained in smart windows designed for exclusive settings by achieving zero transmittance.Each unique chromic mode operates independently and modulates visible and near-infrared(NIR)light in a distinct manner.Hence,these smart windows with thermal and electric dual-stimuli responsiveness demonstrate remarkable heat regulation capabilities,rendering them highly attractive for applications in building facades,energy harvesting,privacy protection,and color display.

Robust Collaborative Optimization Method Based on Dual-response Surface

A novel method for robust collaborative design of complex products based on dual-response surface （DRS-RCO） is proposed to solve multidisciplinary design optimization （MDO） problems under uncertainty. Collaborative optimization （CO） which decomposes the whole system into a double-level nonlinear optimization problem is widely accepted as an efficient method to solve MDO problems. In order to improve the quality of complex product in design process, robust collaborative optimization （RCO） is developed to solve those problems under uncertain conditions. RCO does optimization on the linear sum of mean and standard deviation of objective function and gets an optimal solution with high robustness. Response surfaces method is an important way to do approximation in robust design. DRS-RCO is an improved RCO method in which dual-response surface replaces system uncertainty analysis module of CO. The dual-response surface is the approximate model of mean and standard deviation of objective function respectively. In DRS-RCO, All the information of subsystems is included in dual-response surfaces. As an additional item, the standard deviation of objective function is added to the subsystem optimization. This item guarantee both the mean and standard deviation of this subsystem is reaching the minima at the same time. Finally, a test problem with two coupled subsystems is conducted to verify the feasibility and effectiveness of DRS-RCO.

Utilizing dual-responsive iridium(Ⅲ) complex for hepatocellular carcinoma: Integrating photoacoustic imaging with chemotherapy and photodynamic therapy

Stimuli-triggered release and alleviating resistance of iridium(Ⅲ)-based drugs at tumor sites remains challengeable for clinical hepatoma therapy.Herein,a doxorubicin@iridium-transferrin(DOX@Ir-TF)nanovesicle was synthesized by carboxylated-transferrin(TF)and doxorubicin-loaded amphiphilic iridium-amino with quaternary ammonium(QA)groups and disulfide bonds.The QA groups enhanced photophysical properties and broadened production capacity of photoinduced-reactive oxygen species(ROS),while the disulfide-bridged bonds regulated oxidative stress levels through reacting with glutathione(GSH);simultaneously,modification of TF improved recognition and endocytosis of the nanovesicle for tumor cells.Based on in-vitro results,a controlled-release behavior of DOX upon a dualresponsiveness of GSH and near-infrared ray(NIR)irradiation was presented,along with high-efficiency generation of ROS.After an intravenous injection,the nanovesicle was targeted at tumor sites,realizing TF-navigated photoacoustic imaging guidance and synergistic chemotherapy-photodynamic therapy under NIR/GSH stimulations.Overall,newly-synthesized DOX@Ir-TF nanovesicle provided a potential in subcutaneous hepatocellular carcinoma therapy due to integrations of targeting delivery,dual-stimuli responsive release,synergistic therapy strategy,and real-time monitoring.

Dual-responsive supramolecular photodynamic nanomedicine with activatable immunomodulation for enhanced antitumor therapy

A major challenge facing photodynamic therapy(PDT) is that the activity of the immuneinduced infiltrating CD8^(+)T cells is subject to the regulatory T lymphocytes(Tregs), leaving the tumor at risk of recurrence and metastasis after the initial ablation. To augment the antitumor response and reprogram the immunosuppressive tumor microenvironment(TME), a supramolecular photodynamic nanoparticle(DACss) is constructed by the host-guest interaction between demethylcantharidin-conjugated β-cyclodextrin(DMC-CD) and amantadine-terminated disulfide-conjugated FFVLGGGC peptide with chlorin e6 decoration(Ad-ss-pep-Ce6) to achieve intelligent delivery of photosensitizer and immunomodulator for breast cancer treatment. The acid-labile β-carboxamide bond of DMC-CD is hydrolyzed in response to the acidic TME, resulting in the localized release of DMC and subsequent inhibition of Tregs.The guest molecule Ad-ss-pep-Ce6 can be cleaved by a high level of intracellular GSH, reducing photosensitizer toxicity and increasing photosensitizer retention in the tumor. With a significant increase in the CTL/Treg ratio, the combination of Ce6-based PDT and DMC-mediated immunomodulation adequately achieved spatiotemporal regulation and remodeling of the TME, as well as improved primary tumor and in situ lung metastasis suppression with the aid of PD-1 antibody.

Light/pH dual-responsive magnetic metal-organic frameworks composites for phosphorylated peptide enrichment

Metal-organic frameworks(MOFs)combined with specific ligands are highly adaptable smart materials that can respond to external and physiological stimuli.In this study,we introduced a pyridinyl zwitterionic ligand with light/pH dual response into magnetic MOF composite(Fe_(3)O_(4)@ZW-MOF)for enrichment of phosphorylated peptides for the first time.The introduction of the developed ligand gives MOF material dual response properties.Light stimulation affects the generation/disappearance of free radicals of the pyridine derivative,resulting in a change in the charge gradient of the zwitterion,and zwitterion can also regulate the p H of the solution by adding acid or base.Therefore,the reversible capture and release of phosphorylated peptides can be easily achieved by adjusting light and pH.The established phosphorylated peptide enrichment platform exhibits high sensitivity(detection limit of 1 fmol),high selectivity(β-casein:BSA,1:1000),and good reusability(7 cycles).In addition,the method was applied to the enrichment of phosphorylated peptides in complex systems(non-fat milk and human serum),demonstrating the feasibility of this method for phosphoproteom analysis.In conclusion,the synthesized Fe_(3)O_(4)@ZW-MOF is a promising MOF material,which provides the possibility to advance the application of responsive MOFs materials in proteomics.

Integrated and dual-responsive lipopeptide nanovector with parallel effect to tumor and micro-environment regulation by efficient gene and drug co-delivery

The integrated lipopeptide(RVA)/gene complexes are fabricated with bi-directional regulation on tumor cells and micro-environment.After self-assembling and target coating modification,the poly(γ-glutamic acid)(γ-PGA)/RVA nano-vectors can sequentially respond to pH&redox stimuli,and guarantee efficient therapeutic gene delivery and control release of all-trans retinoic acid.The design provides a facile but promising strategy to treat refractory cancers.

A dual-responsive hyaluronic acid nanocomposite hydrogel drug delivery system for overcoming multiple drug resistance

Chemotherapy is restricted by efficient drug outflow due to the multiple drug resistance(MDR)in heterogenous nature of tumor.Herein,we present a dual-responsive hyaluronic acid(HA)nanocomposite hydrogel that can not only response to the tumor microenvironment but also enhance chemotherapy.This HA hydrogel consists of a core-shell SiO_(2)(GOD@SiO_(2)-Arg)and mesoporous silica nanoparticles(MSNs)with doxorubicin(DOX)as the cargo(DOX@MSN).It could rapidly release the GOD@SiO_(2)-Arg nanoparticles at the low p H tumor-specific environment due to the cleavage of imine bond.GOD@SiO_(2)-Arg activated by over-expressed glutathione(GSH)in tumor cells releases GOD due to the cleavage of disulfide bonds,which could oxidize glucose to produce hydrogen peroxide(H2O2)for in situ NO generation via reaction between Arg and H2O2.The validity of this study might provide a method to modulate the tumor microenvironment for enhancing chemotherapy.

Nanoscale“precision strike”:Tumor microenvironment-responsive smart micelles for efficient targeted drug delivery

To address the limitations of conventional nanotechnology-based drug delivery systems,this work developed enzyme and reduction dual-responsive polymeric micelles.These micelles were synthesized with copolymers composed of TPGS_(3350)-PVGLIG-DOX(TPD)and FA-SS-DOX(FSD),which endow them with tumor-targeted drug delivery capabilities.TPGS_(3350)contributes to extending the circulation of micelles in body,augmenting their accumulation in tumor tissues via the enhanced permeability and retention(EPR)effect.Upon localized the tumor site,matrix metalloproteinase 2(MMP2)cleaves the PVGLIG peptide moiety within the micelles,thereby releasing TPGS_(3350)and exposing the targeting ligand of folate.This approach enables the subsequent internalization of the micelles by tumor cells through folate receptor-mediated endocytosis.After internalization,the high intracellular concentration of glutathione(GSH)triggers the reduction of the disulfide bond within the FA-SS-DOX,leading to the release of the anticancer-drug doxorubicin(DOX),which promotes apoptosis in the tumor cells and enhances the efficacy of chemotherapy.

Glucose and MMP-9 dual-responsive hydrogel with temperature sensitive self-adaptive shape and controlled drug release accelerates diabetic wound healing

Chronic diabetic wounds are an important healthcare challenge. High concentration glucose, high level of matrix metalloproteinase-9 (MMP-9), and long-term inflammation constitute the special wound environment of diabetic wounds. Tissue necrosis aggravates the formation of irregular wounds. All the above factors hinder the healing of chronic diabetic wounds. To solve these issues, a glucose and MMP-9 dual-response temperature-sensitive shape self-adaptive hydrogel (CBP/GMs@Cel&INS) was designed and constructed with polyvinyl alcohol (PVA) and chitosan grafted with phenylboric acid (CS-BA) by encapsulating insulin (INS) and gelatin microspheres con-taining celecoxib (GMs@Cel). Temperature-sensitive self-adaptive CBP/GMs@Cel&INS provides a new way to balance the fluid-like mobility (self-adapt to deep wounds quickly, approximately 37 ◦C) and solid-like elasticity (protect wounds against external forces, approximately 25 ◦C) of self-adaptive hydrogels, while simultaneously releasing insulin and celecoxib on-demand in the environment of high-level glucose and MMP-9. Moreover, CBP/ GMs@Cel&INS exhibits remodeling and self-healing properties, enhanced adhesion strength (39.65 ± 6.58 kPa), down-regulates MMP-9, and promotes cell proliferation, migration, and glucose consumption. In diabetic full-thickness skin defect models, CBP/GMs@Cel&INS significantly alleviates inflammation and regulates the local high-level glucose and MMP-9 in the wounds, and promotes wound healing effectively through the synergistic effect of temperature-sensitive shape-adaptive character and the dual-responsive system.

pH and H2O2 dual-responsive carbon dots for biocatalytic transformation monitoring

Development of sensitive biosensors for biocatalytic transformations monitoring is in high demand but remains a great challenge. It is ascribed to the current strategies that focused on the single metabolite detection, which may bring about the relatively low sensitivity and false diagnosis result. Herein, we report the design and fabrication of novel carbon dots(CDs) with strong orange light emission, pH and H2O2 dual-responsive characteristics. The fluorescence quenching of CDs by H+and H2O2 enables the highly sensitive detection of H+/H2O2-generating biocatalytic transformations. This is exemplified by the glucose oxidase-mediated catalytic oxidation reaction on glucose, in which H+and H2O2 would be formed. As compared to the case in which glucose is present, significant fluorescence reduction is detected, and the fluorescence intensity is negatively proportional to glucose concentration. Thus, highly sensitive detection of glucose was readily achieved with a detection limit down to 10.18 nmol/L. The prepared CDs not only realize the highly sensitive detection of glucose, but also allows the probing other substances by changing the enzymes, thus providing a versatile platform, and demonstrating good potential to be used for biocatalytic transformations effective monitoring.

Novel robust cellulose-based foam with pH and light dual-response for oil recovery

We fabricated pH and light dual-responsive adsorption materials which could induce the transition of surface wettability between hydrophobicity and hydrophilicity by using ATRPo The structure and morphology of adsorption materials were confirmed by ATR-FTIR, XPS, TGA and SEM. It showed that the modified cellulose （CE）- based foam was hydrophobic, which can adsorb a range of oils and organic solvents in water under pH = 7.0 or visible light irradiation （λ〉500 nm）. Meanwhile, the wettability of robust CE-based foam can convert hydrophobicity into hydrophilicity and underwater oleophobicity under pH = 3.0 or UV irradiation （λ = 365 nm）, giving rise to release oils and organic solvents. Most important of all, the adsorption and desorption processes of the modified CE-based foam could be switched by external stimuli. Furthermore, the modified CE-based foam was not damaged and still retained original performance after reversible cycle repeated for many times with variation of surface wettability. In short, it indicates that CE-based foam materials with switchable surface wettability are new responsive absorbent materials and have owned potential application in the treatment of oil recovery.

Stable ZnO/ionic liquid hybrid materials: novel dual-responsive superhydrophobic layers to light and anions

Novel dual-responsive superhydrophobic hybrid materials, ZnO/SAMs （self-assembled monolayers） of ionic liquids （ILs） with different counter-anions （I^-, BF4^-, PF6^- and Tf2N^-）, were synthesized and characterized. ZnO nanoparticles were first deposited on glass surfaces to produce roughness. Next, SAMs of fluorinated-alkyl-3-（3-triethoxysilylpropyl）-4,5-dihydro-imidazoliumiodide （abb. [C8Ftespim]I） were grafted onto these surfaces via -Si-O- covalent bonds using self-assembly technique. The I- ion could be subsequently exchanged with BF4, PF6-or Tf2N- through a simple aqueous anion-exchange reaction. The ZnO/ILs hybrid layers were characterized by atomic-force microscopy （AFM）, scanning-electron microscopy （SEM） and X-ray photoelectron spectroscopy （XPS）. Their wettability was estimated through the measurements of static and dynamic contact angles （CAs）. Compared to corresponding films of ZnO/[CsFtespim]I with CAs 140.7° ±2.0°, films of ZnO/[CsFtespim]PF6 and ZnO/[CsFtespim]Tf2N showed CAs with 154.0° ± 2.0° and 152.0° ± 2.0°, respectively that remained for a long time. This result suggests that anion-exchange can afford superhydrophobic materials. In addition, the wettability of ZnO/[CsFtespim]X hybrid layers can be reversibly switched by altering ultraviolet （UV） irradiation and dark storage, which shows a photo-induced reversible switch of wettability. The synergistic action of ZnO nanoparticles and SAMs of ILs produced light-anion dual-responsive superhydrophobic materials with ideal stability.

Phenylboronic acid-modified hollow silica nanoparticles for dual-responsive delivery of doxorubicin for targeted tumor therapy

This work reports a multifunctional nanocarrier based on hollow mesoporous silica nanoparticles(HMSNs)for targeting tumor therapy.Doxorubicin(DOX)was loaded into HMSNs and blocked with cytochrome C conjugated lactobionic acid(CytC–LA)via redox-cleavable disulfide bonds and pH-disassociation boronate ester bonds as intermediate linkers.The CytC–LA was used both as sealing agent and targeting motif.A series of characterizations demonstrated the successful construction of the drug delivery system.The system demonstrated pH and redox dual-responsive drug release behavior in vitro.The DOX loading HMSNs system displayed a good biocompatibility,which could be specifically endocytosed by HepG2 cells and led to high cytotoxicity against tumor cells by inducing cell apoptosis.In vivo data(tumor volume,tumor weight,terminal deoxynucleotidyl transferase dUTP nick end labeling and hematoxylin and eosin staining)proved that the system could deliver DOX to tumor site with high efficiency and inhibit tumor growth with minimal toxic side effect.

Dual Photo/Thermo-Responsive Polypeptoids

A series of polypeptoids with dual photo/thermo-responsiveness were prepared by incorporating both azobenzene(Azo)group and oligo(ethylene glycol)(OEG)segment into the side chains.Firstly,the N-substituted-N-carboxyanhydride(NNCA)monomers with different Azo and OEG groups were synthesized,and then a single NNCA ring-openning polymerization was performed to afford dual-responsive polypeptoids without any post-polymerization modification.The ultra-violet/visible(UV/Vis)photo-responsive behaviors of the polypeptoids were achieved by cis-trans photoisomerization of the Azo group and confirmed by both ^(1)H-NMR and UV/Vis spectroscopy.The thermo-responsive behaviors were realized by both OEG segment and Azo group and confirmed by UV/Vis spectroscopy and dynamic light scattering.This work demonstrated the synthetic pathway for dual responsive polypeptoids using NNCA monomers with two responsive groups and revealed the potential of polypeptoids as smart materials that could respond to different environmental stimuli.

Dendrimer-decorated nanogels:Efficient nanocarriers for biodistribution in vivo and chemotherapy of ovarian carcinoma

Nanomedicine has revolutionized disease theranostics by the accurate diagnosis and efficient therapy.Here,the PAMAM dendrimer decorated PVCL-GMA nanogels(NGs)were developed for favorable biodistribution in vivo and enhanced antitumor efficacy of ovarian carcinoma.By an ingenious design,the NGs with a unique structure that GMA-rich domains were localized on the surface were synthesized via precipitation polymerization.After G2 dendrimer decoration,the overall charge is changed from neutral to positive,and the NGs-G2 display the whole charge nature of positively charged corona and neutral core.Importantly,the unique architecture and charge conversion of NGs-G2 have a profound impact on the biodistribution and drug delivery in vivo.As a consequence of this alteration,the NGs-G2 as nanocarriers emerge the highly sought biodistribution of reduced liver accumulation,enhanced tumor uptake,and promoted drug release,resulting in the significantly augmented antitumor efficacy with low side effects.Remarkably,this finding is contrary to some reported work that the nanocarriers with positive charge have preferential liver uptake.Moreover,the NGs-G2 also displayed thermal/pH dual-responsive behaviors,excellent biocompatibility,improved cellular uptake,and stimuli-responsive drug release.Encouragingly,this work demonstrates a novel insight into the strategy for optimizing design,improving biodistribution and enhancing theranostic efficacy of nanocarriers.

Programmed albumin nanoparticles regulate immunosuppressive pivot to potentiate checkpoint blockade cancer immunotherapy

The therapeutic efficacy of programmed cell death protein 1/programmed cell death-ligand 1(PD-1/PD-L1)blockade immunotherapy is extremely dampened by complex immunosuppressive mechanisms including regulatory T cells(Treg),M2 macrophages(M2),and prostaglandin E2(PGE2).The pivotal roles of PGE2 have been recognized by directly inactivating CD8+T cells and indirectly inducing Treg and M2.Therefore,PGE2 abolishment through inactivating cyclooxygenase-2(COX-2)could be robust to sensitize tumour toward anti-PD-1/PD-L1 immunotherapy,which has gone into clinical trials.However,exploring this promising strategy in nanomedicine to enhance immunotherapy remains unrevealed.The key challenge to synergistically combine COX-2 inhibition and anti-PD-1/PD-L1 lies in the different pharmacokinetic profiles and the spatial obstacles since PD-1/PD-L1 interaction occurs extracellularly and COX-2 locates intracellularly.Thus,the programmed release nanoparticles(termed as Cele-BMS-NPs)are rationally designed,which are composed of pH-sensitive human serum albumin derivative,BMS-202 compound as PD-1/PD-L1 inhibitor,glutathione(GSH)-activatable prodrug of celecoxib(COX-2 inhibitor).The in vitro experiments demonstrate that this smart Cele-BMS-NPs could extracellularly release BMS-202 under the acidic tumour microenvironment,and the intracellularly release of celecoxib in response to the elevated GSH concentration inside tumour cells.After systemic administration,the intratumoral infiltration of CD8+T cells is significantly enhanced and meanwhile immunosuppressive M2,Treg,and PGE2 are reduced,thereby eliciting the anti-tumour immune responses toward low immunogenic tumours and postsurgical tumour recurrences.