Thiol-Functionalized Conjugated Metal-Organic Frameworks for Stable and Efficient Perovskite Photovoltaics.

Metal-organic frameworks (MOFs) have been investigated recently in perovskite photovoltaics owing to their potential to boost optoelectronic performance and device stability. However, the impact of variations in the MOF side chain on perovskite characteristics and the mechanism of MOF/perovskite film formation remains unclear. In this study, three nanoscale thiol-functionalized UiO-66-type Zr-based MOFs (UiO-66-(SH)2 , UiO-66-MSA, and UiO-66-DMSA) are systematically employed and examined in perovskite solar cells (PSCs). Among these MOFs, UiO-66-(SH)2 , with its rigid organic ligands, exhibited a strong interaction with perovskite materials with more efficient suppression of perovskite vacancy defects. More importantly, A detailed and in-depth discussion is provided on the formation mechanism of UiO-66-(SH)2 -assisted perovskite film upon in situ GIWAXS performed during the annealing process. The incorporation of UiO-66-(SH)2 additives substantially facilitates the conversion of PbI2 into the perovskite phase, prolongs the duration of stage I, and induces a delayed phase transformation pathway. Consequently, the UiO-66-(SH)2 -assisted device demonstrates reduced defect density and superior optoelectronic properties with optimized power conversion efficiency of 24.09% and enhanced long-term stability under ambient environment and continuous light illumination conditions. This study acts as a helpful design guide for desired MOF/perovskite structures, enabling further advancements in MOF/perovskite optoelectronic devices.

Synthesis of Nitrogen-Doped Aza-Helicenes with Chiral Optical Properties.

Aza-helicenes are one of the most important series of heterohelicenes; herein, a series of novel aza-helicenes (5H, 6H, 6S, and 8S) were prepared via Bischler-Napieralski cyclization, and the interconversion dynamic process of these aza-helicenes was revealed using density functional theory calculations. The novel nitrogen-doped [6]helicene (6H) possesses a very high interconversion energy barrier of 36.0 kcal/mol. Two enantiomers of 6H were successfully resolved by high-performance liquid chromatography and showed desired chiral optical properties. 6H with chiral optical activity and lone electrons can be a potential candidate for chiral switches, which was demonstrated using the UV and circular dichroism spectra obtained upon titration with an acid and a base.

Ultra-high quantum yield nitrogen-doped carbon quantum dots and their versatile application in fluorescence sensing, bioimaging and anti-counterfeiting.

The exploration of carbon quantum dots (CQDs) with ultra-high quantum yield, simple synthesis path, and satisfying output to facilitate their wide applications in numerous fields are always the research focus. In this work, nitrogen-doped carbon quantum dots (N-CQDs) with strong blue fluorescence were synthesized with a simple one-step hydrothermal method using citric acid and o-phenylenediamine as raw materials, and the absolute quantum yield was as high as 92.1%. The detailed research results demonstrate that the N-CQDs have outstanding fluorescence stability, high selectivity, and anti-interference in Hg2+ detection. The obtained N-CQDs also possess excellent biocompatibility, which can also be successfully applied in cell imaging and intracellular Hg2+ detection. Most importantly, due to their high quantum yield and excellent dispersibility, the N-CQDs solution can be used as a quick-drying fluorescent ink for ink-jet printing. Therefore, the as-prepared N-CQDs have great potential in fluorescence sensing, biomedical diagnosis, data encryption, and anti-counterfeiting.

Perovskite Quantum Wells Formation Mechanism for Stable Efficient Perovskite Photovoltaics-A Real-Time Phase-Transition Study.

The combination of a bulk 3D perovskite layer and a reduced dimensional perovskite layer (perovskite quantum wells (PQWs)) is demonstrated to enhance the performance of perovskite solar cells (PSCs) significantly in terms of stability and efficiency. This perovskite hierarchy has attracted intensive research interest; however, the in-depth formation mechanism of perovskite quantum wells on top of a 3D perovskite layer is not clearly understood and is therefore the focus of this study. Along with ex situ morphology and photophysical characterization, the time-resolved grazing-incidence wide-angle X-ray scattering (TS-GIWAXS) technique performed in this study provides real-time insights on the phase-transition during the organic cation (HTAB ligand molecule) coating and PQWs/3D architecture formation process. A strikingly strong ionic reaction between the 3D perovskite and the long-chain organic cation leads to the quick formation of an ordered intermediate phase within only a few seconds. The optimal PQWs/3D architecture is achieved by controlling the HTAB casting, which is assisted by time-of-flight SIMS characterization. By controlling the second ionic reaction during the long-chain cation coating process, along with the fluorinated poly(triarylamine) (PTAA) as a hole-transport layer, the perovskite solar cells demonstrate efficiencies exceeding 22% along with drastically improved device stability.

Robust, Reprocessable, and Reconfigurable Cellulose-Based Multiple Shape Memory Polymer Enabled by Dynamic Metal-Ligand Bonds.

Smart materials with multiple shape memory capacities have gradually attracted the interest of a lot of researchers due to their potential application in textiles, smart actuators, and aerospace engineering. However, the design and sustainable synthesis of multiple shape memory polymers (SMPs) simultaneously possessing robust mechanical strength, reprocessability, and reconfigurability still remain full of challenges. Starting from a readily available biomass material cellulose, a well-defined SMP, cellulose-graft-poly(n-butyl acrylate-co-1-vinylimidazole) copolymer (Cell-g-(BA-co-VI)) was facilely synthesized by addition-fragmentation chain transfer polymerization (RAFT) and the subsequent metallosupramolecular cross-linking. Taking advantage of the dynamic bonding, i.e., the rapid reversible fragmentation and the formation of metal ion-imidazole coordination, polymer networks with highly tunable mechanical properties, excellent solid-state plasticity, and quadruple-shape memory capacity are handily attainable. Microscopically, the metal-ligand clusters have a strong tendency to phase segregate from the soft grafted copolymers indicated by atomic force microscopy (AFM), and these serve as netpoints to construct novel SMPs. This article represents our new exploration of the next-generation SMPs based on cellulose backbone where carrying with supramolecular cross-linked soft grafted copolymers. This architecture design allows achieving robust, reprocessable, and reconfigurable thermoplastic SMPs that are difficult to realize by many other methods. Integrating these properties into one system in a synergetic manner also provides a novel approach to the high value addition application of cellulose in the fabrication of advanced functional materials.

Acid Environment-improved fluorescence sensing performance: A quinoline Schiff base-containing sensor for Cd2+ with high sensitivity and selectivity.

The development of acid environment-applicable fluorescence sensor is challenging but attractive topic, which can achieve the rapid and comprehensive evaluation of total soluble heavy metal content in natural water. In this work, a quinoline-containing Schiff base, AMQD, was utilized as fluorescence probe for Cd2+. Interestingly, the obtained chemosensor exhibited much better fluorescence detection sensitivity and selectivity toward Cd2+ in acidic 10% methanol aqueous solution (pH 4) comparing to those in neutral environment. Initially, the fluorescence emission of AMQD was almost invisible with the absence of metal ions, while a significant turn-on fluorescence response (~425 nm) can be observed with the addition of Cd2+. The fluorescence detection possesses excellent selectivity without the interference of any other metal cation. The recognition ratio between the fluorescence sensor AMQD and Cd2+ was confirmed to be 1:1, and the detection limit was calculated to be 2.4 nM.

Near infrared photothermal-responsive poly(vinyl alcohol)/black phosphorus composite hydrogels with excellent on-demand drug release capacity.

Owing to their excellent tissue-penetration ability, near-infrared (NIR) photothermal-responsive intelligent materials show remarkable advantages in biomedical applications. However, the majority the previously reported NIR-absorbing agents are metal- and carbon-based nanoparticles, both of which possess low photothermal conversion efficiency and poor biocompatibility. Herein, polydopamine modified black phosphorus (pBP) nanosheet-containing poly(vinyl alcohol) (PVA) composite hydrogels are facilely fabricated via a freezing/thawing approach. Taking advantage of the high photothermal conversion efficiency of pBP, the prepared composite hydrogels exhibit a fascinating on-demand NIR-responsive drug release behavior. An in vitro cell culture study demonstrates that these composite hydrogels present good biocompatibility and cellular interaction. Moreover, since the incorporated pBP nanosheets can form a strong hydrogen bonding interaction within the PVA matrix, the composite hydrogels also show enhanced mechanical properties. We believe that the robust mechanical properties and excellent biocompatibility accompanied by the highly controllable NIR-responsive drug release performance of the obtained composite hydrogel augur well for its diverse future applications in the biomedical field.

Surface functionality density regulated in situ reduction of nanosilver on hierarchial wrinkled mesoporous silica nanoparticles and their antibacterial activity.

Hierarchical wrinkled mesoporous silica nanoparticles (WMS NPs) bedecked with diverse functionality density of amino groups (WMSs-N2, WMSs-NN and WMSs-NNN) were first synthesized via typical Sol-Gel method, and then utilized for the in situ reduction of nanosilver with sodium borohydride. Elegantly distributed Ag NPs (ca. 7-10 nm, 3-5 nm) on WMSs-N2 and WMSs-NN without any agglomeration were obtained respectively, while Ag NPs (ca. 50 nm) dispersed on WMSs-NNN were obviously larger and slightly agglomerated. Compared to pure Ag NPs, all the obtained Ag@WMSs composites were durable and displayed much better antibacterial performance, with a minimal inhibitory concentration of 12-80 mg L-1 and a minimal bactericidal concentration of 24-108 mg L-1, respectively. Moreover, it was found that the functionality density of amino groups and the specific surface area of WMSs played a crucial role for the antibacterial performance of the obtained nanocomposites. Because WMSs-NN had higher specific surface area and surface amino density than WMSs-N2, the size and dispersion of Ag NPs on WMSs-NN were smaller and superior to those of Ag NPs on WMSs-N2, respectively. Accordingly, Ag@WMSs-NN displayed a better antibacterial capacity than Ag@WMSs-N2. As for Ag@WMSs-NNN, owing to the high loading content of Ag NPs, they exhibited the best antibacterial and bactericidal properties.

Facile synthesis of a water-soluble fluorescence sensor for Al3+ in aqueous solution and on paper substrate.

In this study, a facile water-soluble fluorescence sensor 2-((2-hydroxybenzylidene)-amino)-2-(hydroxymethyl)propane-1,3-diol (ST) was synthesized via one-step reaction, and its fluorescence sensing performance for Al3+ both in aqueous solution and on paper substrate was evaluated. The results showed that ST exhibited an specific fluorescence "turn-on" response to Al3+ over other cations in aqueous solution as well as on the test paper. The limit of detection was found to be 3.2×10-7M, which revealed that the obtained Schiff-base based fluorescence chemosensor ST possessed a great potential for the rapid, quantitative and qualitative detection of Al3+.

Luminescent Poly(vinyl alcohol)/Carbon Quantum Dots Composites with Tunable Water-Induced Shape Memory Behavior in Different pH and Temperature Environments.

Luminescent water-induced shape memory polymer (SMP) composites with tunable shape recovery rate are developed by blending poly(vinyl alcohol) (PVA) and carbon quantum dots (CQDs). The oxygen and active hydrogen-rich CQDs can serve as extra physical cross-linking points in PVA via strong hydrogen bonding interaction, which largely improves the shape memory performances of PVA. At room temperature, water can successfully actuate the shape recovery of deformed PVA/CQDs composite. It is demonstrated that this water-induced shape recovery is mainly attributed to the plasticizing effect of water and its competitive hydrogen bonding. Furthermore, a quantitative bending test suggests that the shape recovery time of this water-induced SMP is tunable by altering the environmental pH value and temperature, and a relatively large shape recovery time window (from 20 to 200 s) can be achieved. In addition, the introduction of CQDs endows the PVA/CQDs SMP composites with excellent luminescent property, which makes the shape change of SMP visible under UV light. It should be noted that the mild stimulus condition and tunable shape recovery performances make the luminescent visible PVA/CQDs SMP feasible for diverse biological applications in smart medical devices, stimuli-responsive drug-release, and intelligent sensors in vivo and in vitro.

In-situ reduction of monodisperse nanosilver on hierarchical wrinkled mesoporous silica with radial pore channels and its antibacterial performance.

Monodisperse silver nanoparticles (Ag NPs) were facilely loaded on the inner and outer surface of hierarchical wrinkled mesoporous silica (WMSs) via an in situ chemical reduction, and the antibacterial capacity of the obtained nanocomposite was investigated in detail. Typical sulfydryl-functionalized wrinkled mesoporous silica nanoparticle with radical pore channels was firstly prepared through sol-gel technique with cetyltrimethylammonium bromide (CTAB) as the templating surfactant. After sulfonation of the as-prepared WMSs, Ag(+) ions were then densely locked up on the inner and outer surface of WMSs via electrostatic interactions. Well distributed Ag NPs (ca. 3-5nm) on WMSs without any agglomeration were finally obtained via a simple in situ reduction reaction with sodium borohydride. Minimal inhibitory concentration (MIC) and minimal bactericidal concentration (MBC) test indicated that the obtained products can achieve durable and much better antibacterial performance both against Gram-negative bacterium Escherichia coli (E. coli) and Gram-positive bacterium Staphylococcus aureus (S. aureus) comparing to pure colloidal silver nanoparticles, which rendered them as favorable candidate for the development of effective antibacterial agents.

A stimuli-responsive nanogel-based sensitive and selective fluorescent sensor for Cr(3+) with thermo-induced tunable detection sensitivity.

Stimuli-responsive poly(N-isopropylacrylamide) nanogel with covalently labeled rhodamine B urea derivatives (P(NIPAM-co-RhBUA)) is utilized as a sensitive fluorescent probe for Cr(3+) in aqueous solution, and its thermo-induced tunable detection capacity is investigated. At 20 °C, non-fluorescent nanogel can selectively bind with Cr(3+) over some other metal ions, leading to prominent fluorescence OFF-ON switching due to the recognition of RhBUA with Cr(3+) . Upon heating above the phase transition temperature, enhanced fluorescence intensity is observed (≈61-fold increase at 45 °C) for the nanogel in the presence of Cr(3+) , accompanied with an improved detection sensitivity, which suggest that hydrophobic microenvironment generated in the collapsed nanogel plays an active role for their detection performance.

Photo-degradable, protein-polyelectrolyte complex-coated, mesoporous silica nanoparticles for controlled co-release of protein and model drugs.

The fabrication of photo-degradable, protein-polyelectrolyte complex (PPC)-coated, mesoporous silica nanoparticles (MSNs) and their controlled co-release of protein and model drugs is reported. Random copolymers composed of oligo(ethylene glycol) monomethyl ether methacrylate (OEGMA), and a photolabile o-nitrobenzyl-containing monomer, 5-(2'-(dimethylamino)ethoxy)-2-nitrobenzyl methacrylate (DENBMA), are first anchored onto the MSNs and then quaternary aminated, to obtain positively charged P(OEGMA-co-TENBMA) which exhibits photo-induced charge conversion characteristics. PPCs consisting of P(OEGMA-co-TENBMA) and the protein bovine serum albumin (BSA) are utilized as capping agents for the nanopores of the MSNs. Upon UV irradiation, charge conversion of P(OEGMA-co-TENBMA) can lead to the disruption of PPCs on MSNs and co-release of BSA and rhodamine B by electrostatic repulsion.

Construction of polymer-protein bioconjugates with varying chain topologies: polymer molecular weight and steric hindrance effects.

We report on the fabrication of well-defined polymer-protein bioconjugates with varying chain architectures, including star polymers, star block copolymers, and heteroarm star copolymers through the specific noncovalent interaction between avidin and biotinylated synthetic polymer precursors. Homopolymer and diblock precursors site-specifically labeled with a single biotin moiety at the chain terminal, chain middle, or diblock junction point were synthesized by a combination of atom-transfer radical polymerization (ATRP) and click reactions. By taking advantage of molecular recognition between avidin and biotin moieties, supramolecular star polymers, star block copolymers, and heteroarm star copolymers were successfully fabricated. This specific binding process was also assessed by using the diffraction optic technology (DOT) technique. We further investigated the effects of polymer molecular weights, location of biotin functionality within the polymer chain, and polymer chain conformations, that is, steric hindrance effects, on the binding numbers of biotinylated polymer chains per avidin within the polymer-protein bioconjugates, which were determined by the standard avidin/2-(4-hydroxyazobenzene)benzoic acid (HABA) assay. The binding numbers vary in the range of 1.9-3.3, depending on the molecular weights, locations of biotin functionality within synthetic polymer precursors, and polymer chain conformations.

pH-disintegrable polyelectrolyte multilayer-coated mesoporous silica nanoparticles exhibiting triggered co-release of cisplatin and model drug molecules.

We report on the fabrication of pH-disintegrable polyelectrolyte multilayer-coated mesoporous silica nanoparticles (MSN) capable of triggered co-release of cisplatin and model drug molecules. The outer polyelectrolyte multilayer was assembled from permanently cationic polyelectrolyte, poly(allyl amine hydrochloride) (PAH), and negatively charged polyelectrolyte, P(DMA-co-TPAMA), consisting of N,N-dimethylacrylamide (DMA) and 3,4,5,6-tetrahydrophthalic anhydride-functionalized N-(3-aminopropyl)methacrylamide (TPAMA) monomer units, which exhibits pH-induced charge conversion characteristics. Thus, the subtle alteration of solution pH from 7.4 to ≈5-6 can lead to the disintegration of outer polyelectrolyte multilayers, accompanied with the co-release of cisplatin and RhB.

Thermoresponsive core cross-linked micelles for selective ratiometric fluorescent detection of Hg2+ ions.

We report on the fabrication of core cross-linked (CCL) micelles possessing thermoresponsive cores and their application as sensitive and selective ratiometric Hg(2+) probes with thermo-tunable detection efficiency. Well-defined double hydrophilic block copolymer (DHBC) bearing naphthalimide-based Hg(2+)-reactive moieties (NUMA, 4), PEO-b-P(NIPAM-co-NAS-co-NUMA), was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, where PEO, NIPAM, and NAS represent poly(ethylene oxide), N-isopropylacrylamide, and N-acryloxysuccinimide. At 25 °C, PEO-b-P(NIPAM-co-NAS-co-NUMA) unimers in aqueous solution can act as ratiometric Hg(2+) probes with a detection limit of ∼10.1 nM. After core cross-linking of the micellar nanoparticles formed at elevated temperatures, structurally stable CCL micelles with well-solvated PEO coronas and thermoresponsive cores embedded with Hg(2+)-reactive NUMA moieties were obtained. Upon Hg(2+) addition, the aqueous dispersion of CCL micelles exhibit a colorimetric transition from yellowish to colorless and a fluorometric emission transition from green to bright blue. Moreover, Hg(2+) detection limits of CCL micelles were considerably enhanced to 3.0 and 1.8 nM at 25 and 40 °C, when the thermoresponsive cores are at their swollen and collapsed state, respectively. The high selectivity of CCL micelles to Hg(2+) over other common cations was also demonstrated. Furthermore, in vitro studies revealed that CCL micelles can effectively enter into living cells and sensitively respond to the presence of Hg(2+) ions via the change of fluorescence emission color. This work represents the first example of DHBC-based CCL micelle acting as highly selective and sensitive ratiometric metal ion probes. The structural stability, water dispersibility, biocompatibility, and most importantly the thermo-tunable detection sensitivity of this novel type of CCL micelle-based sensing systems augur well for their future applications as multifunctional nanocarriers for drug delivery, sensing, imaging, and diagnosis.

Synthesis of amphiphilic tadpole-shaped linear-cyclic diblock copolymers via ring-opening polymerization directly initiating from cyclic precursors and their application as drug nanocarriers.

We report on the facile synthesis of well-defined amphiphilic and thermoresponsive tadpole-shaped linear-cyclic diblock copolymers via ring-opening polymerization (ROP) directly initiating from cyclic precursors, their self-assembling behavior in aqueous solution, and the application of micellar assemblies as controlled release drug nanocarriers. Starting from a trifunctional core molecule containing alkynyl, hydroxyl, and bromine moieties, alkynyl-(OH)-Br, macrocyclic poly(N-isopropylacrylamide) (c-PNIPAM) bearing a single hydroxyl functionality was prepared by atom transfer radical polymerization (ATRP), the subsequent end group transformation into azide functionality, and finally the intramacromolecular ring closure reaction via click chemistry. The target amphiphilic tadpole-shaped linear-cyclic diblock copolymer, (c-PNIPAM)-b-PCL, was then synthesized via the ROP of ε-caprolactone (CL) by directly initiating from the cyclic precursor. In aqueous solution at 20 °C, (c-PNIPAM)-b-PCL self-assembles into spherical micelles consisting of hydrophobic PCL cores and well-solvated coronas of cyclic PNIPAM segments. For comparison, linear diblock copolymer with comparable molecular weight and composition, (l-PNIPAM)-b-PCL, was also synthesized. It was found that the thermoresponsive coronas of micelles self-assembled from (c-PNIPAM)-b-PCL exhibit thermoinduced collapse and aggregation at a lower critical thermal phase transition temperature (T(c)) compared with those of (l-PNIPAM)-b-PCL. Temperature-dependent drug release profiles from the two types of micelles of (c-PNIPAM)-b-PCL and (l-PNIPAM)-b-PCL loaded with doxorubicin (Dox) were measured, and the underlying mechanism for the observed difference in releasing properties was proposed. Moreover, MTT assays revealed that micelles of (c-PNIPAM)-b-PCL are almost noncytotoxic up to a concentration of 1.0 g/L, whereas at the same polymer concentration, micelles loaded with Dox lead to ∼60% cell death. Overall, chain topologies of thermoresponsive block copolymers, that is, (c-PNIPAM)-b-PCL versus (l-PNIPAM)-b-PCL, play considerable effects on the self-assembling and thermal phase transition properties and their functions as controlled release drug nanocarriers.

Fluorescent pH-sensing organic/inorganic hybrid mesoporous silica nanoparticles with tunable redox-responsive release capability.

We report on the fabrication of fluorescent pH-sensing organic/inorganic hybrid mesoporous silica nanoparticles (MSN) capable of tunable redox-responsive release of embedded guest molecules. The reversible addition-fragmentation chain transfer (RAFT) copolymerization of N-(acryloxy)succinimide (NAS), oligo(ethylene glycol) monomethyl ether methacrylate (OEGMA), and 1,8-naphthalimide-based pH-sensing monomer (NaphMA) at the surface of MSN led to fluorescent organic/inorganic hybrid MSN. The obtained hybrid MSN exhibits excellent water dispersibility and acts as sensitive fluorescent pH probes in the range pH 4-8 due to the presence of NaphMA moieties. After loading with rhodamine B (RhB) as a model drug molecule, P(NAS-co-OEGMA-co- NaphMA) brushes at the surface of hybrid MSN were cross-linked with cystamine to block nanopore entrances for the effective retention of guest molecules. Taking advantage of disulfide-containing cross-linkers, the release rate of RhB can be easily adjusted by adding varying concentrations of dithiothreitol (DTT), which can cleave the disulfide linkage to open blocked nanopores. The increase of DTT concentration from 0 to 20 mM led to 20-30 times enhancement of RhB release rate. The reported multifunctional hybrid MSN augurs well for applications in controlled-release nanocarriers, cell and tissue imaging, and clinical diagnosis.

Fabrication of a thermoresponsive biohybrid double hydrophilic block copolymer by a cofactor reconstitution approach.

The fabrication of a thermoresponsive biohybrid double hydrophilic block copolymer (DHBC) by a cofactor reconstitution approach is reported. Poly(N-isopropylacrylamide) (PNIPAM) bearing a porphyrin moiety at the chain terminal, PPIXZn-PNIPAM, is synthesized by the combination of ATRP and a click reaction. The subsequent cofactor reconstitution process between apomyoglobin and PPIXZn-PNIPAM affords well-defined myoglobin-b-PNIPAM protein-polymer bioconjugates. Behaving as typical responsive DHBCs, the obtained myoglobin-b-PNIPAM biohybrid diblock copolymer exhibits thermo-induced aggregation behavior in aqueous solution as a result of the presence of the thermoresponsive PNIPAM block, as revealed by temperature-dependent transmittance, dynamic laser light scattering measurements, transmission electron microscopy, and scanning electron microscopy. This work represents the first report of the preparation of responsive biohybrid DHBCs by the cofactor reconstitution process.

Purely salt-responsive micelle formation and inversion based on a novel schizophrenic sulfobetaine block copolymer: structure and kinetics of micellization.

A novel sulfobetaine block copolymer, poly(N-(morpholino)ethyl methacrylate)-b-poly(4-(2-sulfoethyl)-1-(4-vinylbenzyl)pyridinium betaine) (PMEMA-b-PSVBP), was synthesized via reversible addition-fragmentation chain transfer polymerization. In aqueous solution, PMEMA homopolymer becomes insoluble in the presence of Na2SO4 (>0.6 M), whereas PSVBP homopolymer molecularly dissolves in the presence of NaBr (>0.2 M). Thus, PMEMA-b-PSVBP diblock copolymer exhibits purely salt-responsive "schizophrenic" micellization behavior in aqueous solution, forming two types of micelles with invertible structures, that is, PMEMA-core and PSVBP-core micelles, depending on the concentrations and types of added salts (Scheme 1). The equilibrium structures of these two types of micelles were characterized via a combination of 1H NMR and laser light scattering (LLS). We further investigated the kinetics of salt-induced formation/dissociation of PMEMA-core and PSVBP-core micelles and the structural inversion between them employing the stopped-flow light scattering technique. In the presence of 0.5 M NaBr, the addition of Na2SO4 (>0.6 M) induces the formation of PMEMA-core micelles stabilized with well-solvated PSVBP coronas. Dilution-induced dissociation of PMEMA-core micelles into unimers occurs within the dead time of the stopped-flow apparatus (approximately 2-3 ms) when the final Na2SO4 concentration drops below 0.3 M, while salt-induced breakup of PSVBP-core micelles is considerably slower. The structural inversion from PMEMA-core to PSVBP-core micelles proceeds first with the dissociation of PMEMA-core micelles into unimers, followed by the formation of PSVBP-core micelles. On the other hand, structural inversion from PSVBP-core to PMEMA-core micelles exhibits different kinetic sequences. Immediately after the salt jump, PMEMA corona chains are rendered insoluble, and unstable PSVBP-core micelles undergo intermicellar fusion; this is accompanied and/or followed by the solvation of PSVBP cores and structural inversion into colloidally stable PMEMA-core micelles.