Homo- and hetero-metallophilicity-driven synthesis of highly emissive and stimuli-responsive Au(I)-Cu(I) double salts

2021 ◽  
Author(s):  
Ryosuke Kobayashi ◽  
Takashi Yumura ◽  
Hiroaki Imoto ◽  
Kensuke Naka
Keyword(s):  
Stimuli Responsive ◽  
Double Salts ◽  
Complex Salts ◽  
Tetranuclear Complexes

Complex salts composed of cationic Au(I) and anionic Cu(I) species were synthesized by utilizing bis(diphenylarsino)methane (dpam) and bis(diphenylphosphino)methane (dppm) ligands. The discrete tetranuclear complexes were obtained as crystals, and the...

Amino-functional polyethers: versatile, stimuli-responsive polymers

2020 ◽  
Vol 11 (24) ◽  
pp. 3940-3950 ◽  
Author(s):  
Patrick Verkoyen ◽  
Holger Frey
Keyword(s):  
Ring Opening ◽  
Review Article ◽  
Stimuli Responsive ◽  
New Class ◽  
Stimuli Responsive Polymers ◽  
Responsive Polymers

Amino-functional polyethers have emerged as a new class of “smart”, i.e. pH- and thermoresponsive materials. This review article summarizes the synthesis and applications of these materials, obtained from ring-opening of suitable epoxide monomers.

4D printing technology, modern era: A short review

2020 ◽  
pp. 92-111
Author(s):  
Khodadad Mostakim ◽  
Nahid Imtiaz Masuk ◽  
Md. Rakib Hasan ◽  
Md. Shafikul Islam
Keyword(s):  
Smart Materials ◽  
Computer Aided Design ◽  
Short Review ◽  
Stimuli Responsive ◽  
4D Printing ◽  
Space Applications ◽  
Printing Technology ◽  
Practical Applications ◽  
Biomedical Technologies ◽  
Novel Material

The advancement in 3D printing has led to the rapid growth of 4D printing technology. Adding time, as the fourth dimension, this technology ushered the potential of a massive evolution in fields of biomedical technologies, space applications, deployable structures, manufacturing industries, and so forth. This technology performs ingenious design, using smart materials to create advanced forms of the 3-D printed specimen. Improvements in Computer-aided design, additive manufacturing process, and material science engineering have ultimately favored the growth of 4-D printing innovation and revealed an effective method to gather complex 3-D structures. Contrast to all these developments, novel material is still a challenging sector. However, this short review illustrates the basic of 4D printing, summarizes the stimuli responsive materials properties, which have prominent role in the field of 4D technology. In addition, the practical applications are depicted and the potential prospect of this technology is put forward.

Synthesis of Smart Mesoporous Materials

2003 ◽  
Vol 775 ◽  
Author(s):  
G.V.Rama Rao ◽  
Qiang Fu ◽  
Linnea K. Ista ◽  
Huifang Xu ◽  
S. Balamurugan ◽  
...  
Keyword(s):  
Mesoporous Silica ◽  
Mesoporous Materials ◽  
Fluorescent Dyes ◽  
Thermo Gravimetric Analysis ◽  
Molecular Transport ◽  
Solute Diffusion ◽  
Gravimetric Analysis ◽  
Stimuli Responsive ◽  
Porous Network ◽  
Hybrid Mesoporous Materials

AbstractThis study details development of hybrid mesoporous materials in which molecular transport through mesopores can be precisely controlled and reversibly modulated. Mesoporous silica materials formed by surfactant templating were modified by surface initiated atom transfer radical polymerization of poly(N-isopropyl acrylamide) (PNIPAAm) a stimuli responsive polymer (SRP) within the porous network. Thermo gravimetric analysis and FTIR spectroscopy were used to confirm the presence of PNIPAAm on the silica surface. Nitrogen porosimetry, transmission electron microscopy and X-ray diffraction analyses confirmed that polymerization occurred uniformly within the porous network. Uptake and release of fluorescent dyes from the particles was monitored by spectrofluorimetry and scanning laser confocal microscopy. Results suggest that the presence of PNIPAAm, a SRP, in the porous network can be used to modulate the transport of aqueous solutes. At low temperature, (e.g., room temperature) the PNIPAAm is hydrated and extended and inhibits transport of analytes; at higher temperatures (e.g., 50°C) it is hydrophobic and is collapsed within the pore network, thus allowing solute diffusion into or out of the mesoporous silica. The transition form hydrophilic to hydrophobic state on polymer grafted mesoporous membranes was determined by contact angle measurements. This work has implications for the development of materials for the selective control of transport of molecular solutes in a variety of applications.

Smart Polymers and their Applications: A Review

2017 ◽  
Vol 8 (03) ◽  
Author(s):  
Gore S. A. ◽  
Gholve S. B. ◽  
Savalsure S. M. ◽  
Ghodake K. B. ◽  
Bhusnure O. G. ◽  
...  
Keyword(s):  
Oil Recovery ◽  
Water Soluble ◽  
Solution Temperature ◽  
Smart Polymers ◽  
Stimuli Responsive ◽  
Responsive Materials ◽  
Water Soluble Polymers ◽  
Commercial Applications ◽  
Stimuli Sensitive ◽  
External Stimuli

Smart polymers are materials that respond to small external stimuli. These are also referred as stimuli responsive materials or intelligent materials. Smart polymers that can exhibit stimuli-sensitive properties are becoming important in many commercial applications. These polymers can change shape, strength and pore size based on external factors such as temperature, pH and stress. The stimuli include salt, UV irradiation, temperature, pH, magnetic or electric field, ionic factors etc. Smart polymers are very promising applicants in drug delivery, tissue engineering, cell culture, gene carriers, textile engineering, oil recovery, radioactive wastage and protein purification. The study is focused on the entire features of smart polymers and their most recent and relevant applications. Water soluble polymers with tunable lower critical solution temperature (LCST) are of increasing interest for biological applications such as cell patterning, smart drug release, DNA sequencing etc.

Cobaloxime-Based Double Complex Salts as Efficient and Versatile Catalysts for the Light-Driven Hydrogen Evolution Reaction

2020 ◽  
Author(s):  
Elisabeth Hofmeister ◽  
Jisoo Woo ◽  
Tobias Ullrich ◽  
Lydia Petermann ◽  
Kevin Hanus ◽  
...  
Keyword(s):  
Hydrogen Evolution ◽  
Hydrogen Evolution Reaction ◽  
Systematic Study ◽  
Cobalt Complexes ◽  
Spectroscopic Studies ◽  
Double Complex ◽  
Double Complex Salts ◽  
Noble Metal Catalysts ◽  
Reduction Potentials ◽  
Complex Salts

Cobaloximes and their BF<sub>2</sub>-bridged analogues have emerged as promising non-noble metal catalysts for the photocatalytic hydrogen evolution reaction (HER). Herein we report the serendipitous discovery that double complex salts such as [Co(dmgh)<sub>2</sub>py<sub>2</sub>]<sup>+</sup>[Co(dmgBPh<sub>2</sub>)<sub>2</sub>Cl<sub>2</sub>]<sup>-</sup> can be obtained in good yields by treatment of commercially available [Co(dmgh)<sub>2</sub>pyCl] with triarylboranes. A systematic study on the use of such double complex salts and their single salts with simple counterions as photocatalysts revealed HER activities comparable or superior to existing cobaloxime catalysts and suggests ample opportunities for this compound class in catalyst/photosensitizer dyads and immobilized architectures. Preliminary electrochemical and spectroscopic studies indicate that one key advantage of these charged cobalt complexes is that the reduction potentials as well as the electrostatic interaction with charged photosensitizers can be tuned.

Revisiting the High-Pressure Properties of the Metal-Organic Frameworks ZIF-8 and ZIF-67

2020 ◽  
Author(s):  
Pia Vervoorts ◽  
Stefan Burger ◽  
Karina Hemmer ◽  
Gregor Kieslich
Keyword(s):  
High Pressure ◽  
State Of The Art ◽  
Energy Landscape ◽  
Structural Flexibility ◽  
Zeolitic Imidazolate Frameworks ◽  
Stimuli Responsive ◽  
X Ray Diffraction ◽  
X Ray ◽  
Open Questions ◽  
Metal Organic

The zeolitic imidazolate frameworks ZIF-8 and ZIF-67 harbour a series of fascinating stimuli responsive properties. Looking at their responsitivity to hydrostatic pressure as stimulus, open questions exist regarding the isotropic compression with non-penetrating pressure transmitting media. By applying a state-of-the-art high-pressure powder X-ray diffraction setup, we revisit the high-pressure behaviour of ZIF-8 and ZIF-67 up to <i>p</i> = 0.4 GPa in small pressure increments. We observe a drastic, reversible change of high-pressure powder X-ray diffraction data at <i>p</i> = 0.3 GPa, discovering large volume structural flexibility in ZIF-8 and ZIF-67. Our results imply a shallow underlying energy landscape in ZIF-8 and ZIF-67, an observation that might point at rich polymorphism of ZIF-8 and ZIF-67, similar to ZIF-4(Zn).<br>

Revisiting the High-Pressure Properties of the Metal-Organic Frameworks ZIF-8 and ZIF-67

2020 ◽  
Author(s):  
Pia Vervoorts ◽  
Stefan Burger ◽  
Karina Hemmer ◽  
Gregor Kieslich
Keyword(s):  
High Pressure ◽  
State Of The Art ◽  
Energy Landscape ◽  
Structural Flexibility ◽  
Zeolitic Imidazolate Frameworks ◽  
Stimuli Responsive ◽  
X Ray Diffraction ◽  
X Ray ◽  
Open Questions ◽  
Metal Organic

The zeolitic imidazolate frameworks ZIF-8 and ZIF-67 harbour a series of fascinating stimuli responsive properties. Looking at their responsitivity to hydrostatic pressure as stimulus, open questions exist regarding the isotropic compression with non-penetrating pressure transmitting media. By applying a state-of-the-art high-pressure powder X-ray diffraction setup, we revisit the high-pressure behaviour of ZIF-8 and ZIF-67 up to <i>p</i> = 0.4 GPa in small pressure increments. We observe a drastic, reversible change of high-pressure powder X-ray diffraction data at <i>p</i> = 0.3 GPa, discovering large volume structural flexibility in ZIF-8 and ZIF-67. Our results imply a shallow underlying energy landscape in ZIF-8 and ZIF-67, an observation that might point at rich polymorphism of ZIF-8 and ZIF-67, similar to ZIF-4(Zn).<br>

Carborane Guests for Cucurbit[7]uril Facilitate Strong Binding and on Demand Removal

2020 ◽  
Author(s):  
Anna Kataki-Anastasakou ◽  
Jonathan C. Axtell ◽  
Selena Hernandez ◽  
RafalM. Dziedzic ◽  
Gary J. Balaich ◽  
...  
Keyword(s):  
Free State ◽  
Stimuli Responsive ◽  
Additional Consideration ◽  
Boron Clusters ◽  
High Affinity ◽  
On Demand ◽  
Azide Anion ◽  
Strong Binding

High affinity guest have been reported for the macrocyclic host cucurbit[7]uril (CB[7]), enabling widespread applications, but preventing CB[7] materials from being returned to their guest-free state for reuse. Here we present polyhedral boron clusters (carboranes) as strongly-binding, yet easily removable, guests for CB[7]. Aided by a Pd-catalyzed coupling of an azide anion, we prepared boron-functionalized 9<i>-</i>amino and 9-ammonium modified <i>ortho-</i>carboranes that bind to CB[7] with a <i>K<sub>a</sub></i>=10<sup>10</sup> M<sup>-1</sup>. Upon treatment with base, the <i>ortho</i>-carboranes<i> </i>readily undergo deboronation to yield anionic <i>nido</i>-carborane, a poor guest of CB[7], facilitating recovery of guest-free CB[7]. We showcase the utility of the modified <i>ortho</i>-carborane guest by recycling a CB[7]-functionalized resin. With this report, we introduce stimuli-responsive decomplexation as an additional consideration in the design of high affinity host-guest complexes.

Multi-Stimuli-Responsive Mesoporous Membranes and Effect of Molecular Architecture on Thermo- and pH-Responsive Behavior of the grafted Block Copolymer brushes

2019 ◽  
Author(s):  
Yanchun Tang ◽  
Kohzo Ito ◽  
Hideaki Yokoyama
Keyword(s):  
Polymer Brushes ◽  
Diblock Copolymers ◽  
Neutron Reflectivity ◽  
Molecular Architecture ◽  
Stimuli Responsive ◽  
Responsive Polymer ◽  
The Matrix ◽  
Stable Part ◽  
Copolymer Brushes ◽  
Mesoporous Membranes

In this study, we prepared ultrafiltration membranes with a decoupled responses of filtration property to temperature and pH. The membrane preparation method was developed based on our previous work. We utilized methanol-supercritical carbon dioxide (methanol-scCO<sub>2</sub>) selective swelling method to introduce nanopores to block copolymers containing poly(diethylene glycol) methyl ether methacrylate (PMEO<sub>2</sub>MA), poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and polystyrene (PS) blocks. Formation of the mesoporous barrier layer with PS being the mechanically stable part of the matrix was driven by selective swelling of the PMEO<sub>2</sub>MA-b-PDMAEMA domains. Due to the selective swelling of PMEO<sub>2</sub>MA or PDMAEMA domains to introduce pores, the interior of the pores are covered with PMEO<sub>2</sub>MA or PDMAEMA blocks after pore formation. The PMEO<sub>2</sub>MA-b-PDMAEMA polymer brushes are naturally attached on the pore walls and worked as functional gates. PMEO<sub>2</sub>MA is a non-toxic, neutral thermo-responsive polymer with LCST at 26 ᴼC. PDMAEMA is a typical weak polyelectrolyte with pK<sub>a</sub> value at 7.0-7.5 and also a thermo-responsive polymer revealed a LCST of 20-80 °C in aqueous solution. Therefore, these membranes were expected to have multi dimensions as function of the combination of temperature and pH. Moreover, to understand the detail of the temperature and pH depended conformation transitions of PMEO<sub>2</sub>MA-b-PDMAEMA brushes, those diblock copolymers were end-tethered on flat substrates and analyzed via neutron reflectivity (NR).

Sensitive Mechanocontrolled Luminescence in Cross-Linked Polymer Films

2019 ◽  
Author(s):  
Ayumu Karimata ◽  
Pradnya Patil ◽  
Eugene Khaskin ◽  
Sébastien Lapointe ◽  
robert fayzullin ◽  
...  
Keyword(s):  
Mechanical Stress ◽  
Polymer Films ◽  
Soft Matter ◽  
Small Strain ◽  
Visual Methods ◽  
Photoluminescence Intensity ◽  
Stimuli Responsive ◽  
Responsive Materials ◽  
Highly Sensitive ◽  
Mechanical Stretching

Direct translation of mechanical force into changes in chemical behavior on a molecular level has important implication not only for the fundamental understanding of mechanochemical processes, but also for the development of new stimuli-responsive materials. In particular, detection of mechanical stress in polymers via non-destructive methods is important in order to prevent material failure and to study the mechanical properties of soft matter. Herein, we report that highly sensitive changes in photoluminescence intensity can be observed in response to the mechanical stretching of cross-linked polymer films when using stable, (pyridinophane)Cu-based dynamic mechanophores. Upon stretching, the luminescence intensity increases in a fast and reversible manner even at small strain (< 50%) and applied stress (< 0.1 MPa) values. Such sensitivity is unprecedented when compared to previously reported systems based on organic mechanophores. The system also allows for the detection of weak mechanical stress by spectroscopic measurements or by direct visual methods.<br>

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