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Organic and polymer fluorescent nanomaterials are a frontier research focus. Here in this work, a series of fluorinated zwitterionic random copolymers end‐attached with a quasi‐chromophoric group of pyrene or tetraphenylethylene (TPE) are well synthesized via atom transfer radical polymerization with activators regenerated by electron transfer (ARGET ATRP). Those random copolymers with total degree of polymerization 100 or 200 are able to produce fluorescent single‐chain nanoparticles (SCNPs) through intra‐chain self‐folding assembly with quite uniform diameters in the range of 10–20 nm as characterized by dynamic light scattering and transmission electron microscopy. By virtue of the segregation or confinement effect, both SCNPs functionalized with pyrene or TPE group are capable of emitting fluorescence, with pyrene tethered SCNPs exhibiting stronger fluorescence emission reaching the highest quantum yield ≈20%. Moreover, such kind of fluorescent SCNPs manifest low cytotoxicity and good cell imaging performance for Hela cells. The creation of fluorescent SCNPs through covalently attached one quasi‐chromophore to the end of one fluorinated zwitterionic random copolymer provides an alternative strategy for preparing polymeric luminescence nanomaterials, promisingly serving as a new type of fluorescent nanoprobes for biological imaging applications. [ABSTRACT FROM AUTHOR]

Liquid crystal (LC) dimers with well‐defined composition and structure arouse broad attentions for their exhibiting LC properties beyond conventional low molar mass mesogens and serving as fascinating model compounds for LC polymers. Here in this work, a series of LC dimers bridged with a phosphonic group have been synthesized through a facile free radical mediated addition reaction between hypophosphorous acid and vinyl terminated cyanobiphenyl mesogens with variant length alkyl spacers. In addition, two esterified derivatives and a group of mono‐addition homologues with a terminal phosphonic acid group have also been prepared for comparison study. All the newly synthesized compounds exhibit monotropic nematic (N) phase with typical schlieren textures except for the LC dimer with the longest eleven‐methylene spacer, which surprisingly shows twist‐bend nematic (NTB) phase directly from the isotropic state upon cooling. Moreover, the thermal transition properties such as the nematic‐isotropic transition temperatures and associated entropy changes of the series LC dimers display a modest odd‐even effect. Furthermore, both the LC dimers and the mono‐addition homologues in N phase are quite easy to achieve homeotropic alignment upon annealing thanks to the supramolecular interactions between the introduced phosphonic acid group and the hydroxylated glass surface. This work thus provides a novel synthesis strategy for a class of LC materials bridged with a phosphonic acid group prone to further functionalization, which may serve as promising vertical alignment agents and pave the way for developing a new kind of functionalized LC materials of NTB phase. [ABSTRACT FROM AUTHOR]

A systematical calculation is performed to explore the equilibrium phase behaviors of linear-dendritic triblock copolymer A B ( 2 g + 1 − 2 ) C 2 g + 1 ( g is the generation number of the block B, and G g is short for A B ( 2 g + 1 − 2 ) C 2 g + 1 ) from G1 to G5 by using self-consistent field theory. Eight phases are found: two-colored lamellar phase, three-colored lamellar phase, hexagonal phase, core shell hexagonal phase, tetragonal phase, core shell tetragonal phase, two interpenetrating tetragonal phase, lamellar phase with beads except disordered phase, by varying the interaction parameters between different blocks, the volume fractions of the blocks and the generation number. While investigating the effect of linear coil length on morphology, we find the longer linear length ( f A = 0.5) for G1, G2 can be beneficial to form the lamellar phase, however, tend to form hexagonal phase easily with generation number increasing from 3 to 5, and short linear length ( f A = 0.2) can be better for inducing hexagonal phase from G1 to G5. It becomes more and more difficult to phase separate with generation number increasing from 1 to 5 due to the architectural complexity. However, increasing the interaction parameters is helpful to facilitate phase separation. It is likely to offer new opportunity for designing nanomaterials and applying to template technology by finely controlling the dendron generations, length of the linear chain, interaction parameters of linear-dendritic triblock copolymers. [ABSTRACT FROM AUTHOR]

Overbased calcium sulfonate is oneof the largest commerciallyproduced nanomaterials; the phase transformation mechanism involvedin the key process of carbonation reaction for overbased detergentpreparation has not yet been fully understood. Following our previousinvestigation based on the heavy alkylbenzene sulfonate (HABS) surfactantof industrial byproduct, two commercial products with well-definedchemical compositions and structures, long-chain alkylbenzene sulfonate(LCABS) and comparative short-chain linear alkylbenzene sulfonate(SLABS), are employed in this study as model surfactants for furthermechanism study of this pivotal process by the combination of analyticaltechniques such as potentiometric titration, DLS, TEM, FTIR, and XRD.It has been demonstrated that amorphous calcium carbonate (ACC) isa prerequisite for the preserving and stabilization of the alkalinereserve, especially under thermal work environment. The phase transformationfrom ACC to crystalline vaterite polymorph rather than calcite hasbeen unambiguously confirmed as a universal mechanism for all thealkylbenzene sulfonate based systems. Furthermore, the length andnumber of alkyl tails of alkylbenzene sulfonate surfactants exhibita strong influence on characteristics of detergent products. The LCABSwith long-chain alkyl substituents or HABS with dialkyl substituentsplays an important role not only in inhibiting the agglomeration process,but also in protecting the metastable inorganic cores from fusionto avoid phase transformation. Such understanding should be of crucialimportance for guiding the preparation of overbased detergents andgreases. In addition, the study on the influence of the molar ratioof calcium oxide in the total alkaline calcium salts and the dosageof surfactant LCABS, promoter methanol, and catalyst anhydrous calciumchloride help to determine the suitable work window for detergentproduction, and moreover, the water content provides a handle forbetter understanding the reaction process and achieving good qualitycontrol for detergent manufacturing. [ABSTRACT FROM AUTHOR]

Liquid crystalline elastomers (LCEs) combine the ordering character of a liquid crystal and the elasticity of a polymer network. The development of fully light-driven LCE-based soft actuators with good reshapeability and recyclability is in high demand. In this work, we prepared SWCNT/LCE composite films through the introduction of allyl sulfide-based dynamic covalent crosslinks in the LCE matrix and the well-dispersed filler single-walled carbon nanotubes (SWCNTs) with a strong photothermal effect. The SWCNT/LCE composite films were facilely fabricated with reorientation and remouldable capabilities regulated by 405 nm visible light. The monodomain composite films demonstrated multimode actuations of contraction, bending, curling, stretching recovery, and even shape memory driven by 808 nm near-infrared (NIR) light. Moreover, the monodomain spiral ribbon or stretching flat strip and the original polydomain composite film can be readily transformed into each other, and reshaped through easily achievable fabrication conditions. Therefore, the well-prepared SWCNT/LCE composite films with exchangeable covalent crosslinks showed promise as candidates for the development of multimode NIR photomechanical soft actuators with fully light-driven controllability and good remouldability. [ABSTRACT FROM AUTHOR]

Abstract: In this paper we designed a kind of aggregation‐induced emission (AIE) chiral fluorescence emitters (R/S‐BINOL‐CN enantiomers) in the aggregate state. Chiral emissive nematic liquid crystals (N*‐LCs) prepared by doping this kind of AIE‐active R/S‐BINOL‐CN enantiomers into a common achiral nematic liquid crystal (N‐LC, E7) can self‐assemble as the regularly planar Grandjean texture leading to high luminescence dissymmetry factor (glum) of aggregation‐induced circularly polarized luminescence (AI‐CPL) signal up to 0.41, which can be attributed to dipolar interactions from polar cyano groups and π–π interactions between binaphthyl moiety of the dopant R/S‐BINOL‐CN and biphenyl group of the host molecules (E7). [ABSTRACT FROM AUTHOR]

Nanostructured materials of various shape and dimension have aroused intensive interests, among which copper(i) sulfide (Cu2S) nanomaterials are of particular prominence. In this work, various nanostructured Cu2S have been facilely prepared via solventless thermolysis, with well-controlled shape and dimension determined by and inherited from the layered structures of the azobenzene-containing single-source copper thiolate mesogenic precursors. The precursors with longer alkyl tails exhibit highly ordered layered liquid crystalline mesophases and retain persistent order up to temperatures beyond the clearing points. Under non-vacuum inert atmosphere or with further elevated temperature, large undulations of the constrained lamellar space result in significantly enhanced diffusion, migration and mass transfer, thus leading to the morphologies changing from one-dimensional (1D) ultrathin nanowires into thickened nanorods then to discrete 2D nanodisks. Based on a variety of modern techniques, especially in situ variable-temperature small angle X-ray scattering (SAXS), an extended universal “layered-precursor to lamellar-nanomaterial” (LPLM) mechanism has been proposed to account for the structural evolution of Cu2S nanomaterials. Our findings provide a novel pathway with clearer mechanism for well-controlled preparation of metal chalcogenides of various dimension and shape. In particular, the ultrathin Cu2S nanowires are anticipated to serve as fascinating semiconducting materials for various promising device applications. [ABSTRACT FROM AUTHOR]

ABSTRACT Liquid crystalline block copolymers (LCBCPs) are fascinating for their combining molecular level liquid crystalline orders and microphase separated multidomain morphologies. Here in this article, a series of PEG-containing side-chain discotic LCBCPs of PEG- b- Pm- n with variant spacer length m = 6, 10 and degree of polymerization (DP) of discotic LC block from n = 10 to 45, have been well-synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization. The RAFT process mediated by macromolecular chain transfer agent (macroCTA) shows remarkable monomer concentration dependence. The influence of the introduced PEG block on the nano-scale microphase-segregation and mesophase organization is closely related to the side-chain triphenylene (TP) discogens stacking mode dependent on the spacer length. Wherein, the PEG- b- P6- n series with a six-methylene spacer exhibit consistent microphase separation with slightly disturbed yet ordered columnar structures. While for PEG- b- P10- n series with a longer ten-methylene spacer, the columnar organization in the copolymers is even improved in contrast with the low order of randomly TP stacking in their corresponding homopolymers. This work offers a viable and inspiring pathway for controlled synthesis of block copolymers with bulky side groups, as well as enhances in-depth understanding of the hierarchical superstructure organization in discotic units involved complex block copolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2544-2553 [ABSTRACT FROM AUTHOR]

A dual-responsivesupramolecular network based on pillar[6]arene–ferroceniumredox-controllable recognition motifs in polymeric backbones is constructedwith a ferrocenium-functionalized copolymer and a pillar[6]arene copolymer,in which the first example of pillar[6]arene-functionalized copolymerwas synthesized through the reversible addition/fragmentation chain-transfercopolymerization of an acrylate-functionalized pillar[6]arene andmethyl acrylate. The resulting supramolecular network exhibits dramaticallyincreased viscosity than the non-cross-linked mixtures and demonstratesa gel-like behavior on macroscale with a transient-network behaviorrevealed by rheology study. Furthermore, the viscoelastic propertiesof such supramolecular network can be easily controlled by differentexternal stimuli including redox stimulus and competing host/guestreagents. [ABSTRACT FROM AUTHOR]

Photoresponsive materials (PRMs) have long been a hot topic and photo-modulated smart surface is very appealing. Particularly, liquid crystalline PRMs are able to amplify and stabilize photoinduced orientation thanks to their self-assembling and ordering characteristics. Herein, the first pillararene-based azobenzene liquid crystalline PRM with well-defined structure is presented, which can avoid the usually ill-defined composition drawback of polymer PRMs and prevent the severe H-aggregation from suppressing or even completely blocking photoresponse in simple azobenzene derivatives. The pillar[5]arene-based macrocyclic azobenzenes with variant length spacers show wide temperature range smectic liquid crystalline mesophases and excellent film-formation property. The tubular pillar[5]arene macrocyclic framework provides sufficient free volume for azobenzene moieties to achieve reversible photoisomerization and photoalignment; thus, their thin films demonstrate excellent light-triggered modulation of surface free energy, wettability, and even photoalignment-mediated orientation of an upper layer discotic liquid crystal columnar mesophase. Such pillararene-based azobenzene liquid crystals represent novel and promising PRMs with extensive fascinating applications. [ABSTRACT FROM AUTHOR]

A series of meta-substituted fatty acid octaester derivatives and their transition-metal complexes of meso- tetraphenyl porphyrins (TPP-8OOCR, with R=C n−1H2 n−1, n=8, 12, or 16) have been prepared through very simple synthesis protocols. The thermotropic phase behavior and the liquid crystalline (LC) organization structures of the synthesized porphyrin derivatives were systematically investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable-temperature small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) techniques. The shorter octanoic acid ester substituted porphyrin (C8-TPP) did not show liquid crystallinity and its metal porphyrins exhibited an uncommon columnar mesophase. The lauric acid octaester (C12-TPP) and the palmitic acid octaester (C16-TPP) series porphyrins generated hexagonal columnar mesophase Colh. Moreover, the metal porphyrins C12-TPPM and C16-TPPM with M=Zn, Cu, or Ni, exhibited well-organized Colh mesophases of broad LC temperature ranges increasing in the order of TPPNi

Liquid crystal nanoscience has aroused intensive interests mainly due to their unique and collective properties and a variety of potential applications. In this paper, gold nanoparticles (GNPs) coated with alkoxy azobenzene mesogenic thiol ligands of different length polymethylene spacer and linear alkyl thiol co-ligands have been prepared. The thermal properties, phase behavior of thus obtained hybrid GNPs and photophysical properties of their solid-state films have been investigated by differential scanning calorimetry (DSC), variable-temperature small and wide angle X-ray scattering (SAXS/WAXS) and UV–vis spectroscopy. The hybrid GNPs exclusively passivated with azobenzene mesogenic ligands showed lamellar structure while those with mixed ligands exhibited hexagonal columnar superstructure, and the latter complex hybrid GNPs exhibited noticeably improved thermolysis resistance. Moreover, it is very interesting that the solid-state films of the hybrid GNPs displayed reversible photoresponse owing to the trans – cis transformation of azobenzene mesogenic ligands, and compared with the hybrid GNPs coated with mesogenic ligands only, those with mixed ligands exhibited faster photoisomerization rate upon alternate UV and visible light irradiation, which may have some promising applications. [ABSTRACT FROM AUTHOR]

Abstract: In this paper, based on the synthesis of precursor linear-dendritic block copolymers (LDBCs) with a linear poly(ethylene glycol) (PEG) block of molecular weight around 2000 and dendritic polyamidoamine (PAMAM) segments of generation G0 to G3, a series of azobenzene-containing amphiphilic LDBCs mPEG-dendr[PAMAM-(AZO) n ] (n = 2, 4, 8, 16) have been successfully prepared in moderate yields 45–60%, through complete Michael addition between the peripheral amine groups of dendritic segment and the reactive azobenzene acrylate mesogen units bearing octyloxy tails and flexible decylmethylene spacers. The purified copolymers have been characterized and confirmed by NMR, FT-IR, MALDI-TOF MS, and GPC showing narrow molecular weight distribution in the range 1.09–1.20. A generation-dependent polymeric micellar aggregation behavior of thus obtained amphiphilic LDBCs from nanofibers of uniform diameter around 20 nm to nanospheres/oval sheets, vesicles, and porous large compound micelles (LCMs) of micrometer size has been demonstrated in selective solvent mixture of dioxane/water. Furthermore, photoisomerization transformation of these azobenzene-containing LDBCs and their kinetics of reversible trans-cis-trans photochemical transitions in THF solution have also been investigated, the measured trans-cis photoisomerization rate constant 0.0240 s−1 for G3 copolymer is twice of the 0.0127 s−1 determined for the precursor azobenzene compound, manifesting a kind of promising photoresponsive copolymer materials. [Copyright &y& Elsevier]

Abstract: The preparation and application of overbased nanodetergents with excess alkaline calcium carbonate is a good example of nanotechnology in practice. The phase transformation of calcium carbonate is of extensive concern since CaCO3 serves both as an important industrial filling material and as the most abundant biomineral in nature. Industrially valuable overbased nanodetergents have been prepared based on calcium salts of heavy alkylbenzene sulfonate by a one-step process under ambient pressure, the carbonation reaction has been monitored by the instantaneous temperature changes and total base number (TBN). A number of analytical techniques such as TGA, DLS, SLS, TEM, FTIR, and XRD have been utilized to explore the carbonation reaction process and phase transformation mechanism of calcium carbonate. An enhanced understanding on the phase transformation of calcium carbonate involved in calcium sulfonate nanodetergents has been achieved and it has been unambiguously demonstrated that amorphous calcium carbonate (ACC) transforms into the vaterite polymorph rather than calcite, which would be of crucial importance for the preparation and quality control of lubricant additives and greases. Our results also show that a certain amount of residual Ca(OH)2 prevents the phase transformation from ACC to crystalline polymorphs. Moreover, a vaterite nanodetergent has been prepared for the first time with low viscosity, high base number, and uniform particle size, nevertheless a notable improvement on its thermal stability is required for potential applications. [Copyright &y& Elsevier]

Abstract: A series of carboxylic acid functionalized hybrid linear-dendritic block copolymers (LDBCs) derived from methoxy poly(ethylene glycol) (MPEG) and variant generation dendrons from 2,2-bis(hydroxymethyl) propionic acid were synthesized and employed as CaCO3 crystallization growth modifiers. Mainly spherical vaterite particles of gradually reduced sizes were produced with the increase of the polymer additive concentration and/or the dendron segment generation number, while the incorporated polymer organic components in the particles increased for the promoted binding efficiency and ever enhanced adsorption ability. A higher mineralization temperature resulted in significantly larger particle size and partly calcite formation. Under the same molar concentration of carboxylic acid, the same size level particles were obtained which manifested the crucial role of the functional group, meanwhile, the slight decrease of the spherical vaterite diameters with increasing generation number and especially the formation of particular pine-cone shaped calcite crystals also revealed the significant effect of the architectural structure of variant generations and some special characters of the hybrid LDBC structures. [Copyright &y& Elsevier]

Azobenzene-containing polymers (azopolymers) are a kind of intensively explored fascinating photoresponsive materials, liquid crystalline (LC) azopolymers with excellent film-forming, ordered structure and self-repairing capability are endowed with enhanced photoisomerization and photoalignment characteristics capable of developing into photo-modulated smart surfaces. Here in this work, two azobenzene side-chain LC polynorbornenes of PNB-Azo-n with different DP of n = 50 and 100 have been well synthesized through ring-opening metathesis polymerization (ROMP). The polynorbornene backbone of less flexibility with larger spacing between adjacent azobenzene side groups endows stronger inhibition for H-aggregation and better photoresponsiveness. The high-DP azopolynorbornene of PNB-Azo-100 thin films well behave as command surface for the upper layer nematic LC molecules thanks to their better performance in photoisomerization and photoalignment, together with their good compatibility and dissolution-resistance to the nematic LC mixture of E7. Selectively optically readable LC graphic writings at normal size through various photomasks have been demonstrated, and higher grid resolution up to sub-ten micrometer with a digital micromirror device (DMD) based dynamic photopatterning system has been achieved. Therefore, such kind of LC azopolynorbornenes demonstrate promising applications in LC photoalignment system and photoresponsive devices for potential anti-forgery document security and smart card technology. Image 1 • Synthesis of LC polynorbornenes with side-chain azobenzene via ROMP (DP 50, 100). • Semi-rigid polynorbornene inhibiting H-aggregation and promoting photoresponse. • Photoaligned high-DP azopolymer thin films as command surface for LC E7 patterning. • High grid resolution up to sub-ten-micrometer from DMD based dynamic photopatterning. • LC photoalignment and photoresponsive systems promising for anti-forgery application. [ABSTRACT FROM AUTHOR]