Influence of VO2 based structures and smart coatings on weather resistance for boosting the thermochromic properties of smart window applications

Vanadium dioxide (VO₂)-based energy-saving smart films or coatings aroused great interest in scientific research and industry due to the reversible crystalline structural transition of VO₂ from the monoclinic to tetragonal phase around room temperature, which can induce significant changes in transmittance and reflectance in the infrared (IR) range. However, there are still some obstacles for commercial application of VO₂-based films or coatings in our daily life, such as the high phase transition temperature (68 °C), low luminous transmittance, solar modulation ability, and poor environmental stability. Particularly, due to its active nature chemically, VO₂ is prone to gradual oxidation, causing deterioration of optical properties during very long life span of windows. In this review, the recent progress in enhancing the thermochromic properties of VO₂-hybrid materials especially based on environmental stability has been summarized for the first time in terms of structural modifications such as core–shell structures for nanoparticles and nanorods and thin-films with single layer, layer-by-layer, and sandwich-like structures due to their excellent results for improving environmental stability. Moreover, future development trends have also been presented to promote the goal of commercial production of VO₂ smart coatings.

VO₂ based energy saving smart coatings are of great interest in research and industry due to the reversible crystalline structural transition of VO₂ which can induce significant transmittance and reflectance changes in the infrared range.     

3D mesoporous structure assembled from monoclinic M-phase VO2 nanoflakes with enhanced thermochromic performance

Monoclinic M-phase VO₂ is a promising candidate for thermochromic materials due to its abrupt change in the near infrared (NIR) transmittance along with the metal-to-insulator transition (MIT) at a critical temperature ∼68 °C. However, low luminous transmittance (T_lum), poor solar energy modulation ability (ΔT_sol), and high phase transition temperature (T_c) can limit the application of VO₂ for smart windows. To overcome these limitations, 3D mesoporous structure can be employed in VO₂ films. Herein, 3D mesoporous structures assembled from monoclinic M-phase VO₂ nanoflakes with a pore size of about 2–10 nm were synthesized by a hydrothermal method using Ensete ventricosum fiber (EF) as a template followed by calcination at 450 °C. The prepared film exhibited excellent thermochromic performance with balanced T_lum = 67.3%, ΔT_sol = 12.5%, and lowering T_c to 63.15 °C. This is because the 3D mesoporous structure can offer the uniform dispersion of VO₂ nanoflakes in the film to enhance T_lum, ensure sufficient VO₂ nanoflakes in the film for high ΔT_sol and lower T_c. Therefore, this work can provide a green approach to synthesize 3D mesoporous structures assembled from monoclinic M-phase VO₂ nanoflakes and promote their application in smart windows.

Herein, 3D mesoporous structures assembled from monoclinic M-phase VO₂ nanoflakes were successfully synthesized for enhanced thermochromic performance.     

Hybrid hollow silica particles: synthesis and comparison of properties with pristine particles

In the past decade, interest in hollow silica particles has grown tremendously because of their applications in diverse fields such as thermal insulation, drug delivery, battery cathodes, catalysis, and functional coatings. Herein, we demonstrate a strategy to synthesize hybrid hollow silica particles having shells made of either polymer-silica or carbon–silica. Hybrid shells were characterized using electron microscopy. The effect of hybrid shell type on particle properties such as thermal and moisture absorption was also investigated.

Hybrid hollow silica particles, which show different properties compared to their pristine counterparts, have been synthesized.

In the past decade, hollow particles have attracted a great deal of interest because of their unique properties (e.g., high surface area, low density, and encapsulated cavity) compared with their dense counterparts. Hollow particles of several materials, including polymers, silica, titania, carbon, and zinc oxide have been reported.^1–9 Among these, hollow silica particles have attracted great attention from scientists because of their low material cost; well understood chemistry; and potential applications in widespread areas such as thermal insulation, drug delivery, energy storage, phase change encapsulation, catalysis, and superhydrophobic coatings.^10–18 Hollow silica particles can be synthesized using various approaches, such as by employing polymer micelles, immiscible solvent emulsions, inorganic or polymer (e.g., polystyrene) particles, and bacterial or virus cells as templates; by etching solid silica particles; or by spray pyrolysis.^19–25 Polymer micelles or emulsions provide very small particles, but making larger particles and tuning particle size are challenges in this approach. Similarly, the obtained particles typically fuse with one another, and achieving individually separated particles is a challenging task. Inorganic template etching is a time-consuming process, and in many cases, rudiments of inorganic templates remain in the hollow particle cavity if etching is incomplete. Unconventional techniques such as spray drying are inexpensive, but particle size control is difficult. The use of polystyrene particles as templates is attracting much attention because polystyrene particles can be synthesized at low cost with controlled sizes. Polystyrene particle-based synthesis of hollow silica particles involves three steps: (1) synthesis of polystyrene particles, (2) deposition of silica shells on polystyrene particles, and (3) removal of the polystyrene core by burning or dissolving to obtain hollow silica particles.Synthesis of hollow silica particles having shells made of silica alone (pristine hollow particles) is well reported. Some previous efforts have been made to attach surfactant molecules to the surfaces of mesoporous (not hollow) hollow particles. For example, Zhang et al.²⁶ first made porous silica particles by using cetyltrimethylammonium bromide (CTAB) as the template. In the next step, sodium carbonate-based etching was used to create cavities inside the porous particles, thus leading to porous-hollow silica particles. Then, 3-mercaptopropyl-trimethoxysilane (MPTS) was used to attach thiol-group ending surfactants to the surface. Similarly, Ribeiro et al.²⁷ coated solid silica particles with poly(butyl methacrylate) to make superhydrophobic coatings. Similarly, hollow polymer particles have been reported by depositing a polymer layer around solid silica particles, followed by etching the silica core. The same hollow polymer particles were also converted to hollow carbon particles by pyrolysis of polymer.^28,31 However, in this work, shell is made of a single material – polymer or carbon.^28,31 To the best of our knowledge, no work has reported hollow particles with a hybrid shell – shell made of two layers of different materials (inner layer: silica and outer layer: polymer or carbon). Additionally, no previous report has investigated the effect of such an additional layer on the properties of the hollow silica particles. We envisage that such additional layers can change the properties, such as stability against moisture and thermal conductivity, of pristine hollow silica particles.We report the synthesis of hybrid hollow silica particles, characterize these hybrid particles, and compare their properties with the properties of pristine hollow silica particles. Our investigations reveal that by changing the coating material, several intrinsic properties of hollow silica particles can be modified.Hollow silica particles were synthesized by modifying previously reported strategies based on the use of polystyrene particles (synthesis details in ESI S1^†) as a template.¹ For synthesizing hollow silica particles, in a typical experiment, 0.25 g of polystyrene particles were mixed into 100 mL of ethanol/water (ethanol 80 mL, water 20 mL). A suitable amount of tetraethyl orthosilicate was added to make complete shells around the polystyrene particles. To increase the TEOS hydrolysis, 28–30% of ammonium hydroxide was used as a catalyst. Fig. 1a depicts a schematic of hollow particle formation. Fig. 1b shows an SEM image of the polystyrene particles used as templates, and Fig. 1c shows a transmission electron microscope (TEM) image of polystyrene core-silica shell particles. Fig. 1d shows an SEM and Fig. 1e shows a high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image of hollow silica particles obtained after burning the polystyrene core by keeping the sample at 550 °C for 4 h.Open in a separate windowFig. 1(a) Schematic showing synthesis of hollow silica particles. (b) SEM image of polystyrene particles. (c) TEM image of polystyrene core coated with silica shell (core–shell). (d) SEM and (e) HAADF-STEM image of hollow silica particles.There are several polymers that can be used to form coatings on silica.^28–31 Among these, the use of resorcinol is well studied.^28,31 In a typical experiment, 0.25 g of hollow particles (0.25 g) were mixed in water (100 mL). Ammonium hydroxide (28–30%, 500 μL), resorcinol (0.1 g), and formaldehyde (150 μL) were added to this reaction mixture. The reaction was allowed to proceed overnight (≈16 h) to completion. Expected mechanism for polymer coating formation is explained in ESI S3.^†Fig. 2a shows a schematic of the process used to make a polymer (polyresorcinol) coating on a silica shell. Fig. 2b shows low-magnification (i) and high-magnification (ii) TEM images of polymer-coated hollow silica particles. The polymer coating can be clearly seen (light in contrast) around the silica shell (dense in contrast). Though TEM imaging confirmed the presence of a polymer coating on the surface of the silica, to further confirm the formation of the coating, we applied electron energy loss spectroscopy (EELS). Energy dispersive X-ray (EDX) imaging is easy to use and is a readily available technique for analysing materials; however, EDX has a very low sensitivity to low-atomic-weight elements such as carbon and oxygen. Therefore, it was not a suitable technique for confirming the polymer presence. In contrast, EELS is known for its high sensitivity to low-atomic-weight elements (e.g., carbon and oxygen). Fig. 2c shows scanning HAADF-STEM (i) and EELS (ii) images of the polymer-silica hybrid shell. The coating was quite uniform, with some thicker areas on the free surfaces of particles and some thinner areas at the joints in aggregated particles (ESI S2^†). Therefore, if individual uniform coatings are required, the original hollow particle samples must be properly disaggregated.Open in a separate windowFig. 2(a) Schematic showing the polymer coating process. (b) TEM images of polymer-coated silica particles. (c) HAADF-TEM (i) and EELS S map (ii) showing polymer and silica layers of hybrid shell.Additionally, we demonstrated the formation of hybrid hollow silica particles with outer layers made of carbon and inner layers made of silica. To form a carbon layer on a silica shell, the initial polymer coating was sintered in an inert atmosphere (argon) at 550 °C for 4 h. Fig. 3a shows a schematic of polymer layer conversion to a carbon layer. Under these conditions, polymer converts into carbon instead of being completely oxidized into carbon dioxide and water. After heating under an inert atmosphere, brown polymer-coated particles changed to black carbon-coated particles. Separate carbon (outer) and silica (inner) layers were observed in TEM (Fig. 3b) and EELS images (Fig. 3c).Open in a separate windowFig. 3(a) Schematic showing conversion of polymer coating to carbon coating. (b) TEM images of carbon-coated particles. (c) EELS element map showing the carbon layer on a silica shell.In addition to making hybrid shell hollow particles, we investigated whether the coating affected the properties (e.g., thermal conductivity and moisture absorption) of the pristine hollow silica particles. We measured the thermal conductivity of pristine, polymer-coated, and carbon-coated particles. The results showed that polymer-coated particles had the lowest thermal conductivity and carbon-coated particles had the highest thermal conductivity of the three types. The Fig. 4 plot shows the thermal conductivities of the three types of particles, and respective insets show photos of corresponding particle samples. More details of the measurements are provided in ESI-S3.^† As expected, the polymer silica particles had lower thermal conductivity (0.022 ± 0.002 W m⁻¹ K⁻¹) than pristine hollow particles (0.024 ± 0.002 W m⁻¹ K⁻¹), whereas carbon-coated particles had higher thermal conductivity (0.036 ± 0.004 W m⁻¹ K⁻¹) than both the pristine and the polymer-coated particles. This information provides a new tool to achieve or tune thermal properties of hollow silica particles as desired. For example, for high-thermal-insulation materials, polymer-coated particles are ideal; whereas carbon-coated particles are more suitable where somewhat higher thermal conductivity, but hydrophobicity is required. We were expecting that a carbon coating will increase electrical conductivity of hollow particles, however, we observed that even carbon coated particles had an electrical resistance in the megaOhm range, i.e., behave as electrically insulators (measurement details in ESI S3^†). Although the thermal conductivity of polymer-coated or carbon-coated hollow silica particles can be further modified by modifying the coating thickness, in the present work, we did not investigate the effect of coating thickness on thermal conductivity in detail. We expect the thinner the coating, the lower the thermal conductivity will be. We observed in both the polymer- and carbon-coated particles that the coatings were not uniform. Some particles had thick and others thin coatings, indicating that coating nucleation was not uniform, and the coatings may have begun forming earlier on some particles than on others. We observed that carbon–silica hollow particles are hydrophobic in nature, staying afloat on water for several hours (ESI Fig. S4^†) and mixing in water only after vigorous stirring. It appears that, with stirring, water molecules enter the hollow particle cavities through the pores present in the carbon and silica shells and wet the inner parts of the cavities, thus causing the particles to mix in water.Open in a separate windowFig. 4Effect of different types of coatings on the thermal conductivity of hollow silica particles. Insets show the photos of respective particles.Additionally, we compared the moisture absorption properties of pristine hollow silica particles with those of polymer- and carbon-coated hollow silica particles (Fig. 5). Moisture absorption/desorption experiments were performed using a dual vapor gravimetric sorption analyser. We observed that polymer-coated particles absorbed less humidity compared with pristine particles at the same relative humidity. However, both materials had similar isotherm profiles in which the moisture adsorption capacity increased at relatively higher moisture concentrations. The carbon-coated particles, on the other hand, showed a completely different isotherm behaviour: an immediate increase in adsorption capacity was observed between 30% and 50% relative humidity. A sharp increase in moisture absorption at higher relative humidity (between 30–50%) appears due to the entry of water vapors inside the particles because of porous nature of carbon layer. Similar shape of isotherms for pristine and polymer coated particles indicates that both of these particles had similar surface groups (–OH), but lower absorption in polymer coated particles compared to pristine particles indicates that its surface has a small number of moisture absorbing groups (–OH) compared to pristine particles. The hysteresis between adsorption and desorption isotherms was found to be minimal, indicating that the samples had similar performance for adsorption or desorption process. We expect this information to be helpful for applications such as developing water-stable coatings or insulation materials by using hollow silica particles.Open in a separate windowFig. 5Effect on moisture adsorption and desorption process. Plot showing behaviour of hollow particles under different relative humidity conditions for pristine and coated samples.     

First cycloruthenation of 2-alkenylpyridines: synthesis,characterization and properties

Several cyclometalated ruthenium complexes 1–5 with 2-alkenylpyridines as C,N-chelating ligands were synthesized and then characterized by NMR, MS, IR and UV-Vis spectra. According to the single crystal of complex 2, it is evident that carbon from vinyl group is successfully bonded to Ru(ii) center. Moreover, the Ru–N bond trans to the Ru–C bond is elongated (2.127(5) Å), which is consistent with the strong trans effect of the carbon atom compared to that of the nitrogen atom. With different electron-donating groups linked to vinyl, these complexes exhibited regular changes in MLCT absorption bands, which were identified by UV-Vis and CV spectra in combination with DFT and TD-DFT. Interestingly, protonated intermediate species of these complexes in acidic solutions were tracked by the absorption changes and MS spectra, which displayed a possible protonation process of these complexes with the cleavage of Ru–C σ bonds.

Five cycloruthenated 2-(alkenyl)pyridine derivatives and their protonated species without the release of cyclometalating ligands were first captured.     

Influence of low Bi contents on phase transformation properties of VO2 studied in a VO2:Bi thin film library

A thin-film materials library in the system V–Bi–O was fabricated by reactive co-sputtering. The composition of Bi relative to V was determined by Rutherford backscattering spectroscopy, ranging from 0.06 to 0.84 at% along the library. The VO₂ phase M1 was detected by X-ray diffraction over the whole library, however a second phase was observed in the microstructure of films with Bi contents > 0.29 at%. The second phase was determined by electron diffraction to be BiVO₄, which suggests that the solubility limit of Bi in VO₂ is only ∼0.29 at%. For Bi contents from 0.08 to 0.29 at%, the phase transformation temperatures of VO₂:Bi increase from 74.7 to 76.4 °C by 8 K per at% Bi. With X-ray photoemission spectroscopy, the oxidation state of Bi was determined to be 3+. The V⁵⁺/V⁴⁺ ratio increases with increasing Bi content from 0.10 to 0.84 at%. The similarly increasing tendency of the V⁵⁺/V⁴⁺ ratio and T_c with Bi content suggests that although the ionic radius of Bi³⁺ is much larger than that of V⁴⁺, the charge doping effect and the resulting V⁵⁺ are more prominent in regulating the phase transformation behavior of Bi-doped VO₂.

A VO₂:Bi thin-film library was fabricated by reactive co-sputtering. The phase transformation temperature of VO₂:Bi increases from 74.7 to 76.4 °C by 8 K/at% Bi in the range of 0.08–0.29 at% suggesting an effect of charge doping from Bi³⁺.     

Alterations in VO2max and the VO2 plateau with manipulation of sampling interval

Background: The most accepted criterion for confirming attainment of VO₂max is a plateau in oxygen consumption (VO₂) at VO₂max, but its incidence varies. Aims: To compare VO₂max and VO₂ plateau incidence across various sampling intervals, and to examine predictors of the change in VO₂ (ΔVO₂) at VO₂max. Methods: Sedentary, recreationally‐active, and endurance‐trained subjects (n = 108, age = 24·2 ± 6·2 year) completed incremental exercise on the treadmill or cycle ergometer. Gas exchange data were obtained breath‐by‐breath and time‐averaged every 15, 30, and 60 s. VO₂max attainment was verified with the Taylor et al. (1955) criterion (ΔVO₂ at VO₂max ≤2·1 ml kg^?1 min^?1). Multiple regression was used to examine predictors of ΔVO₂ at VO₂max. Results: VO₂ plateau incidence was higher using breath‐by‐breath (81%) and 15 (91%) and 30 s time averaging (89%) versus 60 s averaging (59%). Compared to 60 s averaging, VO₂max was significantly higher (P<0·05) when data were obtained breath‐by‐breath and with 15 and 30 s time‐averaging compared to 60 s sampling. VO₂max was not related to VO₂ plateau incidence. Respiratory rate was a significant predictor of ΔVO₂ at VO₂max in endurance‐trained subjects. Conclusion: More frequent data acquisition revealed higher VO₂max and incidence of the VO₂ plateau compared to 60 s time averaging. Secondary criteria to verify VO₂max attainment should not be used, as they do not discern between subjects who do and do not reveal a plateau in VO₂ at VO₂max.     

Coated silver nanoparticles: synthesis,cytotoxicity, and optical properties

Coated silver nanoparticles (AgNPs) have recently become a topic of interest due to the fact that they have several applications such as in electronic, antimicrobial, industrial, optical, and medical fields as biosensors and drug delivery systems. However, the use of AgNPs in medical fields remains somewhat limited due to their probable cytotoxic effect. Researchers have succeeded in reducing the toxicity of silver particles by coating them with different substances. Generally, the coating of AgNPs leads to change in their properties depending on the type of the coating material as well as the layer thickness. This review covers the state-of-the-art technologies behind (a) the synthesis of coated AgNPs including coating methods and coating materials, (b) the cytotoxicity of coated AgNPs and (c) the optical properties of coated AgNPs.

Coated silver nanoparticles (AgNPs) have recently become a topic of interest due to the fact that they have several applications such as in electronic, antimicrobial, industrial, optical, and medical fields as biosensors and drug delivery systems.     

Atomic and electronic structures of charge-doping VO2: first-principles calculations

The atomic and electronic structures of charge-doping VO₂ are investigated by using first-principles calculations. Hole doping is more conducive to stabilizing the structure of VO₂ than electron doping. The controllable phase transition temperature is coupled with changes in atomic and electronic structures. With the increase in hole density, the V–V chains and twisting angle experience a dramatic change, and the band gap (0.69–0 eV) is rapidly reduced due to orbital switching between the d_x²−y² and d_z²/d_yz orbitals. However, as the electron density increases, the band gap (0.69–0.502 eV) narrows slightly, while the V–O bond lengths significantly increase. The current results provide up a variable way to tune the VO₂ phase transition temperature through charge-doping.

The controllable phase transition temperature in charge doping VO₂ is coupled with changes in the atomic and electronic structures. The current results provide a variable way to tune the VO₂ phase transition temperature through charge doping.     

Schwertmannite: occurrence,properties, synthesis and application in environmental remediation

Schwertmannite is a typical iron-derived mineral, which was originally discovered in acid mine drainings and subsequently synthesized in the laboratory. Increasingly, it is seen as having considerable potential as an adsorbent material, which could be used for environmental remediation (such as the treatment/remediation of arsenic, chromium, antimony, fluoride, and organic contaminants). This study reviews current developments, mainly in the preparation, structure, and water treatment of Schwertmannite. Several key issues are discussed in detail, such as synthetic strategy, the structure–property relationships, potential environmental applications, and related mechanisms. Soil remediation by schwertmannite is compared to water treatment, and its application is further evaluated. Finally, the methodologies for water treatment and soil remediation using schwertmannite are also taken into consideration from an environmental point of view.

Schwertmannite is a typical iron-derived mineral, which was originally discovered in acid mine drainings and subsequently synthesized in the laboratory.     

New chalcone derivatives: synthesis,antiviral activity and mechanism of action

In this work, twenty-eight chalcone derivatives containing a purine (sulfur) ether moiety were synthesized and their antiviral activities were evaluated. Biological results showed that compound 5d exhibited outstanding inactive activity against tobacco mosaic virus (TMV) in vivo (EC₅₀ = 65.8 μg mL⁻¹), which is significantly superior to that of ribavirin (EC₅₀ = 154.3 μg mL⁻¹). Transmission electron microscopy indicated that compound 5d can break the integrity of TMV particles. The results of microscale thermophoresis, fluorescence titration and molecular docking showed that compound 5d had stronger combining affinity (K_a = 1.02 ×10⁵ L mol⁻¹, K_d = 13.4 μmol L⁻¹) with TMV coat protein (TMV-CP), which is due to the formation of five hydrogen bonds between compound 5d and the amino-acid residues of TMV-CP. These findings revealed that compound 5d can effectively inhibit the infective ability of TMV. This work provides inspiration and reference for the discovery of new antiviral agents.

The chalcone derivatives containing a purine (sulfur) ether moiety were synthesized. The antiviral mechanism suggested that the antiviral activity of compound 5d may depend on its stronger binding affinity with TMV-CP.     

Chemical and thermal properties of VO2 mechanochemically derived from V2O5 by co-milling with paraffin wax

A novel mechanochemical reduction process of V₂O₅ to VO₂ was established by milling with paraffin wax (PW, average molecular weight 254–646), serving as a reductant. The reduction progressed with increasing milling time and mass ratio V₂O₅ : PW (MRVP). The mechanochemically derived VO₂ became phase pure after milling for 3 h with an MRVP of 30 : 1 and exhibited a reversible polymorphic transformation between tetragonal and monoclinic phases at around 53–60 °C and 67–79 °C during heating and cooling, respectively. The latent heat was above 20 J g⁻¹ in both processes, being superior to those of commercial VO₂. Doping of starting V₂O₅ with Cr, Mo or W at 1 at% in the form of oxide did not increase the latent heat. This is another difference from the conventionally prepared doped VO₂. These anomalous heat storage properties of mechanochemically derived VO₂ were discussed mainly on the basis of X-ray photoelectron spectroscopy V_2p3/2 peaks combined with ion etching. The observed relatively high heat storage capacity of undoped VO₂ is primarily ascribed to the abundance of V⁴⁺ ionic states introduced during milling with PW, which were stabilized with simultaneously introduced structural degradation throughout the entire particles. The possible role of a remaining small amount of PW was also discussed.

Reduction of V₂O₅via a mechano-chemical route brings about unique electronic states of vanadium. The resulting VO₂ exhibits high latent heat storage during heating (a) and cooling (b).     

Anisotropic quasi-one-dimensional layered transition-metal trichalcogenides: synthesis,properties and applications

The strong in-plane anisotropy and quasi-1D electronic structures of transition-metal trichalcogenides (MX₃; M = group IV or V transition metal; X = S, Se, or Te) have pronounced influence on moulding the properties of MX₃ materials. In particular, the infinite trigonal MX₆ prismatic chains running parallel to the b-axis are responsible for the manifestation of anisotropy in these materials. Several marvellous properties, such as inherent electronic, optical, electrical, magnetic, superconductivity, and charge density wave (CDW) transport properties, make transition-metal trichalcogenides (TMTCs) stand out from other 2D materials in the fields of nanoscience and materials science. In addition, with the assistance of pressure, temperature, and tensile strain, these materials and their exceptional properties can be tuned to a superior extent. The robust anisotropy and incommensurable properties make the MX₃ family fit for accomplishing quite a lot of compelling applications in the areas of field effect transistors (FETs), solar and fuel cells, lithium-ion batteries, thermoelectricity, etc. In this review article, a precise audit of the distinctive crystal structures, static and dynamic properties, efficacious synthesis schemes, and enthralling applications of quasi-1D MX₃ materials is made.

The strong in-plane anisotropy and quasi-1D electronic structures of transition-metal trichalcogenides (MX₃; M = group IV or V transition metal; X = S, Se, or Te) have pronounced influence on moulding the properties of MX₃ materials.     

Schweinfurthins A–Q: isolation,synthesis, and biochemical properties

Stilbene analogues have shown remarkable structural diversity constituting simple or tangled structures, which have attracted the synthetic as well as the medicinal chemistry communities. Schweinfurthins are a family of prenylated/geranylated/farnesylated stilbenes that are isolated from an African plant belonging to the Macaranga species. These compounds have displayed potency towards central nervous system, renal and breast cancer cell lines. Specifically, these compounds have been found to be potent and selective inhibitors of cell growth in the National Cancer Institute''s 60 cell-line screen. In this review article, we described the isolation, synthesis, and biochemical properties of schweinfurthins.

An overview of the isolation, synthesis, and biochemical properties of the stilbene-based natural products schweinfurthins A–Q (1999–2017).     

A julolidine-fused anthracene derivative: synthesis,photophysical properties,and oxidative dimerization

We describe the synthesis and characterization of a julolidine-fused anthracene derivative J-A, which exhibits a maximum absorption of 450 nm and a maximum emission of 518 nm. The fluorescent quantum yield was determined to be 0.55 in toluene. J-A dimerizes in solution via oxidative coupling. Structure of the dimer was characterized using single crystal X-ray diffraction.

A julolidine fused anthracene derivative with unique photophysical and redox properties was presented.

Julolidine¹ is a popular structural subunit in various fluorescent dyes (Chart 1).² The restricted motion and strong electron-donating capability of the fused julolidine moiety are quite effective for improving the photophysical properties. For instance, julolidine-fused fluorophores normally display desirable photophysical characteristics, such as high quantum yield, red-shifted absorption and emission, and good photostability. Recently, julolidine derivatives have been widely exploited in various applications such as sensing,³ imaging,⁴ and nonlinear optical materials.⁵ Several julolidine dyes have been used in dye-sensitized solar cells due to their large π-conjugated system and the promising electron donating property.⁶Open in a separate windowChart 1The structure of julolidine, J-A and DAA.In this paper, we report a julolidine-fused anthracene derivative J-A, which exhibits attractive photophysical properties not observed in DAA, a dimethyl-amino substituted analogue. Both the absorption and emission of J-A show a dramatic red-shift (ca. 74 and 131 nm, respectively), compared with the unmodified anthracene (Fig. 2). The fluorescence quantum yield of J-A was determined to be 0.55 in toluene, while the emission of DAA was completely quenched. The observed spectral properties were rationalized by DFT calculations. In addition, we found that J-A was stable in the solid state, but reactive in solution. J-A dimer was formed through oxidative coupling at the para-position of the N-atom in a dichloromethane solution under air atmosphere. The structure of the dimerized product was characterized using single crystal X-ray diffraction, which unambiguously reveals the structural feature of the julolidine-fused anthracene compound. Preparation of J-A is shown in Scheme 1. Detailed synthesis and characterizations are provided in the ESI.^†Open in a separate windowScheme 1Synthetic route of J-A.Open in a separate windowFig. 2(A) Absorption spectra of J-A, AN, and DAA (1 × 10⁻⁴ mol L⁻¹ in dichloromethane); (B) emission spectra of J-A, AN, and DAA (1 × 10⁻⁵ mol L⁻¹ in dichloromethane). Excitation wavelength: 350 nm. 1 cm cuvette was used in both of the experiments. Inset: visualized fluorescence in solution was shown. ¹H-NMR signals of J-A shift to the high-field significantly, compared with DAA (Fig. 1), which indicates that the fused structure of J-A facilitates electron delocalization from the nitrogen atom to the anthracene moiety, and thus resulting in a stronger shielding effect. In the case of DAA, however, electron delocalization from the dimethyl amino group to the anthracene core is essentially inhibited due to steric hindrance, which will explain the fact that it displays a spectral feature similar to that of the unmodified anthracene.Open in a separate windowFig. 1Comparison of the ¹H-NMR spectrum between J-A and DAA in CDCl₃. Partial resonance signals in aromatic region are shown.Fusing with julolidine will exert significant effects on the photophysical properties of anthracene. The absorption and fluorescence spectra of J-A, DAA, and anthracene are shown in Fig. 2. The maximum absorption of J-A is 450 nm, which displays a red-shift of about 70 nm compared with the unmodified anthracene. J-A emits green light (^maxλ_em = 518 nm, Φ = 0.55), while anthracene emits blue light (^maxλ_em = 380 nm, Φ = 0.22). In contrast, the absorption of DAA essentially overlaps with that of anthracene, with only a minor red shift of ca. 10 nm, but its fluorescence is quenched significantly (Fig. 2). This spectral feature indicates that the dimethyl amino group is electronically separated from the anthracene moiety in the ground state, a result in good accordance with the ¹H-NMR data shown above. The quenched fluorescence of DAA may result from the photo-induced electron transfer⁷ from the lone pair of the nitrogen atom to the anthracene moiety in the excited state.The observed photophysical properties of J-A were reproduced by DFT calculations. The HOMO and LUMO orbitals are evenly distributed over the anthracene moiety and the N-atom in the julolidine, indicating the existence of a conjugated structure. The HOMO–LUMO transition (f = 0.10) corresponds to the absorption band at 450 nm. The sharper absorption at 390 nm can be assigned to the HOMO to LUMO + 1 transition. In contrast, the HOMO and LUMO orbitals of DAA resemble those of anthracene, because the dimethyl-amino group is orthogonal to the conjugated π-system (Fig. 3).Open in a separate windowFig. 3Molecular orbitals of J-A and DAA calculated at the B3LYP/6-31G(d) level of theory (iso value = 0.02). Orbital energies were given in parentheses. Excitation energies were computed by TD-DFT at the same level. Values in parentheses represent the oscillator strengths (f).J-A is stable in the solid state, but reactive in solution. The cyclic voltammetry (CV) diagram of J-A shows an irreversible oxidation potential at 0.007 V (vs. Fc/Fc⁺), indicating that J-A is easy to be oxidized (Fig. S3^†). Single crystals suitable for X-ray diffraction study were obtained by slow evaporation of a dichloromethane solution of J-A under air atmosphere. To our surprise, instead of J-A, X-ray data discloses the formation of a dimeric product (Scheme 2) of J-A. We hypothesized that the dimeric compound 5 formed via oxidative coupling reaction, a mechanism well-documented for the dimerization of the dimethylaniline compounds.⁸ The ¹H-NMR spectrum of 5 is distinct from that of J-A. All protons of the anthracene part (b′–d′) appear as a group of multiplet resonance signals (6.93–7.04 ppm) (Scheme 2). In addition, mass spectrometric analysis indicates that two hydrogen atoms were removed after the dimerization of J-A. Compound 5 exhibits a maximum absorption at 460 nm and a very weak emission (^maxλ_em = 530 nm, Φ = 0.03, Fig. S1^†). Two quasi-reversible oxidation waves were identified in the CV diagram of 5 at −0.010 V and 0.135 V (vs. Fc/Fc⁺), respectively (Fig. S5^†).Open in a separate windowScheme 2Oxidative dimerization of J-A. Inset: partial ¹H-NMR of 5 is shown.X-ray structure of 5 is shown in Fig. 4. The two connected anthracene planes are found to be orthogonal to each other with a dihedral angle of 90.17°, as a result of steric repulsion. Specifically, the bond length of N–C3 is 1.389 Å, which is similar to those of the other reported julolidine compounds (1.359–1.393 Å), while significantly shorter than that of the dimethyl-amino anthracene (1.433 Å).⁹ This result testifies the presence of electron delocalization between the fused julolidine nitrogen and the anthracene π-plane, which is in good agreement with the DFT calculations (Fig. 3). However, the two anthracene π-planes connected by the single bond (C4–C5, 1.489 Å) might not exhibit electron delocalization because of the orthogonal conformation. The fused julolidine ring-i and -ii are symmetric to each other, and both of them adopt an “envelope” conformation. The fused julolidine is nonplanar (bond angle, C3–N–C2, 115.73°, C3–N–C1, 115.92°, C1–N–C2, 113.81°). 5 is closely packed in the crystal (Fig. 4B), and no intercalated solvent molecules were observed. The closest distance between two adjacent anthracene planes is 3.922 Å, indicating a weak π–π stacking. Detailed crystal data are summarized in Table S5.^†Open in a separate windowFig. 4(A) Single crystal X-ray structure of 5. (B) View along a-axis.In summary, we report the synthesis and characterizations of a julolidine-fused anthracene derivative J-A, which demonstrates significantly red-shifted absorption (^maxλ_ab = 450 nm) and emission (^maxλ_em = 518 nm, Φ = 0.55), compared with the unmodified anthracene. The photophysical properties of J-A also contrast dramatically with a dimethyl-amino analogue DAA, which were rationalized by DFT calculations. In addition, J-A could be transformed into 5, a dimeric product, whose single crystal X-ray structure unambiguously confirmed the structural feature of the julolidine-fused anthracene.     

Polyvinylpyrrolidone-drug conjugate: synthesis and release mechanism.

Covalent conjugates of polyvinylpyrrolidone (PVP) with para-nitroaniline (PNA) were synthesized as a model PVP-drug conjugate, and PNA release was evaluated in vitro. Pyrrolidone ring opening with subsequent t-BOC protection of the pyrrolidone nitrogen and reaction with PNA in methylene chloride (CH2Cl2) produced a PVP-PNA conjugate with 3% of the pyrrolidone groups modified. Rates of PNA release from N-deprotected conjugates were twofold greater than those that were N-protected, indicating participation of the pyrrolidone N in release. Additional studies with monomeric analogs supported intramolecular base catalysis rather than lactam formation as the mechanism of this involvement. The approach serves as a prototype for the conjugation of other drugs with primary and secondary amine functional groups with PVP, including peptides and proteins.     

High-pressure synthesis and electrochemical properties of tetragonal LiMnO2

Tetragonal structured LiMnO₂ (t-LiMnO₂) samples were synthesized under pressures above 8 GPa and investigated as a positive electrode material for lithium-ion batteries. Rietveld analyses based on X-ray diffraction measurements indicated that t-LiMnO₂ belongs to a γ-LiFeO₂-type crystal structure with the I4₁/amd space group. The charge capacity during the initial cycle was 37 mA h g⁻¹ at 25 °C, but improved to 185 mA h g⁻¹ at 40 °C with an average voltage of 4.56 V vs. Li⁺/Li. This demonstrated the superiority of t-LiMnO₂ over other lithium manganese oxides in terms of energy density. The X-ray diffraction measurements and Raman spectroscopy of cycled t-LiMnO₂ indicated an irreversible transformation from the γ-LiFeO₂-type structure into a Li_xMn₂O₄ spinel structure by the displacement of 25% of the Mn ions to vacant octahedral sites through adjacent octahedral sites.

Tetragonal structured LiMnO₂ (t-LiMnO₂) samples were synthesized under pressures above 8 GPa and investigated as a positive electrode material for lithium-ion batteries.     

Novel azobenzene-based amphiphilic copolymers: synthesis,self-assembly behavior and multiple-stimuli-responsive properties

A series of novel azobenzene-based amphiphilic random copolymers P(POSSMA-co-AZOMA-co-DMAEMA) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. A light and reduction dual-responsive azo group, pH-responsive tertiary amine group and super hydrophobic POSS moiety were incorporated into the polymer chain to generate multi-stimuli-responsiveness. Self-assembly of these amphiphilic copolymers led to the formation of spherical micelles in aqueous solution. The light, pH and reduction responsive properties of the micelles were investigated systematically by DLS, TEM, UV-vis, FTIR and NMR. The azo groups can undergo trans–cis isomerization under UV light irradiation, thus causing a diameter change of the micelles. Owing to the large proportion of tertiary amine groups in amphiphiles, these micelles showed sensitive pH-response behavior. The hydrophobic azo pendant in the polymer chain completely reduced to a more hydrophilic substituted aniline in a reductive environment, resulting in the increase of overall hydrophilicity of amphiphiles and the disassembly of polymeric micelles. Owing to these multi-stimuli–responses, the polymeric micelles showed rapid and efficient release properties of hydrophobic molecules in response to pH and reductive stimuli.

Polymeric micelles encapsulating and releasing hydrophobic guest molecules.     

Xanthan gum derivatives: review of synthesis,properties and diverse applications

Natural polysaccharides are well known for their biocompatibility, non-toxicity and biodegradability. These properties are also inherent to xanthan gum (XG), a microbial polysaccharide. This biomaterial has been extensively investigated as matrices for tablets, nanoparticles, microparticles, hydrogels, buccal/transdermal patches, tissue engineering scaffolds with different degrees of success. However, the native XG has its own limitations with regards to its susceptibility to microbial contamination, unusable viscosity, poor thermal and mechanical stability, and inadequate water solubility. Chemical modification can circumvent these limitations and tailor the properties of virgin XG to fulfill the unmet needs of drug delivery, tissue engineering, oil drilling and other applications. This review illustrates the process of chemical modification and/crosslinking of XG via etherification, esterification, acetalation, amidation, and oxidation. This review further describes the tailor-made properties of novel XG derivatives and their potential application in diverse fields. The physicomechanical modification and its impact on the properties of XG are also discussed. Overall, the recent developments on XG derivatives are very promising to progress further with polysaccharide research.

Due to presence of hydroxy and carboxy functional groups, xanthan gum is amenable to various chemical modification for producing derivatives such as carboxymethyl xanthan and carboxymethyl hydroxypropyl xanthan with desirable properties for end use.     

Silica coated iron nanoparticles: synthesis,interface control,magnetic and hyperthermia properties

This work provides a detailed study on the synthesis and characterization of silica coated iron nanoparticles (NPs) by coupling Transmission Electronic Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS) and magnetic measurements. Remarkably, iron NPs (of 9 nm of mean diameter) have been embedded in silica without any alteration of the magnetization of the iron cores, thanks to an original protocol of silica coating in non alcoholic medium. Tuning the synthesis parameters (concentration of reactants and choice of solvent), different sizes of Fe@SiO₂ composites can be obtained with different thicknesses of silica. The magnetization of these objects is fully preserved after 24 h of water exposure thanks to a thick (14 nm) silica layer, opening thus new perspectives for biomedical applications. Hyperthermia measurements have been compared between Fe and Fe@SiO₂ NPs, evidencing the self-organization of the free Fe NPs when a large amplitude magnetic field is applied. This phenomenon induces an increase of heating power which is precluded when the Fe cores are immobilised in silica. High-frequency hysteresis loop measurements allowed us to observe for the first time the increase of the ferrofluid susceptibility and remanence which are the signature of the formation of Fe NPs chains.

A novel method has been developed for the silica coating of iron nanoparticles while preserving the magnetic properties.     

Correction: Novel azobenzene-based amphiphilic copolymers: synthesis,self-assembly behavior and multiple-stimuli-responsive properties

Correction for ‘Novel azobenzene-based amphiphilic copolymers: synthesis, self-assembly behavior and multiple-stimuli-responsive properties’ by Yiting Xu et al., RSC Adv., 2018, 8, 16103–16113.

The final entry for Table 1 relating to Sample C-4 in the published paper showed an incorrect entry for the column [POSSMA] : [AZOMA] : [DMAEMA] : [CDB] : [AIBN]; this should read 12 : 50 : 100 : 0 : 0.20.The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.