Mitochondria-targeted curcumin loaded CTPP–PEG–PCL self-assembled micelles for improving liver fibrosis therapy

Liver fibrosis, originating from activated hepatic stellate cells (HSCs), is receiving much attention in the treatment of clinical liver disease. In this study, mitochondria-targeted curcumin (Cur) loaded 3-carboxypropyl-triphenylphosphonium bromide–poly(ethylene glycol)–poly(ε-caprolactone) (CTPP–PEG–PCL) micelles were constructed to prolong the systemic circulation of Cur, improve the bioavailability of Cur and play a precise role in anti-fibrosis. The prepared Cur–CTPP–PEG–PCL micelles with a spherical shape had satisfactory dispersion, low critical micelle concentration (CMC) and high encapsulation efficiency (92.88%). The CTPP modification endowed good endosomal escape ability to the CTPP–PEG–PCL micelles, and micelles could be selectively accumulated in mitochondria, thereby inducing the enhanced cell proliferation inhibition of HSC-T6 cells. Mitochondrial Membrane Potential (MMP) was greatly reduced due to the mitochondrial-targeting of Cur. Moreover, the system circulation of Cur was extended and bioavailability was significantly enhanced in vivo. As expected, Cur loaded CTPP–PEG–PCL micelles were more effective in improving liver fibrosis compared with Cur and Cur–mPEG–PCL micelles. In conclusion, the Cur–CTPP–PEG–PCL based micelles can be a potential candidate for liver fibrosis treatment in future clinical applications.

A mitochondria-targeting micelle system based on CTPP–PEG–PCL polymer was designed to deliver curcumin to active HSC-T6 cells and prolong the systemic circulation and bioavailability of curcumin in vivo for effective treatment of liver fibrosis.     

Reduction-responsive diblock copolymer-modified gold nanorods for enhanced cellular uptake

Reduction-responsive polymer micelles are highly promising drug carriers with better tumor therapeutic effect, which can be achieved by controlled drug release under stimulation. Gold nanorods (AuNRs) have attracted considerable attention due to their unique optical and electronic properties when used for biomedical applications. Herein, the lipoic-acid-functionalized reduction-responsive amphiphilic copolymer poly(ε-caprolactone)-b-poly[(oligoethylene glycol) acrylate] (LA–PCL–SS–POEGA) with a disulfide group between the two blocks was prepared to modify AuNRs via Au–S bonds. The size and morphology of AuNRs@LA–PCL–SS–POEGA were measured by dynamic laser light scattering (DLS) and transmission electron microscopy (TEM) methods. The stabilities of AuNRs@LA–PCL–SS–POEGA in different types of media were studied by UV/vis spectroscopy and DLS techniques. The results show that AuNRs@LA–PCL–SS–POEGA gradually aggregate in a concentrated salt solution containing 150 mM dithiothreitol (DTT), but exhibit high stability in a non-reducing environment. Near infrared (NIR)-induced heating of AuNRs@LA–PCL–SS–POEGA was investigated in an aqueous solution under NIR laser irradiation (808 nm), revealing that AuNRs@LA–PCL–R–POEGA maintain excellent photothermal conversion efficiency after modification. When compared with non-reduction responsive AuNRs@LA–PCL–CC–POEGA, the in vitro internalization of AuNRs@LA–PCL–SS–POEGA demonstrates that the reduction-responsive polymer could enhance the cellular uptake of nanoparticles measured by inductively coupled plasma mass spectrometry (ICP-MS) and TEM.

Gold nanorod (AuNRs) modified by reduction-responsive amphiphilic copolymer poly(ε-caprolactone)-b-poly[(oligoethylene glycol)acrylate] (LA–PCL–SS–POEGA) can enhance the cellular uptake of AuNRs, presumably due to the aggregation under reducing environment in the cells.     

Direct β-selectivity of α,β-unsaturated γ-butyrolactam for asymmetric conjugate additions in an organocatalytic manner

The β-selective asymmetric addition of γ-butyrolactam with cyclic imino esters catalyzed by a bifunctional chiral tertiary amine has been developed, which provides an efficient access to optically active β-position functionalized pyrrolidin-2-one derivatives in both high yield and enantioselectivity (up to 78% yield and 95 : 5 er). This is the first catalytic method to access chiral β-functionalized pyrrolidin-2-one via a direct organocatalytic approach.

The asymmetric addition of γ-butyrolactam with cyclic imino esters catalyzed by (DHQD)₂AQN has been developed, which provides an access to β-position functionalized pyrrolidin-2-one derivatives in high levels yield and enantioselectivity.

Metal-free organocatalytic asymmetric transformations have successfully captured considerable enthusiasm of chemists as powerful methods for the synthesis of various kinds of useful chiral compounds ranging from the preparation of biologically important molecules through to novel materials.¹ Chiral pyrrolidin-2-ones have been recognized as important structural motifs that are frequently encountered in a variety of biologically active natural and synthetic compounds.² In particular, the β-position functionalized pyrrolidin-2-one backbones, which can serve as key synthetic precursors for inhibitory neurotransmitters γ-aminobutyric acids (GABA),³ selective GABA_B receptor agonists⁴ as well as antidepressant rolipram analogues,⁵ have attracted a great deal of attention. Therefore, the development of highly efficient, environmentally friendly and convenient asymmetric synthetic methods to access these versatile frameworks is particularly appealing.As a direct precursor to pyrrolidin-2-one derivatives, recently, α,β-unsaturated γ-butyrolactam has emerged as the most attractive reactant in asymmetric organometallic or organocatalytic reactions for the synthesis of chiral γ-position functionalized pyrrolidin-2-ones (Scheme 1). These elegant developments have been achieved in the research area of catalytic asymmetric vinylogous aldol,⁶ Mannich,⁷ Michael⁸ and annulation reactions⁹ in the presence of either metal catalysts or organocatalysts (a, Scheme 1). These well-developed catalytic asymmetric methods have been related to the γ-functionalized α,β-unsaturated γ-butyrolactam to date. However, in sharp contrast, the approaches toward introducing C-3 chirality at the β-position of butyrolactam through a direct catalytic manner are underdeveloped (b, Scheme 1)¹⁰ in spite of the fact that β-selective chiral functionalization of butyrolactam can directly build up α,β-functionalized pyrrolidin-2-one frameworks.Open in a separate windowScheme 1Different reactive position of α,β-unsaturated γ-butyrolactam in catalytic asymmetric reactions.So far, only a few metal-catalytic enantioselective β-selective functionalized reactions have been reported. For examples, a rhodium/diene complex catalyzed efficient asymmetric β-selective arylation^10a and alkenylation^10b have been reported by Lin group (a, Scheme 2). Procter and co-workers reported an efficient Cu(i)–NHC-catalyzed asymmetric silylation of unsaturated lactams (b, Scheme 2).^10c Despite these creative works, considerable challenges still exist in the catalytic asymmetric β-selective functionalization of γ-butyrolactam. First, the scope of nucleophiles is limited to arylboronic acids, potassium alkenyltrifluoroborates and PhMe₂SiBpin reagents. Second, the catalytic system and activation mode is restricted to metal/chiral ligands. To our knowledge, an efficient catalytic method to access chiral β-functionalized pyrrolidin-2-one via a direct organocatalytic approach has not yet been established. Therefore, the development of organocatalytic asymmetric β-selective functionalization of γ-butyrolactam are highly desirable. In conjunction with our continuing efforts in building upon chiral precedents by using chiral tertiary amine catalytic system,¹¹ we rationalized that the activated α,β-unsaturated γ-butyrolactam might serve as a β-position electron-deficient electrophile. This γ-butyrolactam may react with a properly designed electron-rich nucleophile to conduct an expected β-selective functionalized reaction of γ-butyrolactam under a bifunctional organocatalytic fashion, while avoiding the direct γ-selective vinylogous addition reaction or β,γ-selective annulation as outlined in Scheme 2. Herein we report the β-selective asymmetric addition of γ-butyrolactam with cyclic imino esters¹² catalyzed by a bifunctional chiral tertiary amine, which provides an efficient and facile access to optically active β-position functionalized pyrrolidin-2-one derivatives with both high diastereoselectivity and enantioselectivity.Open in a separate windowScheme 2β-Selective functionalization of γ-butyrolactam via metal- (previous work) or organo- (this work) catalytic approach.To begin our initial investigation, several bifunctional organocatalysts¹³ were firstly screened to evaluate their ability to promote the β-selective asymmetric addition of γ-butyrolactam 2a with cyclic imino ester 3a in the presence of 15 mol% of catalyst loading at room temperature in CH₂Cl₂ (entries 1–6,

Functionalization of α-hydroxyphosphonates as a convenient route to N-tosyl-α-aminophosphonates

Direct conversion of the α-hydroxyl group by para-toluenesulfonamide to yield α-(N-tosyl)aminophosphonates is reported. α-Aminophosphonates 23a,b–37a,b were obtained from the corresponding α-hydroxyphosphonates 6a,b–21a,b in the presence of K₂CO₃, via the retro-Abramov reaction of the appropriate aldehydes, 1–5. The subsequent formation of imines with simultaneous addition of diethyl phosphite provided access to the α-sulfonamide phosphonates 23a,b–37a,b with better diastereoselectivity than in the case of the Pudovik reaction. The mechanism for this transformation is proposed herein. When Cbz N-protected aziridine 9a,b and phenylalanine analogue 12a,b were exploited, intramolecular substitution was observed, leading to the corresponding epoxide 38 as the sole product, or oxazolidin-2-one 39 as a minor product. Analogous substitution was not observed in the case of proline 18a,b and serine 21a,b derivatives.

The reaction mechanism and diastereoselectivity of the direct transformation of α-hydroxyphosphonates 6a,b–21a,b by para-toluenesulfonamide, yielding α-(N-tosyl)aminophosphonates 23a,b–37a,b under K₂CO₃ conditions are presented.     

Nanostructured poly(l-lactic acid)–poly(ethylene glycol)–poly(l-lactic acid) triblock copolymers and their CO2/O2 permselectivity

Biodegradable poly(l-lactic acid)–poly(ethylene glycol)–poly(l-lactic acid) (PLLA–PEG–PLLA) copolymers were synthesized by ring-opening polymerization of l-lactide using dihydroxy PEG as the initiator. The effects of different PEG segments in the copolymers on the mechanical and permeative properties were investigated. It was determined that certain additions of PEG result in composition-dependent microphase separation structures with both PLLA and PEG blocks in the amorphous state. Amorphous PEGs with high CO₂ affinity form gas passages that provide excellent CO₂/O₂ permselectivity in such a nanostructure morphology. The gas permeability and permselectivity depend on the molecular weight and content of the PEG and are influenced by the temperature. Copolymers that have a higher molecular weight and content of PEG present better CO₂ permeability at higher temperatures but provide better CO₂/O₂ permselectivity at lower temperatures. In addition, the hydrophilic PEG segments improve the water vapor permeability of PLLA. Such biodegradable copolymers have great potential for use as fresh product packaging.

Biodegradable PLLA copolymers, containing higher molecular weight and content of PEG present better CO₂ permeability and CO₂/O₂ permselectivity, have great potential for use as fresh product packaging.     

Effect of stereocomplex crystal and flexible segments on the crystallization and tensile behavior of poly(l-lactide)

The effects of poly(ethylene glycol) (PEG) and/or poly(d-lactide) (PDLA) blocks on the crystallization and mechanical properties of poly(l-lactide) (PLLA) were investigated systematically via differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD) and tensile testing. The structural evolution during uniaxial stretching of the obtained blends above the glass transition temperature was studied by in situ WAXD. It was observed that the stereocomplex (SC) crystals promoted the nucleation of PLLA homocrystals (α/α′ crystal), and flexible PEG blocks could enhance the spherulitic growth rate. The PLLA/PDLA–PEG–PDLA had a higher elongation at break than that of PLLA/PDLA without significant loss in tensile strength and stiffness. In situ WAXD showed that the PLLA/PDLA–PEG–PDLA crystallized faster during stretching. It was shown that the incorporation of SC crystals and flexible PEG blocks could not only accelerate the crystallization but also improve the toughness of PLLA.

Effect of stereocomplex crystal and PEG segments in blends on the crystallization and tensile behavior of PLLA.     

Synthesis,physicochemical characterization,toxicity and efficacy of a PEG conjugate and a hybrid PEG conjugate nanoparticle formulation of the antibiotic moxifloxacin

Antibiotic resistance is increasing at such an alarming rate that it is now one of the greatest global health challenges. Undesirable toxic side-effects of the drugs lead to high rates of non-completion of treatment regimens which in turn leads to the development of drug resistance. We report on the development of delivery systems that enable antibiotics to be toxic against bacterial cells while sparing human cells. The broad-spectrum fluoroquinolone antibiotic moxifloxacin (Mox) was successfully conjugated to poly(ethylene glycol) (PEG) which was further encapsulated into the hydrophobic poly(ε-caprolactone) (PCL) nanoparticles (NPs) with high efficiency, average particle size of 241.8 ± 4 nm and negative zeta potential. Toxicity against erythrocytes and MDBK cell lines and drug release in human plasma were evaluated. Hemocompatibility and reduced cytotoxicity of the PEG–Mox and PCL(PEG–Mox) NPs were demonstrated in comparison to free Mox. Antimicrobial activity was assessed against drug sensitive and resistant: Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and Klebsiella pneumoniae. The antibacterial activity of Mox was largely maintained after conjugation. Our data shows that the toxicity of Mox can be effectively attenuated while, in the case of PEG–Mox, retaining significant antibacterial activity. At the conditions employed in this study for antimicrobial activity the encapsulated conjugate (PCL(PEG–Mox) NPs) did not demonstrate, conclusively, significant antibacterial activity. These systems do, however, hold promise if further developed for improved treatment of bacterial infections.

Moxifloxacin was conjugated to polyethylene glycol to segregate host cell toxicity from antimicrobial activity. The conjugate was then encapsulated into a polycaprolactone nanoparticle to assist the simultaneous delivery of multiple drugs to the site of microbial infection.     

Aromatic fluorocopolymers based on α-(difluoromethyl)styrene and styrene: synthesis,characterization, and thermal and surface properties

A study on the α-(difluoromethyl)styrene (DFMST) reactivity under conventional radical copolymerization conditions is presented. Although the homopolymerization of DFMST failed, its radical bulk copolymerization with styrene (ST) led to the synthesis of fluorinated aromatic polymers (FAPs). The resulting novel poly(DFMST-co-ST) copolymers were characterized by ¹H, ¹⁹F and ¹³C NMR spectroscopies that evidenced the successful incorporation of DFMST units into copolymers and enabled the assessment of their respective molar percentages (10.4–48.2 mol%). The molar masses were in the range of 1900–17 200 g mol⁻¹. The bulkier CF₂H group in the α-position induced the lower reactivity of the DFMST comonomer. ST and DFMST monomer reactivity ratios (r_DFMST = 0.0 and r_ST = 0.70 ± 0.05 at 70 °C) were determined based on linear least-square methods. These values indicate that DFMST monomer is less reactive than ST, retards the polymerization rate, and thus reduces the molar masses. Moreover, the thermal properties (T_g, T_d) of the resulting copolymers indicate that the presence of DFMST units incorporated into poly(ST) structure promotes an increase of the T_g values up to 109 °C and a slightly better thermal stability than that of poly(ST). Additionally, the thermal decomposition of poly(DFMST-co-ST) copolymer (10.4/89.6) was assessed by simultaneous thermal analysis coupled with Fourier-transform infrared spectroscopy and thermogravimetric analysis coupled with mass spectrometry showing that H₂O, CO₂, CO and styrene were released. The surface analysis was focused on the effects of the –CF₂H group at the α-position of styrene comonomers on surface free energy of the copolymer films. Water and diiodomethane contact angle (CA) measurements confirmed that these copolymers (M_n = 2300–17 200 g mol⁻¹) are not exactly the same as polystyrenes (M_n = 2100–21 600 g mol⁻¹) in the solid state. The CA hysteresis for poly(ST) (6–8°) and poly(DFMST-co-ST) copolymers (3–5°) reflected these differences even more accurately.

A study on the α-(difluoromethyl)styrene (DFMST) reactivity under conventional radical (co)polymerization conditions is presented.     

Aerobically stable and substitutionally labile α-diimine rhenium dicarbonyl complexes

New synthetic routes to aerobically stable and substitutionally labile α-diimine rhenium(i) dicarbonyl complexes are described. The molecules are prepared in high yield from the cis–cis–trans-[Re(CO)₂(^tBu₂bpy)Br₂]⁻ anion (2, where ^tBu₂bpy is 4,4′-di-tert-butyl-2,2′-bipyridine), which can be isolated from the one electron reduction of the corresponding 17-electron complex (1). Compound 2 is stable in the solid state, but in solution it is oxidized by molecular oxygen back to 1. Replacement of a single bromide of 2 by σ-donor monodentate ligands (Ls) yields stable neutral 18-electron cis–cis–trans-[Re(CO)₂(^tBu₂bpy)Br(L)] species. In coordinating solvents like methanol the halide is replaced giving the corresponding solvated cations. [Re(CO)₂(^tBu₂bpy)Br(L)] species can be further reacted with Ls to prepare stable cis–cis–trans-[Re(CO)₂(^tBu₂bpy)(L)₂]⁺ complexes in good yield. Ligand substitution of Re(i) complexes proceeds via pentacoordinate intermediates capable of Berry pseudorotation. In addition to the cis–cis–trans-complexes, cis–cis–cis- (all cis) isomers are also formed. In particular, cis–cis–trans-[Re(CO)₂(^tBu₂bpy)(L)₂]⁺ complexes establish an equilibrium with all cis isomers in solution. The solid state crystal structure of nearly all molecules presented could be elucidated. The molecules adopt a slightly distorted octahedral geometry. In comparison to similar fac-[Re(CO)₃]⁺complexes, Re(i) diacarbonyl species are characterized by a bend (ca. 7°) of the axial ligands towards the α-diimine unit. [Re(CO)₂(^tBu₂bpy)Br₂]⁻ and [Re(CO)₂(^tBu₂bpy)Br(L)] complexes may be considered as synthons for the preparation of a variety of new stable diamagnetic dicarbonyl rhenium cis-[Re(CO)₂]⁺ complexes, offering a convenient entry in the chemistry of the core.

New synthetic routes to aerobically stable and substitutionally labile α-diimine rhenium(i) dicarbonyl complexes offer a convenient entry in the chemistry of the cis-[Re(CO)₂]⁺ core.     

Chemical stability of Ca3Co4−xO9+δ/CaMnO3−δ p–n junction for oxide-based thermoelectric generators

An all-oxide thermoelectric generator for high-temperature operation depends on a low electrical resistance of the direct p–n junction. Ca₃Co_4−xO_9+δ and CaMnO_3−δ exhibit p-type and n-type electronic conductivity, respectively, and the interface between these compounds is the material system investigated here. The effect of heat treatment (at 900 °C for 10 h in air) on the phase and element distribution within this p–n junction was characterized using advanced transmission electron microscopy combined with X-ray diffraction. The heat treatment resulted in counter diffusion of Ca, Mn and Co cations across the junction, and subsequent formation of a Ca₃Co_1+yMn_1−yO₆ interlayer, in addition to precipitation of Co-oxide, and accompanying diffusion and redistribution of Ca across the junction. The Co/Mn ratio in Ca₃Co_1+yMn_1−yO₆ varies and is close to 1 (y = 0) at the Ca₃Co_1+yMn_1−yO₆–CaMnO_3−δ boundary. The existence of a wide homogeneity range of 0 ≤ y ≤ 1 for Ca₃Co_1+yMn_1−yO₆ is corroborated with density functional theory (DFT) calculations showing a small negative mixing energy in the whole range.

The heat treatment beneficially affects the performance of an all-oxide thermoelectric generator through phase and element distribution within this p–n junction.     

High pressure as a novel tool for the cationic ROP of γ-butyrolactone

In this study, we report the acid-catalyzed and high pressure assisted ring-opening polymerization (ROP) of γ-butyrolactone (GBL). The use of a dually-catalyzed approach combining an external physical factor and internal catalyst (trifluoromethanesulfonic acid (TfOH) or p-toluenesulfonic acid (PTSA)) enforced ROP of GBL, which is considered as hardly polymerizable monomer still remaining a challenge for the modern polymer chemistry. The experiments performed at various thermodynamic conditions (T = 278–323 K and p = 700–1500 MPa) clearly showed that the high pressure supported polymerization process led to obtaining well-defined macromolecules of better parameters (M_n = 2200–9700 g mol⁻¹; Đ = 1.05–1.46) than those previously reported. Furthermore, the parabolic-like dependence of both the molecular weight (M_W) and the yield of obtained polymers on variation in temperature and pressure at either isobaric or isothermal conditions was also noticed, allowing the determination of optimal conditions for the polymerization process. However, most importantly, this strategy allowed to significantly reduce the reaction time (just 3 h at room temperature) and increase the yield of obtained polymers (up to 0.62 g_PGBL/g_GBL). Moreover, despite using a strongly acidic catalyst, synthesized polymers remained non-toxic and biocompatible, as proven by the cytotoxicity test we performed in further analysis. Additional investigation (including MALDI-TOF measurements) showed that the catalyst selection affected not only M_W and yield but also the linear/cyclic form content in obtained macromolecules. These findings show the way to tune the properties of PGBL and obtain polymer suitable for application in the biomedical industry.

Well-defined poly(γ-butyrolactone) was synthesized with great efficiency via high pressure assisted cationic ROP of hardly polimerizable γ-butyrolactone.     

High-pressure synthesis of ε-FeOOH from β-FeOOH and its application to the water oxidation catalyst

Research on materials under extreme conditions such as high pressures provides new insights into the evolution and dynamics of the earth and space sciences, but recently, this research has focused on applications as functional materials. In this contribution, we examined high-pressure/high-temperature phases of β-FeO_1−x(OH)_1+xCl_x with x = 0.12 (β-FeOOH) and their catalytic activities of water oxidation, i.e., oxygen evolution reaction (OER). Under pressures above 6 GPa and temperatures of 100–700 °C, β-FeOOH transformed into ε-FeOOH, as in the case of α-FeOOH. However, the established pressure–temperature phase diagram of β-FeOOH differs from that of α-FeOOH, probably owing to its open framework structure and partial occupation of Cl⁻ ions. The OER activities of ε-FeOOH strongly depended on the FeOOH sources, synthesis conditions, and composite electrodes. Nevertheless, one of the ε-FeOOH samples exhibited a low OER overpotential compared with α-FeOOH and its parent β-FeOOH, which are widely used as OER catalysts. Hence, ε-FeOOH is a potential candidate as a next-generation earth-abundant OER catalyst.

Research on materials under extreme conditions such as high pressures provides new insights into the evolution and dynamics of the earth and space sciences, but recently, this research has focused on applications as functional materials.     

Theoretical study of D–A′–π–A/D–π–A′–π–A triphenylamine and quinoline derivatives as sensitizers for dye-sensitized solar cells

We have designed four dyes based on D–A′–π–A/D–π–A′–π–A triphenylamine and quinoline derivatives for dye-sensitized solar cells (DSSCs) and studied their optoelectronic properties as well as the effects of the introduction of alkoxy groups and thiophene group on these properties. The geometries, single point energy, charge population, electrostatic potential (ESP) distribution, dipole moments, frontier molecular orbitals (FMOs) and HOMO–LUMO energy gaps of the dyes were discussed to study the electronic properties of dyes based on density functional theory (DFT). And the absorption spectra, light harvesting efficiency (LHE), hole–electron distribution, charge transfer amount from HOMO to LUMO (Q_CT), D index, H_CT index, S_m index and exciton binding energy (E_coul) were discussed to investigate the optical and charge-transfer properties of dyes by time-dependent density functional theory (TD-DFT). The calculated results show that all the dyes follow the energy level matching principle and have broadened absorption bands at visible region. Besides, the introduction of alkoxy groups into triarylamine donors and thiophene groups into conjugated bridges can obviously improve the stability and optoelectronic properties of dyes. It is shown that the dye D4, which has had alkoxy groups as well as thiophene groups introduced and possesses a D–π–A′–π–A configuration, has the optimal optoelectronic properties and can be used as an ideal dye sensitizer.

We have designed four dyes based on D–A′–π–A/D–π–A′–π–A triphenylamine and quinoline derivatives for DSSCs and studied their optoelectronic properties as well as the effects of the introduction of alkoxy groups and thiophene group on the properties.     

Lanthanide complexes combined with chiral salen ligands: application in the enantioselective epoxidation reaction of α,β-unsaturated ketones

Readily available lanthanide amides Ln[N(SiMe₃)₂]₃ (Ln = Nd (1), Sm (2), Eu (3), Yb (4), La (5)), combined with chiral salen ligands H₂L^a ((S,S)-N,N′-di-(3,5-disubstituted-salicylidene)-1,2-cyclohexanediamine) and H₂L^b ((S,S)-N,N′-di-(3,5-disubstituted-salicylidene)-1,2-diphenyl-1,2-ethanediamine) were employed in the enantioselective epoxidation of α,β-unsaturated ketones. It was found that the salen–La complex shows the highest efficiency and enantioselectivity. A relatively broad scope of α,β-unsaturated ketones was investigated, and excellent yields (up to 99%) and moderate to good enantioselectivities (37–87%) of the target molecules were achieved.

The enantioselective epoxidation of α,β-unsaturated ketones was catalysed by readily available lanthanide amides La[N(SiMe₃)₂]₃ combined with chiral salen ligands.     

Improvement of thermoelectric performance of copper-deficient compounds Cu2.5+δIn4.5Te8 (δ = 0–0.15) due to a degenerate impurity band and ultralow lattice thermal conductivity

Cu–In–Te ternary chalcogenides have unique crystal and band structures; hence they have received much attention in thermoelectrics. In this work we have observed an enhancement in Hall carrier concentration (n_H) and ultralow lattice thermal conductivity (κ_L) when Cu was added to ternary Cu_2.5+δIn_4.5Te₈ (δ = 0–0.15) compounds. The enhancement in n_H is attributed to a degenerate impurity band at the G point in the valence band maximum (VBM), while the extremely low κ_L results from the increased lattice disorder. We thus obtained the minimum κ_L value of only 0.23 W K⁻¹ m⁻¹ in the sample at δ = 0.1 and 820 K, which is in good agreement with the calculation using the Callaway model. The highest thermoelectric figure of merit ZT is 0.84 for the material at δ = 0.1, which is about 0.38 higher than that of the pristine Cu_2.5In_4.5Te₈.

Improvement of thermoelectric performance of copper-deficient compounds Cu_2.5+δIn_4.5Te₈ (δ = 0–0.15) due to degenerate impurity band (IB) and ultralow lattice thermal conductivity.     

Cationic palladium(ii)-catalyzed synthesis of substituted pyridines from α,β-unsaturated oxime ethers

An efficient method for the synthesis of multi-substituted pyridines from β-aryl-substituted α,β-unsaturated oxime ethers and alkenes via Pd-catalyzed C–H activation has been developed. The method, using Pd(OAc)₂ and a sterically hindered pyridine ligand, provides access to various multi-substituted pyridines with complete regioselectivity. Mechanistic studies suggest that the pyridine products are formed by Pd-catalyzed electrophilic C–H alkenylation of α,β-unsaturated oxime followed by aza-6π-electrocyclization. The utility of this method is showcased by the synthesis of 4-aryl-substituted pyridine derivatives, which are difficult to synthesize efficiently using previously reported Rh-catalyzed strategies with alkenes.

An efficient method for the synthesis of multi-substituted pyridines from α,β-unsaturated oxime ethers via cationic Pd(ii)-catalyzed C–H activation has been developed.     

Effect of molecular weight of polyethylene glycol on crystallization behaviors,thermal properties and tensile performance of polylactic acid stereocomplexes

In this work, the poly(d-lactic acid)–polyethylene glycol–poly(d-lactic acid) (PDLA–PEG–PDLA) triblock copolymer as a novel modification agent was incorporated into poly(l-lactic acid) (PLLA) to improve the thermal and mechanical properties of PLLA. The influences of molecular weight of PEG in the triblock copolymer on the structure, crystallization behaviors, heat resistance and tensile properties of PDLA–PEG–PDLA/PLLA blends were investigated by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), differential scanning calorimetry (DSC), polarized optical microscopy (POM), thermogravimetric analysis (TGA) and tensile testing. The results from FTIR, XRD and DSC confirm the formation of a polylactide stereocomplex in the PLLA blends. The structure and properties of the stereocomplex crystals are different from those of pure PLLA. The melting temperature (T_m) of the stereocrystal is near 200 °C, which is significantly higher than that of the homogeneous crystal of PLLA. The effect of molecular weight of PEG on the crystal morphology of PLLA blends is also obvious. The improvement of tensile properties for PLLA blends is attributed to the crystal morphological features, which will potentially enhance the utility of the PLLA based polymer.

In this work, the poly(d-lactic acid)–polyethylene glycol–poly(d-lactic acid) (PDLA–PEG–PDLA) triblock copolymer as a novel modification agent was incorporated into poly(l-lactic acid) (PLLA) to improve the thermal and mechanical properties of PLLA.     

Elucidating π–π interaction-induced extension effect in sandwich phthalocyaninato compounds

Electrochemical and theoretical investigations over triple-quadruple-, quintuple-, and sextuple-decker sandwich-type compounds {[(Pc*)Sm][(Pc*)Cd_n(Pc*)_n][Sm(Pc*)]} (n = 0–3) elucidate successive π–π interaction-linked extension in the perpendicular direction of the phthalocyanine plane along with increasing the stacked tetrapyrrole number, significantly improving the nonlinear optical properties including effective imaginary third order molecular hyperpolarizability and optical limiting threshold.

π–π interaction-linked extension in the perpendicular direction to the monomers and corresponding effect on nonlinear optic properties have been clearly disclosed over the multiple-decker sandwich-type phthalocyaninato metal compounds.     

Additive effects of alkali metals on Cu-modified CH3NH3PbI3−δClδ photovoltaic devices

We investigated the addition of alkali metal elements (namely Na⁺, K⁺, Rb⁺, and Cs⁺) to Cu-modified CH₃NH₃PbI_3−δCl_δ photovoltaic devices and their effects on the photovoltaic properties and electronic structure. The open-circuit voltage was increased by CuBr₂ addition to the CH₃NH₃PbI_3−δCl_δ precursor solution. The series resistance was decreased by simultaneous addition of CuBr₂ and RbI, which increased the external quantum efficiencies in the range of 300–500 nm, and the short-circuit current density. The energy gap of the perovskite crystal increased through CuBr₂ addition, which we also confirmed by first-principles calculations. Charge carrier generation was observed in the range of 300–500 nm as an increase of the external quantum efficiency, owing to the partial density of states contributed by alkali metal elements. Calculations suggested that the Gibbs energies were decreased by incorporation of alkali metal elements into the perovskite crystals. The conversion efficiency was maintained for 7 weeks for devices with added CuBr₂ and RbI.

Addition of alkali metal elements (Na⁺, K⁺, Rb⁺, and Cs⁺) to Cu-modified CH₃NH₃PbI_3−δCl_δ devices improved the photovoltaic properties.     

Crystallization,rheology and mechanical properties of the blends of poly(l-lactide) with supramolecular polymers based on poly(d-lactide)–poly(ε-caprolactone-co-δ-valerolactone)–poly(d-lactide) triblock copolymers

In this study, we investigated the blending of poly(l-lactide) (PLLA) with supramolecular polymers based on poly(d-lactide)–poly(ε-caprolactone-co-δ-valerolactone)–poly(d-lactide) (PDLA–PCVL–PDLA) triblock copolymers as an efficient way to modify PLLA. The supramolecular polymers (SMP) were synthesized by the terminal functionalization of the PDLA–PCVL–PDLA copolymers with 2-ureido-4[1H]-pyrimidinone (UPy). The structure, thermal properties and rheological behavior of the synthesized supramolecular polymers were studied; we found that the formation of the UPy dimers expanded the molecular chain of the polymer and the incorporation of the UPy groups suppressed the crystallization of polymers. In addition, the synthesized supramolecular polymers had a low glass transition temperature of about −50 °C, showing the characteristics of elastomers. On this basis, superior properties such as a fast crystallization rate, high melt strength, and toughness of fully bio-based, i.e., PLA-based materials were achieved simultaneously by blending PLLA with the synthesized supramolecular polymers. In the PLLA/SMP blends, PLLA could form a stereocomplex with its enantiomeric PDLA blocks of supramolecular polymers, and the stereocomplex crystals with the cross-linking networks reinforced the melt strength of the PLLA/SMP blends. The influences of the SMP composition and the SMP content in the PLLA matrix on crystallization and mechanical properties were analyzed. The supramolecular polymers SMP0.49 and SMP1.04 showed a reverse effect on the crystallization of PLLA. Tensile tests revealed that the lower content of the synthesized supramolecular polymers could achieve toughening of the PLLA matrix. Therefore, the introduction of supramolecular polymers based on PDLA–PCVL–PDLA is an effective way to control the crystallization, rheology and mechanical properties of PLLA.

Supramolecular polymer based on PDLA–PCVL–PDLA triblock copolymer was used for the modification of PLLA, and the results showed that it is an effective way to control the crystallization, rheology and mechanical properties of PLLA.