Synthesis and UCST‐type phase behavior of polypeptide with alkyl side‐chains in alcohol or ethanol/water solvent mixtures

A series of thermoresponsive polypeptides bearing 1‐butyl, 1‐hexyl, or 1‐dodecyl side‐chains (i.e., 6a ‐ 6c ) were synthesized by copper‐mediated 1,3‐dipolar cycloaddition with high grafting efficiency (>95%) between side‐chain “clickable” polypeptide, namely poly(γ‐4‐(propargoxycarbonyl)benzyl‐_L‐glutamate) ( 5 ) and 1‐azidoalkanes. 5 with different degree of polymerization (DP = 48–86) were prepared from triethylamine initiated ring‐opening polymerization of γ‐4‐(propargoxycarbonyl)benzyl‐_L‐glutamic acid based N‐carboxyanhydride ( 4 ). ¹H NMR, FTIR, and GPC results revealed the successful preparation of the resulting polypeptides. 6a ‐ 6c showed reversible UCST‐type phase behaviors in methanol, ethanol, and ethanol/water solvent mixtures depending on the polymer main‐chain length, alkyl side‐chain length, weight percentage of ethanol (f_w) in the binary solvent, and so forth. FTIR analysis revealed the presence of the van der Waals interaction between the alkyl pendants of polypeptides and alkyl groups of alcoholic solvents. Variable‐temperature UV‐vis spectroscopy revealed that the UCST‐type phase transition temperature (T_pt) increased as polymer main‐chain length or concentration increased. In ethanol/water solvent mixtures, polypeptide with short alkyl pendant (i.e., 1‐butyl group) and short main‐chain length (DP = 41) showed the widest f_w range and T_pts in the range of 61.0–71.1 °C. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3425–3435     

Lanthanum trilactate: Vibrational spectroscopic study − infrared/Raman spectroscopy

In this study lanthanum trilactate was prepared by neutralization reaction of lactic acid and lanthanum oxide, purified and identified by X-ray powder diffraction. Infrared spectra (Mid-IR region 4000–650 cm⁻¹) and Raman spectra (Stokes region 4000–100 cm⁻¹) of the high quality crystalline samples have been recorded and presented for the first time. For comparison DFT calculations were performed using Gaussian 09 D.01 and agreement between predicted and measured spectral data has been achieved. Acquired information can be utilized for substance identification for example in various industrial applications or in biological systems.     

Extraordinary transport behavior of gases in isothermally annealed poly(4‐methyl‐1‐pentene) membranes

Poly(4‐methyl‐1‐pentene) (PMP) membranes were modified through isothermal annealing to investigate the change of their crystalline structure and rigid and mobile amorphous fractions (RAF and MAF), assuming a three‐phase model, affected the gas transport behavior. The crystalline structure was characterized by wide‐angle X‐ray diffraction (WAXD) and small‐angle X‐ray scattering (SAXS) techniques, and the free volume properties were analyzed by positron annihilation lifetime spectroscopy. Compared with the pristine membrane, the annealed membranes show higher crystallinity; the crystals undergo partial structural change from form III to form I. The lamellar crystal thickness, rigid amorphous fraction thickness, and long period in the lamellar stacks increase with crystallinity. The annealed PMP membranes exhibit higher permeability due to the increase in larger size free volumes in MAF and higher selectivity due to the increase in smaller size free volumes in RAF, respectively. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2368–2376     

Ultrafast Preparation of Black Phosphorus Quantum Dots for Efficient Humidity Sensing

Black phosphorus quantum dots (BPQDs) have been prepared by a high turbulent shear rate generated from a household kitchen blender. A layer‐by‐layer disintegration mechanism of bulk BP crystals is suggested. As‐synthesized BPQDs have shown excellent humidity sensing and photothermal converting properties. Importantly, this work not only explores potential applications for the BPQDs but also provides a successful paradigm for preparing the QDs of other layered materials.     

Thieno[3,4-c]pyrrole-4,6-dione based copolymers for high performance organic solar cells and organic field effect transistors

Donor-acceptor type copolymers have wide applications in organic field-effect transistors and organic photovoltaic devices. Thieno[3,4-c]pyrrole-4,6-dione (TPD), as an electron-withdrawing unit, has been widely used in D-A type copolymers recently. Till now, the highest power conversion efficiency and mobility of TPD-based copolymers are over 8% and 1.0 cm² V^-1 s^-1 respectively. In this review, the recent progress of TPD-based copolymers in organic solar cells and organic transistors is summarized.     

Prediction of 195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

¹⁹⁵Pt NMR chemical shifts of octahedral Pt(IV) complexes with general formula [Pt(NO₃)_n(OH)_{6 ? n}]^2?, [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} (n = 1–6), and [Pt(NO₃)_{6 ? n ? m}(OH)_m(OH₂)_n]^{?2 + n ? m} formed by dissolution of platinic acid, H₂[Pt(OH)₆], in aqueous nitric acid solutions are calculated employing density functional theory methods. Particularly, the gauge‐including atomic orbitals (GIAO)‐PBE0/segmented all‐electron relativistically contracted–zeroth‐order regular approximation (SARC–ZORA)(Pt) ∪ 6–31G(d,p)(E)/Polarizable Continuum Model computational protocol performs the best. Excellent second‐order polynomial plots of δ_calcd(¹⁹⁵Pt) versus δ_exptl(¹⁹⁵Pt) chemical shifts and δ_calcd(¹⁹⁵Pt) versus the natural atomic charge Q_Pt are obtained. Despite of neglecting relativistic and spin orbit effects the good agreement of the calculated δ ¹⁹⁵Pt chemical shifts with experimental values is probably because of the fact that the contribution of relativistic and spin orbit effects to computed σ^{iso 195}Pt magnetic shielding of Pt(IV) coordination compounds is effectively cancelled in the computed δ ¹⁹⁵Pt chemical shifts, because the relativistic corrections are expected to be similar in the complexes and the proper reference standard used. To probe the counter‐ion effects on the ¹⁹⁵Pt NMR chemical shifts of the anionic [Pt(NO₃)_n(OH)_{6 ? n}]^2? and cationic [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} (n = 0–3) complexes we calculated the ¹⁹⁵Pt NMR chemical shifts of the neutral (PyH)₂[Pt(NO₃)_n(OH)_{6 ? n}] (n = 1–6; PyH = pyridinium cation, C₅H₅NH⁺) and [Pt(NO₃)_n(H₂O)_{6 ? n}](NO₃)_{4 ? n} (n = 0–3) complexes. Counter‐anion effects are very important for the accurate prediction of the ¹⁹⁵Pt NMR chemical shifts of the cationic [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} complexes, while counter‐cation effects are less important for the anionic [Pt(NO₃)_n(OH)_{6 ? n}]^2? complexes. The simple computational protocol is easily implemented even by synthetic chemists in platinum coordination chemistry that dispose limited software availability, or locally existing routines and knowhow. Copyright © 2016 John Wiley & Sons, Ltd.     

Temperature and pH dual‐sensitive polyaspartamide derivatives for antitumor drug delivery

The pH‐sensitive tertiary amino groups were introduced to synthesize temperature and pH dual‐sensitive degradable polyaspartamide derivatives (phe/DEAE‐g‐PHPA) containing pendant aromatic structures and ionizable tertiary amino groups. The thermo/pH‐responsive behavior of phe/DEAE‐g‐PHPA polymer can be tuned by adjusting the graft copolymer composition. Due to the pH sensitivity of the phe/DEAE‐g‐PHPA‐g‐mPEG polymer with hydrophilic long PEG chain, the micelles and the anticancer drug‐loaded micelles were prepared by a quick pH‐changing method without using toxic organic solvent. The obtained polymeric micelles, paclitaxel‐loaded micelles and doxorubicin‐loaded micelles were stable under physiological conditions. Both the drug‐loaded micelles showed much faster release at pH 5 than at pH 7.4. The doxorubicin‐loaded micelles showed obvious and better anticancer activity against both HepG2 and HeLa cells than free doxorubicin. Thus these nontoxic, dual thermo‐ and pH‐sensitive phe/DEAE‐g‐PHPA‐g‐mPEG micelles may be a promising anticancer drug delivery system. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 879–888