High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

Reinventing Hsp90 Inhibitors: Blocking C‐Terminal Binding Events to Hsp90 by Using Dimerized Inhibitors

Heat shock protein 90 (Hsp90) is a molecular chaperone (90 kDa) that functions as a dimer. This protein facilitates the folding, assembly, and stabilization of more than 400 proteins that are responsible for cancer development and progression. Inhibiting Hsp90’s function will shut down multiple cancer‐driven pathways simultaneously because oncogenic clients rely heavily on Hsp90, which makes this chaperone a promising anticancer target. Classical inhibitors that block the binding of adenine triphosphate (ATP) to the N‐terminus of Hsp90 are highly toxic to cells and trigger a resistance mechanism within cells. This resistance mechanism comprises a large increase in prosurvival proteins, namely, heat shock protein 70 (Hsp70), heat shock protein 27 (Hsp27), and heat shock factor 1 (HSF‐1). Molecules that modulate the C‐terminus of Hsp90 are effective at inducing cancer‐cell death without activating the resistance mechanism. Herein, we describe the design, synthesis, and biological binding affinity for a series of dimerized C‐terminal Hsp90 modulators. We show that dimers of these C‐terminal modulators synergistically inhibit Hsp90 relative to monomers.     

Crosslinkable high dielectric constant polymer dielectrics for low voltage organic field‐effect transistor memory devices

I n this study, we successfully synthesized water/methanol soluble random copolymers with a high dielectric constant, poly(n‐(hydroxymethyl) acrylamide‐co‐5‐(9‐(5‐(diethylamino)pentyl)?2‐(4‐vinylphenyl)?9H‐fluorene(P(NMA‐co‐F6NSt)), which contained chemical crosslinkable segment (NMA) and hole trapping building block (F6NSt). The feeding molar ratios of two monomers (NMA:F6NSt) were set as 100:0, 95:5, 80:20, and 67:33 for the copolymers of P1 , P2 , P3, and P4 , respectively. The crosslinked P(NMA‐co‐F6NSt) thin film could serve as both dielectric and charge storage layers in organic field‐effect transistor (OFET) memory device and exhibited high k (i.e., 4.91–6.47) characteristics, leading to a low voltage operation and a small power consumption. Devices based on the P1 ‐ P4 dielectrics showed excellent insulating properties and good charge storage performance under a low operating voltage in a range of ±5V because of tightly network structures and well‐dispersed trapping cites. In particular, P3 ‐based memory device exhibited a large memory window of 4.13 V with stable data retention stability over 10⁴ s, a large on/off ratio of 10⁴, and good endurance characteristics as high as 200 cycles. The above results suggested that a high‐performance OFET memory device could be facilely achieved using the novel crosslinkable high‐k copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3224–3236     

Pincer‐Type Platinum(II) Complexes Containing N‐Heterocyclic Carbene (NHC) Ligand: Structures,Photophysical and Anion‐Binding Properties,and Anticancer Activities

Two classes of pincer‐type Pt^II complexes containing tridentate N‐donor ligands ( 1 – 8 ) or C‐deprotonated N^C^N ligands derived from 1,3‐di(2‐pyridyl)benzene ( 10 – 13 ) and auxiliary N‐heterocyclic carbene (NHC) ligand were synthesized. [Pt(trpy)(NHC)]²⁺ complexes 1 – 5 display green phosphorescence in CH₂Cl₂ (Φ: 1.1–5.3 %; τ: 0.3–1.0 μs) at room temperature. Moderate‐to‐intense emissions are observed for 1 – 7 in glassy solutions at 77 K and for 1 – 6 in the solid state. The [Pt(N^C^N)(NHC)]⁺ complexes 10 – 13 display strong green phosphorescence with quantum yields up to 65 % in CHCl₃. The reactions of 1 with a wide variety of anions were examined in various solvents. The tridentate N‐donor ligand of 1 undergoes displacement reaction with CN^? in protic solvents. Similar displacement of the N^C^N ligand by CN^? has been observed for 10 , leading to a luminescence “switch‐off” response. The water‐soluble 7 containing anthracenyl‐functionalized NHC ligand acts as a light “switch‐on” sensor for the detection of CN^? ion with high selectivity. The in vitro cytotoxicity of the Pt^II complexes towards HeLa cells has been evaluated. Complex 12 showed high cytotoxicity with IC₅₀ value of 0.46 μM , whereas 1 – 4 and 6 – 8 are less cytotoxic. The cellular localization of the strongly luminescent complex 12 traced by using emission microscopy revealed that it mainly localizes in the cytoplasmic structures rather than in the nucleus. This complex can induce mitochondria dysfunction and subsequent cell death.     

Ba3V2S4O3: A Mott Insulating Frustrated Quasi‐One‐Dimensional S=1 Magnet

Through a solid‐state reaction, a practically phase pure powder of Ba₃V₂S₄O₃ was obtained. The crystal structure was confirmed by X‐ray single‐crystal and synchrotron X‐ray powder diffraction (P6₃, a=10.1620(2), c=5.93212(1) Å). X‐ray absorption spectroscopy, in conjunction with multiplet calculations, clearly describes the vanadium in charge‐disproportionated V^IIIS₆ and V^VSO₃ coordinations. The compound is shown to be a strongly correlated Mott insulator, which contradicts previous predictions. Magnetic and specific heat measurements suggest dominant antiferromagnetic spin interactions concomitant with a weak residual ferromagnetic component, and that intrinsic geometric frustration prevents long‐range order from evolving.     

Synthesis and characterization of double hydrophilic block copolymers containing semi-rigid and flexible segments

3-Methyl-(E)-stilbene (3MSti) and 4-(diethylamino)-(E)-stilbene (DEASti) monomers are synthesized and polymerized separately with maleic anhydride (MAn) in a strictly alternating fashion using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques. The optimal RAFT chain transfer agents (CTAs) for each copolymerization affect the reaction kinetics and CTA compatibilities. Psuedo-first order polymerization kinetics are demonstrated for the synthesis of poly((3-methyl-(E)-stilbene)-alt-maleic anhydride) (3MSti-alt-MAn) with a thiocarbonylthio CTA (methyl 2-(dodecylthiocarbonothioylthio)−2-methylpropionate, TTCMe). In contrast, a dithioester CTA (cumyl dithiobenzoate, CDB) controls the synthesis of poly((4-(diethylamino)-(E)-stilbene)-alt-maleic anhydride) (DEASti-alt-MAn) with pseudo-first order polymerization kinetics. DEASti-alt-MAn is chain extended with 4-acryloylmorpholine (ACMO) to synthesize diblock copolymers and subsequently converted to a double hydrophilic polyampholyte block copolymers (poly((4-(diethylamino)-(E)-stilbene)-alt-maleic acid))-b-acryloylmorpholine) (DEASti-alt-MA)-b-ACMO) via acid hydrolysis. The isoelectric point and dissociation behavior of these maleic acid-containing copolymers are determined using ζ-potential and acid–base titrations, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 219–227     

Iron porphyrin catalysed light driven C–H bond amination and alkene aziridination with organic azides

Visible light driven nitrene transfer and insertion reactions of organic azides are an attractive strategy for the design of C–N bond formation reactions under mild reaction conditions, the challenge being lack of selectivity as a free nitrene reactive intermediate is usually involved. Herein is described an iron(iii) porphyrin catalysed sp³ C–H amination and alkene aziridination with selectivity by using organic azides as the nitrogen source under blue LED light (469 nm) irradiation. The photochemical reactions display chemo- and regio-selectivity and are effective for the late-stage functionalization of natural and bioactive compounds with complexity. Mechanistic studies revealed that iron porphyrin plays a dual role as a photosensitizer and as a catalyst giving rise to a reactive iron–nitrene intermediate for subsequent C–N bond formation.

An iron(iii) porphyrin catalysed sp³ C–H amination and alkene aziridination with broad substrate scope under mild conditions is conducted, with selectivity through the use of organic azides as the nitrogen source under blue LED light irradiation.     

OH+C2H3F的反应机理及产物支化比反应的理论研究

本文对HOC₂H₃F可能解离通道的势能面进行从头算CCSD(T)/CBS//B3LYP/6-311G(d，p)计算，同时对速率常数进行Rice-Ramsperger-Kassel-Marcus计算. 生成主要产物CH₂CHO+HF最有利的反应途径是OHC₂H₃F→i2→TS14→i6→TS9→i3→TS3→CH₂CHO+HF，其中速率决定步骤是HF通过TS11从CO桥接位置解离，能量比反应物高3.8 kcal/mol. 借助中间态TS14，F原子从C_α迁移到C_β位置生成CH₂O+CH₂F，然后通过中间态TS16，H从O迁移到C_α位置；通过中间态TS5，C-C键断裂生成产物，其能量比反应物低1.8 kcal/mol，比TS11低4.0 kcal/mol.     

分光技术在自由电子激光结合里德堡态氢原子飞行时间谱装置中的应用

本文描述了一种应用于自由电子激光结合高里德堡态氢原子飞行时间谱装置中的分光方法，以及该方法应用于小分子(如₂S)光解动力学研究中的必要性. 拉曼-α辐射(121.6 nm)，用作H原子产物探测的激光，是在Kr/Ar气介质中利用四波混频产生的. 利用透镜对不同波长的光有不同的折射率，四波混频后的混合光在经过一片离轴的氟化锂透镜后，121.6 nm的激光将会与212.6和845 nm在空间上分开. 在激光到达反应中心前利用挡板挡住212.6和845 nm的激光，只让121.6 nm的光经过反应中心，从而消除212.6 nm激光产生的背景信号对实验的干扰. 结合自由电子激光，成功地研究了H₂S在122.95 nm波长下的光解动力学，采集到了产物时间飞行谱. 本文展示了转换得到的产物总平动能谱，解离机理与121.6 nm波长下的结果相似. 实验结果显示，该方法成功地解决了分子在VUV波段进行光解动力学研究的难题，消除了这些分子在紫外光波段因为强烈吸收而产生的背景信号.