A Comparative Pilot Study of Symptom Improvement Before and After Phototherapy in Korean Patients with Perennial Allergic Rhinitis

Although allergic rhinitis is not life threatening, it significantly influences the quality of a patient's life. This study is intended to evaluate the safety and efficacy of phototherapy with low‐level energy of a 650 nm laser irradiation system in perennial allergic rhinitis patients. This clinical trial was an open‐label, single‐center study with 42 perennial allergic rhinitis subjects. Following laser irradiation in the nasal cavity with a laser irradiation system, the efficacy at weeks 1 through 4 was determined. The symptoms were scored with four parameters (nasal obstruction, rhinorrhea, sneezing and itching) before and after illumination of the laser, and the total score was recorded. A survey of Rhinoconjunctivitis Quality of Life Questionnaire (RQLQ) was conducted by patients before and after treatment. Following treatment, significant improvement in the clinical symptoms of nasal obstruction (P < 0.001), rhinorrhea (P = 0.005), sneezing (P = 0.001) and itching (P = 0.003) was reported by 68% of perennial allergic rhinitis patients. The overall RQLQ scores significantly improved by 45% from the baseline with the treatment after 4 weeks. These results indicate that phototherapy is an effective modality for treating perennial allergic rhinitis and is another option in the steroid‐free management of immune‐mediated mucosal diseases.     

Electropolymerization and conductivity of inhibitors with 2–(5–aminopentyl) benzimidazole

Polymer layers of inhibitors are supposed to be electronically and ionically insulating. Potentiostatic investigations of film growth with PAB demonstrated a self-inhibiting process which is explained by the limiting electron conductivity of the polymer. Correspondingly, the electrode capacity C decreases with film thickness d, but the potential drop extends over a thin inner film only with an effective thickness d_eff << d. These results are consistent with the decrease of the current density i of electron transfer reactions. The long-time behaviour of the films is more complex since ions can slowly diffuse into the film. Small ions, like protons, and molecules, like water, can rapidly move through the film. Hence, oxide formation can take place at the metal/PPAB interface. Conductivity data are estimated.     

A Practical and Enantiospecific Synthesis of (−)‐(R)‐ and (+)‐(S)‐Piperidin‐3‐ols

A highly enantiospecific, azide‐free synthesis of (?)‐(R)‐ and (+)‐(S)‐piperidin‐3‐ol in excellent yield was developed. The key step of the synthesis involves the enantiospecific ring openings of enantiomerically pure (R)‐ and (S)‐2‐(oxiran‐2‐ylmethyl)‐1H‐isoindole‐1,3(2H)‐diones with the diethyl malonate anion and subsequent decarboxylation.     

Complex Formation in the Region of Metal Hydrolysis and M(OH)2 Precipitation. A Glass Electrode Potentiometric and Polarographic Study of Cd–(AMPSO)x–(OH)y and Zn–(AMPSO)x–(OH)y Systems

The interaction between cadmium or zinc and AMPSO was investigated by DCP and GEP, at fixed total ligand to total metal concentration ratios and various pH values, at 25.0 °C and 0.1 M KNO₃ ionic strength. For Cd–(AMPSO)_x–(OH)_y system, CdL and CdL(OH) species, were identified, with stability constants values set to (as log β): 2.1±0.1 and 6.2±0.2, respectively. For Zn–(AMPSO)_x–(OH)_y system, the proposed final model with stability constants set to (as log β) is: ZnL=2.5±0.1 and ZnL(OH)₂=12.9±0.2. For both systems, the fact that AMPSO deprotonation occurs in the metal hydrolysis and M(OH)₂ precipitation and the complexes formed are not too strong added a real challenge to data interpretation.     

Theoretical mapping of new L–(N)–L family of species with donor–acceptor bonding between N and ligand L

We perform a computational mapping study of a family of new inorganic species, based on idea of donor–acceptor type bonding between N⁺ and a ligand L with a terminal electron lone pair. The nitrogen ion is seen as being in an atomic ¹D state, with empty 2p acceptor orbitals [I.S.K. Kerkines., A. Papakondylis, A. Mavridis, J. Phys. Chem. A, 2002, 106, 4435]. We consider a series of small ligands, such as PN, CCH⁻, CCCN⁻, , and others. Chemical bonding analysis confirms the suggested bonding picture as characteristic for experimentally known and as well as for most of the predicted species. A number of these new compounds is found to be thermodynamically stable with respect to the existing or . They are candidates for new synthetic targets.     

One donor–two acceptor (D–A1)‐(D–A2) random terpolymers containing perylene diimide,naphthalene diimide,and carbazole units

A series of one donor–two acceptor (D–A₁)‐(D–A₂) random terpolymers containing a 2,7‐carbazole donor and varying compositions of perylene diimide (PDI) and naphthalene diimide (NDI) acceptors was synthesized via Suzuki coupling polymerization. The optical properties of the terpolymers are weighted sums of the constituent parent copolymers and all show strong absorption over the 400 to 700 nm range with optical bandgaps ranging from 1.77 to 1.87 eV, depending on acceptor composition. The copolymers were tested as acceptor materials in bulk heterojunction all‐polymer solar cells using poly[(4,8‐bis‐(2‐ethylhexyloxy)‐benzo[1,2‐b;4,5‐b′]dithiophene)‐2,6‐diyl‐alt‐(4‐(2‐ethylhexanoyl)‐thieno[3,4‐b]thiophene)‐2,6‐diyl] (PBDTTT‐C) as the donor material. In contrast to the optoelectronic properties, the measured device parameters are not composition dependent, and rather depend solely on the presence of the NDI unit, where the devices containing any amount of NDI perform half as well as those using the parent polymer containing only carbazole and PDI. Overall this is the first example of a one donor–two acceptor random terpolymer system containing perylene diimide (PDI) and naphthalene diimide (NDI) acceptor units, and demonstrates a facile method of tuning polymer optoelectronic properties while minimizing the need for complicated synthetic and purification steps. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3337–3345     

Hydrogen bonding structure and many‐body interactions in 1,3,5‐triazine–(water)3 and 1,2,4‐triazine–(water)3 complexes

The hydrogen bonding structure and many‐body interactions between 1,3,5‐triazine (1,2,4‐triazine) and three water molecules are studied using the density functional theory (DFT) B3LYP method and 6‐31++G** basis set. Various structures of 1,3,5‐triazine–(water)₃ and 1,2,4‐triazine–(water)₃ complexes are investigated, and the seven and eight stable structures are reported for 1,3,5‐triazine–(water)₃ and 1,2,4‐triazine–(water)₃, respectively. Many‐body analysis is also carried out to obtain relaxation energy and many‐body interaction energy (two‐, three‐, and four‐body), and the most stable conformer has the basis set superposition error corrected interaction energy of ?92.09 and ?99.53 kJ/mol. The two‐ and three‐body interactions have significant contribution to the total interaction energy, whereas the relaxation energy, four‐body interactions are very small for 1,3,5‐triazine–(water)₃ and 1,2,4‐triazine–(water)₃ complexes. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

A Facile Synthesis of Substituted 2‐(5‐(Benzylthio)‐1,3,4‐oxadiazol‐2‐yl)pyrazine Using Microwave Irradiation and Conventional Method with Antioxidant and Anticancer Activities

A series of novel substituted 2‐(5‐(benzylthio)‐1,3,4‐oxadiazol‐2‐yl)pyrazine derivatives ( 6a – n ) were synthesized under microwave irradiation and conventional conditions with less reaction time with good to excellent yields. All the synthesized compounds were screened for antioxidant and anticancer activities. Out of the 14 prepared derivatives, compounds 6f and 6m were most potent and active with antioxidant and anticancer activities, respectively. Also, the developed technique was simple, easy, and less time consuming.     

Facile coupling of 2‐(1‐ethylthioethenyl)pyrroles with amines: A route to 2‐(1‐aminoethenyl)pyrroles and 1‐amino‐3‐iminopyrrolizines

2‐(2‐Cyano‐1‐ethylthioethenyl)pyrroles are readily coupled (50–55°) with primary and secondary amines at the position 1 of the ethenyl moiety to eliminate ethanethiol and afford 2‐(1‐amino‐2‐cyanoethenyl)pyrroles and/or their cyclic isomers ‐ functionalized 1‐amino‐3‐iminopyrrolizines in good to high yields.     

Synthesis and structures of photoactive manganese–carbonyl complexes derived from 2‐(pyridin‐2‐yl)‐1,3‐benzothiazole and 2‐(quinolin‐2‐yl)‐1,3‐benzothiazole

PhotoCORMs (photo‐active CO‐releasing molecules) have emerged as a class of CO donors where the CO release process can be triggered upon illumination with light of appropriate wavelength. We have recently reported an Mn‐based photoCORM, namely [MnBr(pbt)(CO)₃] [pbt is 2‐(pyridin‐2‐yl)‐1,3‐benzothiazole], where the CO release event can be tracked within cellular milieu by virtue of the emergence of strong blue fluorescence. In pursuit of developing more such trackable photoCORMs, we report herein the syntheses and structural characterization of two Mn^I–carbonyl complexes, namely fac‐tricarbonylchlorido[2‐(pyridin‐2‐yl)‐1,3‐benzothiazole‐κ²N ,N ′]manganese(I), [MnCl(C₁₂H₈N₂S)(CO)₃], (1), and fac‐tricarbonylchlorido[2‐(quinolin‐2‐yl)‐1,3‐benzothiazole‐κ²N ,N ′]manganese(I), [MnCl(C₁₆H₁₀N₂S)(CO)₃], (2). In both complexes, the Mn^I center resides in a distorted octahedral coordination environment. Weak intermolecular C—H…Cl contacts in complex (1) and Cl…S contacts in complex (2) consolidate their extended structures. These complexes also exhibit CO release upon exposure to low‐power broadband visible light. The apparent CO release rates for the two complexes have been measured to compare their CO donating capacity. The fluorogenic 2‐(pyridin‐2‐yl)‐1,3‐benzothiazole and 2‐(quinolin‐2‐yl)‐1,3‐benzothiazole ligands provide a convenient way to track the CO release event through the `turn‐ON' fluorescence which results upon de‐ligation of the ligands from their respective metal centers following CO photorelease.     

Ru修饰前后Pd(111)面的性质及对糠醛吸附的比较研究

采用密度泛函理论研究了Pd(111)面和Ru-Pd(111)面的性质及对糠醛的吸附.原子尺寸因素、相对键长、形成能及d带中心等计算结果表明,Ru-Pd(111)面比Pd(111)面稳定且活性强,Ru的修饰优化了Pd(111)面的几何构型.糠醛在Pd(111)面及Ru-Pd(111)面的初始吸附位分别为P(top-bridge)位及P(Pd-fcc-Ru-fcc)位时,吸附能最大,吸附构型最稳定.由电荷布局和差分电荷密度可得,糠醛在Ru-Pd(111)面上电荷转移数更多,相互作用更强烈,因此吸附能更大.分析态密度可知,产生吸附的主要原因是位于-7.34 eV处至费米能级处的p,d轨道杂化.吸附于Ru-Pd(111)面后糠醛分子的p轨道向低能级偏移程度更明显,使Ru改性后的Pd催化剂具有更好的催化活性.     

A linear solvation energy relationship study for the reactivity of 2‐(4‐substituted phenyl)‐cyclohex‐1‐enecarboxylic, 2‐(4‐substituted phenyl)‐benzoic,and 2‐(4‐substituted phenyl)‐acrylic acids with diazodiphenylmethane in various solvents

The reactivities of 2‐(4‐substituted phenyl)‐cyclohex‐1‐enecarboxylic acids, 2‐(4‐substituted phenyl)‐benzoic acids, and 2‐(4‐substituted phenyl)‐acrylic acids with diazodiphenylmethane in various solvents were investigated. To explain the kinetic results through solvent effects, the second‐order rate constants of the examined acids were correlated using the Kamlet–Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of multiple linear regression analysis, and the solvent effects on the reaction rates were analyzed in terms of initial and transition state contributions. The signs of the equation coefficients support the proposed reaction mechanism. The solvation models for all investigated carboxylic acids are suggested. The quantitative relationship between the molecular structure and the chemical reactivity is discussed, as well as the effect of geometry on the reactivity of the examined molecules. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 430–439, 2010     

A 2D coordination polymer assembled from a nickel(II) tetraazamacrocyclic cation and 4,4′‐(dimethylsilanediyl)diphthalate(3–) linker

The preformed nickel(II) complex of the 14‐membered macrocyclic ligand 1,4,8,11‐tetraazacyclotetradecane (cyclam, L), when treated with 4,4′‐(dimethylsilanediyl)diphthalic acid (H₄A) in a DMF/H₂O mixture (4:1 v/v) under heating, leads to [Ni(L)]₃(HA)₂·3DMF ( I·DMF ). Redissolution of this compound in a DMF/H₂O/MeOH mixture (4:1:30 v/v/v) with mild acidification under gentle heating results in the formation of a similar compound but containing water and methanol molecules of crystallization, [Ni(L)]₃(HA)₂·5H₂O·2MeOH ( II·H₂O ). At lower temperature and concentration of reactants and longer reaction time, single crystals of composition {[{Ni(L)}₃(HA)₂]·4CH₃OH}_n ( II·MeOH ) were isolated. Single‐crystal X‐ray diffraction analysis of this compound, which, according to PXRD is isostructural with II·H₂O but different from I·DMF , revealed its two‐dimensional (2D) polymeric structure, i.e. poly[[bis{μ₃‐4‐[(4‐carboxy‐3‐carboxylatophenyl)dimethylsilyl]benzene‐1,2‐dicarboxylato‐κ³O¹:O²:O^3′}tris(1,4,8,11‐tetraazacyclotetradecane‐κ⁴N)trinickel(II)] methanol tetrasolvate], {[Ni₃(C₁₈H₁₃O₈Si)₂(C₁₀H₂₄N₄)₃]·4CH₃OH}_n. It is built up of the monoprotonated tricarboxylate HA^3? ligand coordinated in a monodentate manner in the axial positions of two crystallographically independent Ni^II cations, one of which is located on a crystallographic inversion centre. Both metal ions adopt a slightly tetragonally elongated trans‐N₄O₂ octahedral geometry. The compound has a lamellar structure with polymeric layers oriented parallel to the (10) plane, which are in turn linked via hydrogen bonds involving protonated carboxylic acid groups of the ligand. Bulk compounds I·DMF and II·H₂O were characterized by FT–IR and diffuse reflectance spectroscopy and thermogravimetry, which provide evidence of their structural differences.     

Synthesis,Structure, and Solution Study of a Mercury(II) Complex with the Ligand [1‐(2‐Methoxyphenyl)‐3‐(4‐chlorophenyl)]triazene

The title ligand, [1‐(2‐methoxyphenyl)‐3‐(4‐chlorophenyl)]triazene, H L ( 1 ), was prepared. In a reaction with Hg(NO₃)₂ it forms the complex [Hg(C₂₆H₂₂Cl₂N₆O₂)], [Hg L ₂] ( 2 ). Both compounds were characterized by means of X‐ray crystallography, CHN analysis, FT‐IR, ¹H NMR, and ¹³C NMR spectroscopy. In the structure of compound 1 , two independent fragments are present in the unit cell. They exhibit trans arrangement about the –N=N– double bond. The dihedral angles between two benzene rings in both fragments are 4.36 and 18.79 Å, respectively. Non‐classic C–H ··· N hydrogen bonding and C–H ··· π interactions form a layer structure along the crystallographic ab plane [110]. In compound 2 , the Hg^II atom is hexacoordinated by two tridentate [1‐(2‐methoxyphenyl)‐3‐(4‐chlorophenyl)]triazenide ligands through a N₂O₂ set. In addition, in the structure of 2 , monomeric complexes are connected to each other by C–H ··· π stacking interactions, resulting in a 2D architecture. These C–H ··· π edge‐to‐face interactions are present with H ··· π distances of 3.156 and 3.027 Å. The results of studies of the stoichiometry and formation of complex 2 in methanol solution were found to support its solid state stoichiometry.     

A Study on the Intramolecular Mitsunobu Reaction of N6‐(ω‐Hydroxyalkyl)adenines

The cyclization of N ⁶‐(ω‐hydroxyalkyl)adenines with a N⁶H‐group leads to N⁶,N1 ring closure regardless of the method of the cyclization that was used. Five‐membered to eight‐membered rings were obtained using NBS/PPh₃; however, under Mitsunobu conditions, the eight‐membered fused purine was not formed. Surprisingly, the cyclization of N ⁶‐methyl‐N ⁶‐(4‐hydroxybutyl)adenine only leads to N⁶,N7 ring closure using both methods.     

Growth and kinetics of in vitro poly([R]‐(–)‐3‐hydroxybutyrate) granules interpreted as particulate polymerization with coalescence

Transmission electron microscopy (TEM) and Cryo‐TEM were used to study the growth kinetics of poly(3‐hydroxybutyrate) granules produced by in vitro polymerization. The in vitro formation of poly(3‐hydroxybutyrate) uses a recombinant form of the PHA synthase to polymerize [R]‐(–)‐3‐hydroxybutyryl‐CoA. Since the in vitro reaction contains only synthase and monomer, it is a simpler system than the in vivo biosynthesis of poly(3‐hydroxybutyrate). TEM and Cryo‐TEM were used in conjunction with image analysis to examine the granules that were formed in the in vitro reaction. The in vitro reaction yielded spherical granules of rapidly increasing size; the initially observed granules were already larger than 0.1 μm. While the average granule diameter and volume increased with reaction time, the number of granules decreased throughout the reaction due to coalescence. Basic kinetic parameters, including K_M and V_max were determined and compared to those reported for the in vivo biosynthesis of poly(3‐hydroxybutyrate). In addition it was found that the granules formed by this process were essentially noncrystalline. A computer simulation of the reaction, based on initial formation of relatively large microporous granules that consolidate by expulsion of water during polymerization, accounted for the shape of the kinetic curves.     

A Facile and Simple Synthesis of Novel 2‐(substituted)‐5‐(1‐methyl‐1H‐indazol‐3‐yl)‐Oxazole Derivatives

Novel 2‐(substituted)‐5‐(1‐methyl‐1H‐indazol‐3‐yl)‐oxazoles ( 13 ) were synthesized in moderate yields, from 1‐methyl‐1H‐Indazole 3‐carboxylic acid ( 1 ), by converting it into a variety of amides ( 12 ) and further its heterocyclization. The structures of all the compounds have been elucidated on the basis of IR, ¹H‐NMR, and HRMS.