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In this work, five 3,6,11-trisubstituted-dibenzo[a,c]phenazine (2–6) derivatives were synthesized by employing Palladium-catalyzed Suzuki–Miyaura ‘C–C bond’ coupling reaction and characterized. Absorption spectra of 2–6 show the formation of charge-transfer complexes. Dyes exhibit blue-green fluorescence with emission maxima 434–506 nm in various solvents and neat solid film. To elucidate AIE phenomenon, photophysical properties of dye 2 and 3 in different THF/water mixture were studied. The HOMO and LUMO energy level were found in the range of − 6.38 to − 6.82 eV and − 3.67 to − 3.75 eV with an electrochemical bandgap of 2.71–3.08 eV. The HOMO and LUMO distribution in molecules were further studied by DFT/TD–DFT calculations. Herein, characteristic blue emission, comparable energy levels with n-type materials, and good thermal stability of derivatives make them a potential candidate for their application in optoelectronics.

To understand the structure–property relationship, we have designed and synthesized seven novel donor–acceptor based phenazine–amines, 2–8, by the Buchwald–Hartwig coupling amination reaction in moderate yield. The synthesized molecules were fully characterized and the influence of modulating the donor and phenazine core on the optoelectrochemical properties was studied. The absorption spectra of 2–8 display intramolecular charge transfer (ICT) transitions in the range of 431–501 nm. Dyes 2–8 exhibit positive solvatofluorochromism and emit in the cyan blue-red region with emission maxima at 498–641 nm on excitation at their respective ICT maxima in toluene, chloroform, DCM and neat solid film. The photophysical studies of the dyes in different THF/water mixtures revealed aggregation induced emission (AIE) features in dyes 2, 3 and 5. The HOMO and LUMO energy levels were found to be in the ranges of −5.39 to −5.68 eV and −3.59 to −3.71 eV, respectively, with electrochemical band gaps within the range 1.73–2.04 eV. Theoretical studies of the molecules were also carried out by using TD-DFT calculations. The comparable electrochemical energy levels to ambipolar materials, solid state luminescence with AIE characteristics and good thermal stability of the synthesized dyes signify their potential to be used as solid state emitters and ambipolar materials in optoelectronics.

BackgroundCD8 T cell are a crucial part of the immune response to tumors, with CD8 infiltration predicting disease progression in numerous cancer types. Recently two subsets of CD8 T cells that respond to tumors have been described, a stem-like (TCF1+) CD8 T cell that can give rise to a more cytotoxic terminally differentiated (TD) (TCF1-Tim3+) CD8 T cell. In this study we aimed to understand the origin of stem-like TCF1+ CD8 T cells within tumors.MethodsHuman patient TDLN and tumor samples from kidney and prostate cancer were processed after resection and used for flow cytometry, RNA-seq, TCR-seq and whole genome DNA methylation analysis. We also used a prostate cancer mouse model that expresses the LCMV GP protein (TRAMPC1-LCMV-GP) to track tumor-specific CD8 T cells in both TDLNs and tumors.ResultsWe studied human prostate and kidney cancer tumor-draining lymph nodes (TDLN) and found that CD8 T cells are activated but fail to acquire an effector phenotype within the TDLN. Instead, they share functional, transcriptional, and epigenetic traits with stem-like cells in the tumor. We also found that activated CD8 T cells from TDLNs shared TCR overlap with both CD8 subsets within tumors. This suggests that these activated cells are a precursor to the stem-like CD8 T cells in tumors. To further test this hypothesis, we used our TRAMPC1-LCMV-GP tumor model to study tumor-specific CD8 T cell activation. We found that CD8 T cells are activated in TDLNs but fail to acquire an effector program. These cells then establish the stem-like CD8s within tumor where they require additional co-stimulation from antigen presenting cells to differentiate into TCF1- TD CD8 T cells. This is strikingly different from canonical CD8 T cell activation to acute viruses, where the effector program is acquired immediately. We also showed that human stem-like CD8 T cells require co-stimulation and TCR stimulation to divide and differentiate into terminally differentiated CD8s in-vitro, and DCs from autologous tumors can also induce this differentiation.ConclusionsOverall this work shows a model of CD8 T cell activation in response to tumors that has two distinct phases. The first occurs in the TDLN where CD8 T cells are initially activated, the second occurs in the tumor where CD8 T cells acquire an effector function after additional co-stimulation. This model of T cell differentiation adds to our understanding of basic CD8 T cell biology and has important implications to improve our current immunotherapies.

A series of eight novel donor‒acceptor based quinoxaline‒amine derivatives 2–9 were prepared by modulating donor species on quinoxaline core with Buchwald‒Hartwig coupling amination reaction. The synthesized molecules were fully characterized and studied for impact of D−A interaction on optoelectrochemical properties of derivatives. Absorption spectra of 2−9 display intramolecular charge transfer (ICT) transitions in the range of 377–456 nm. Dyes 2–9 show positive solvatochromism in emission and emit in blue‒orange region with emission maxima 472–592 nm on excitation at their respective ICT maxima in toluene, chloroform, DCM and neat solid film. Herein, dyes 2, 3 and 7 which possess intense emission in solid state were further studied for Aggregation Induced Emission (AIE) effect. The HOMO and LUMO energy level for compound 2–9 obtained by CV were found in the range of −5.23 to −5.83 eV and −3.55 to −3.74 eV. Theoretical studies of molecules were also carried out by using TD‒DFT calculations. The comparable HOMO and LUMO energy level of 2−9 with reported ambipolar materials and efficient solid state emission make synthesized compounds potential candidate for solid state emissive, ambipolar materials in organic electronics.

In this study, a series of bipolar, donor–acceptor–donor (D–A–D)-based quinoxaline diarylamine/heterocyclic amine derivatives were synthesized in good yield by the Buchwald–Hartwig amination reaction and fully characterized by different spectroscopic methods. The optoelectronic properties of the dyes were scrutinised using electronic absorption and fluorescence spectroscopy, cyclic voltammetry, thermogravimetric analysis, and differential scanning calorimetry and further by the DFT and TDDFT study. The photophysical properties of dyes are influenced by their peripheral amines and the nature of solvents used. The presence of intramolecular charge transfer (ICT) transitions in the absorption spectra of amine derivatives is attributed to the existence of the D–A building units, which induces blue to yellow emission in both the solution and the neat solid film. Strikingly intense solid-state emission in some of the dyes has moved the area of study toward aggregation induced emission (AIE) phenomenon and showed the formation of nanoaggregates at above 50% water fraction (fw) of THF/H2O solvent mixtures, which was further confirmed by the FEG-SEM technique. The linkage of different amines with the quinoxaline core moiety tunes the electrochemical properties with lower band gaps and comparable HOMO–LUMO energy levels in reported ambipolar materials. Thus, the existence of a strong solid-state emission with AIE activity, ambipolar nature and good thermal properties of dyes attribute their use as solid-state emitters and ambipolar materials in optoelectronic devices.

A series of donor–acceptor-based 6H-indolo[2,3-b]quinoxaline amine derivatives were synthesized with different donor amines. The impact of the different donor moieties on 6H-indolo[2,3-b]quinoxaline was systematically examined by absorption-emission spectroscopy, cyclic voltammetry and theoretical studies. The photophysical properties of these molecules, such as intramolecular charge transfer transitions (400 to 462 nm) and emission (491 to 600 nm), were influenced by the nature of the peripheral amines. Further, the solid-state emission demonstrated by some of the dyes aroused our interest in performing photophysical studies on the aggregation-induced emission phenomenon; these dyes showed nanoparticle formation in THF/H2O solvent mixtures. Varying the strength of the peripheral amines in the derivatives also tuned the electrochemical data, with lower band gaps (1.56 to 2.21 eV) and comparable HOMO–LUMO energy levels with reported ambipolar materials. The donor–acceptor architectures and HOMO–LUMO energies were further rationalized using DFT/TDDFT calculations. Thus, the opto-electrochemical studies and high thermal stability of these molecules indicate their potential application as solid-state emissive, ambipolar materials in optoelectronic devices.

Parasitic worms have a remarkable ability to modulate host immune responses through several mechanisms including excreted/secreted proteins (ESP), yet the exact nature of these proteins and their targets often remains elusive. Here, we performed mass spectrometry analyses of ESP (TsESP) from larval and adult stages of the pig whipworm Trichuris suis (Ts) and identified ~350 proteins. Transcriptomic analyses revealed large subsets of differentially expressed genes in the various life cycle stages of the parasite. Exposure of bone marrow-derived macrophages and dendritic cells to TsESP markedly diminished secretion of the pro-inflammatory cytokines TNFα and IL-12p70. Conversely, TsESP exposure strongly induced release of the anti-inflammatory cytokine IL-10, and also induced high levels of nitric oxide (NO) and upregulated arginase activity in macrophages. Interestingly, TsESP failed to directly induce CD4+ CD25+ FoxP3+ regulatory T cells (Treg cells), while OVA-pulsed TsESP-treated dendritic cells suppressed antigen-specific OT-II CD4+ T cell proliferation. Fractionation of TsESP identified a subset of proteins that promoted anti-inflammatory functions, an activity that was recapitulated using recombinant T. suis triosephosphate isomerase (TPI) and nucleoside diphosphate kinase (NDK). Our study helps illuminate the intricate balance that is characteristic of parasite-host interactions at the immunological interface, and further establishes the principle that specific parasite-derived proteins can modulate immune cell functions.

Here, pyridopyrazino[2,3-b]indole based D–A assembly was designed and synthesized with modulation of various electron-donating/withdrawing substituent and characterized by various spectroscopic methods. Pyridopyrazino[2,3-b]indole derivatives show inbuilt intramolecular charge transfer (ICT) transition which established D–A building in molecules and induces blue-green emission in the solution state. However, solid-state emission characteristics explore the emission property of some molecules towards aggregation-induced emission (AIE) effect which leads to the formation of emissive nano aggregates in THF/H2O mixture. Alteration of substituent on pyridopyrazino[2,3-b]indole segment effectively tune electrochemical property and resulting LUMO energy level was found to be comparable with reported electron transporting/n-type materials. These properties and good thermal stability indicate that molecules have the potential to be used as solid-state emitter and n-type materials in optoelectronic devices. Pyridopyrazino[2,3-b]indole derivatives possess inbuilt intramolecular charge-transfer to reveal donor-acceptor assembly within a molecule. Opto-electrochemical properties of it greatly influenced by an inductive and mesomeric effect caused by a substituted group. Strong solid-state emission owned by some molecule display AIE phenomenon. Additionally, LUMO value of derivatives exhibits electron-transporting ability hence could be used in organic electronics.

We herein report the design and synthesis of six new donor–acceptor (D–A) type, bipolar compounds containing 2,3-di(pyridin-2-yl)quinoxaline as an acceptor and diaryl/heterocyclic amine donors prepared by palladium catalyzed Buchwald‒Hartwig coupling reaction. The synthesized compounds have been characterized by different spectroscopic techniques, electrochemical analysis and thermal method. Further, the structure of compound 4 was confirmed by single crystal X−ray analysis. The characteristic absorption (λmax) with ICT feature and emission maxima (λemm) in various solvents of 2–7 are found in the range of 389–440 nm and 460–555 nm, respectively, with stoke's shift within 3664−6945 cm−1. The positive solvatochromism due to solvent polarity observed in dyes confirmed by the Mc−Rae and Weller's plots. The dyes 2–7 show cyan blue to orange emission (λemm = 493–581 nm) in solid film. The cyclic voltammetry (CV) was used to analyze the HOMO and LUMO energy levels of the molecules and further it was correlated by density functional theory (DFT) calculations. The excellent thermal stability and opto-electronic properties warrants the application of these dyes in opto−electronic devices.

In this work, we have synthesized a series of donor-acceptor type molecules involving electron donor diarylamines/heterocyclic amines and electron acceptor 9,10-anthraquinone by employing palladium catalyzed C−N bond forming amination reaction in good yield and fully characterized. Absorption spectra of all the synthesized molecules showed an intramolecular charge transfer (ICT) transitions in the range of 417−554 nm. Electrochemical properties of the compounds were studied by cyclic voltammetry (CV). The HOMO and LUMO energy levels of synthesized compounds were found in the range of −5.18 to −5.79 eV and −3.22 to −3.53 eV respectively as calculated by CV. Theoretical studies were also carried out by using DFT and TD-DFT calculation. On the basis of HOMO and LUMO energy levels, synthesized compounds could be used as ambipolar materials in organic electronics.

Imidazoanthraquinone derivatives with extended π conjugation were synthesized and characterized. Palladium-catalyzed Suzuki–Miyaura and Sonogashira couplings were employed to synthesize these derivatives. Photophysical and electrochemical studies of the new imidazoanthraquinone derivatives were performed, and their absorption and emission maxima were observed in a wide visible range. The photophysical studies revealed the formation of charge-transfer complexes. Cyclic voltammetry provided good estimates of the reduction and oxidation potentials of these compounds and eventually the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels. Electrochemical studies revealed low-lying ELUMO values of ca. –3.7 eV for these compounds. The donor–acceptor architecture and HOMO–LUMO energies were further studied through DFT calculations. On the basis of the ELUMO values of these compounds, photoquenching experiments were performed in the presence of the electron donor poly(3-hexylthiophene) (P3HT). These experiments suggest that these compounds could be used as electron acceptors in heterojunction solar cells.

A series of five novel dyes based on indolo[2,3-b]quinoxaline skeleton, derived from anthraquinone, have been synthesized through cyclo-condensation reaction in good yield. The photophysical, electrochemical and thermal properties along with computed HOMO-LUMO energy levels were studied for the synthesized compounds. Their absorption and photoluminescence properties were investigated in various solvents and in neat solid film and found to possess characteristic electronic absorption and emission spectra which strongly depend on the nature of solvents used. Compounds show intramolecular charge transfer transitions (ICT) in the range of 501–561 nm with high molar absorption coefficient (e). These indoloquinoxaline derivatives emit in the range of 580–648 nm in solutions and 672–700 nm (red region) in neat solid films. Electrochemical data indicate that the dyes possess relatively low–lying LUMO levels in the range −3.29 to −3.43 eV. The thermal stability observed for these compounds suggests their use under ambient conditions. The in–built donor–acceptor architecture and HOMO–LUMO energies were further rationalized using DFT calculations. This study suggests that these compounds have potential to be used as n–type materials for optoelectronic devices.

A series of novel donor–acceptor type of molecules (2–6) based on dibenzo[a,c]phenazine were synthesized by employing a palladium = catalyzed C–N bond forming amination reaction in a good yield and were then fully characterized, whereby the optical properties of 2–6 were determined by UV-vis absorption, fluorescence spectroscopy, and the electrochemical properties by cyclic voltammetry. The absorption spectra of 2–6 showed intramolecular charge transfer (ICT) transitions in the range of 447–513 nm in solution. The HOMO and LUMO energy levels of 2–6 were in the range from −5.03 to −5.29 eV and −2.75 to −2.87 eV, respectively, with an electrochemical band gap within 2.26–2.45 eV. The HOMO energy levels of 2–6 are comparable with those of the most commonly used hole-transporting materials, which makes them potential candidates for hole-transporting materials in organic electronics.

Magnetic binary oxide particles (MBOP) were prepared by template method using chitosan in the laboratory for the removal of As(III) from water. The prepared MBOP has super paramagnetic property which is sufficient for magnetic separation. Column study was performed at two different flow rates of 2.0ml/min and 5.0ml/min and comparison was made with regenerated MBOP, commercial activated carbon and commercial activated alumina. It is observed that fresh MBOP has higher breakthrough time and capacity than regenerated MBOP by a factor of 1.25 and 1.37 respectively. In Logit method, the values of K (adsorption rate constant) and N (adsorption capacity coefficient) were obtained as 0.2066 (L/mgh) and 1014(mg/L) for 5.0ml/min flow rate. All the drinking water parameters are within the limit of BIS 10500-2012. Toxicity characteristic leaching procedure (TCLP) and semi dynamic tests were performed for the mix ratios of 01:02:01, 01:02:05 and 01:02:10 and were found safe for the disposal.

We herein report the design and synthesis of novel donor‒acceptor (D‒A) type 2,3-di(thiophene-2-yl)pyrido[2,3-b]pyrazine and 2,3-di(furan-2-yl)pyrido[2,3-b]pyrazine amine derivatives by employing palladium catalyzed Buchwald‒Hartwig coupling reaction. The synthesized compounds have been characterized by spectroscopic, electrochemical and thermal methods. Absorption spectra of all dyes showed an intramolecular charge transfer (ICT) transitions (λmax = 438–473 nm) in solution and positive solvatochromism with emission maxima in blue‒orange region (λemm = 489–617 nm). Further, solid state emission was studied for aggregation‒induced emission (AIE) effect in THF–water system due to the nanoparticles formation, as confirmed by FEG‒SEM technique. The HOMO (−5.22 to −5.75 eV) and LUMO (−3.35 to −3.45 eV) energy level of these molecules were measured by cyclic voltammetry and correlated by DFT calculations. On the basis of comparable HOMO and LUMO energy level with reported ambipolar materials and efficient solid state emission warrants the application of synthesized compounds as emitter and ambipolar charge transport materials in organic electronics.

Background: Cases of chronic obstructive pulmonary disease (COPD) increasing day by day. Smoking is the major causative agent for COPD. The present study undertaken to estimate the deterioration of liver functions in COPD patients due to smoking. Aims and Objectives: This study aims to investigate various liver function tests (LFTs) such as total bilirubin, alanine amino transferase/serum glutamic pyruvic transaminase (SGPT), aspartate amino transferase/SGPT, alkaline phosphatase (ALP), serum ammonia, and serum albumin among COPD patients. To correlate LFTs with forced expiratory volume at end of 1 second (FEV1) and FEV1/Forced vital capacity (FVC) ratio. Materials and Methods: In our present study, we selected 86 cases of COPD in the age group of 41–60 years. All subjects were smokers and having FEV1

In this work, we have prepared a series of 2,3-disubstituted naphtho[2,3-f]quinoxaline-7,12-dione derivatives by condensing 1,2-diaminoanthraquinone and various benzil compounds in glacial acetic acid with excellent yield and fully characterized. Optical properties of the synthesized compounds were studied in solvents of varying polarity and thin solid film. Electrochemical properties of the compounds were studied by the cyclic voltammetry. The ionization potentials (HOMO) and electron affinity (LUMO) were found to be in the range of −6.364 to −6.644 eV and −3.247 to −3.511 eV, respectively. Thermal investigations were carried out by thermogravimetric analysis and differential scanning calorimetry.

In this work, five novel 3,6-disubstituted-tribenzo[a,c,i]phenazine (2–6) derivatives were synthesized in good yield by employing a palladium catalyzed C–N bond forming amination reaction and fully characterized. Photophysical properties of 2–6 were studied both in solvent and neat solid film by UV-vis absorption, fluorescence spectroscopy and electrochemical properties by cyclic voltammetry. Absorption spectra of 2–6 showed intramolecular charge transfer (ICT) transitions in the range of 460–512 nm in solution. The HOMO and LUMO energy levels of 2–6 are in the range of −5.18 to −5.35 eV and −3.06 to −3.17 eV respectively with electrochemical bandgap within the range of 2.12–2.29 eV. HOMO energy levels of 2–6 are comparable with most commonly used hole transporting materials such as TPD, α-NPD and spiro-OMe-TAD etc. and thus make them potential candidates for the hole transporting material in organic electronics.

A series of new donor–acceptor molecules based on acridone-amine containing four aryl substituted 2,7-diaminoacridones (1–4) and morpholine substituted acridone compounds (5) were synthesized in good yields using palladium catalysed Buchwald–Hartwig C–N amination. Their absorption, photoluminescence and electrochemical properties were investigated in solution and in thin films. Photophysical properties were found to be affected by the electron donating capability of the substituents on the diaryl amines. Absorption showed intramolecular charge transfer transitions (ICT) in a range of 447–479 nm. These acridone amine derivatives emit in the green region (500–527 nm). Reversible oxidation waves were observed for compounds 1–5 in cyclic voltammetry. The HOMO (−4.95 to −5.11 eV) and LUMO (−2.36 to −2.56 eV) energy levels of 1–5 were calculated. The EHOMO for compounds 1–5 are similar with the most widely used hole transporting materials NPD, TPD and spiro-OMe-TAD. Hence we believe that these compounds have the potential to be used as hole transporting materials in optoelectronic devices.

In this work, we have synthesized a new series of donor–acceptor system (2–7) involving electron donor triarylamines and electron acceptor naphtho[2,3-f]quinoxaline-7,12-dione by employing palladium catalyzed C–N bond forming amination reaction in good yields and fully characterized. Absorption spectra of all the synthesized molecules showed an intramolecular charge transfer (ICT) transitions in the range of 405–561 nm. Electrochemical properties of the compounds were studied by cyclic voltammetry and differential pulse voltammetry. The HOMO and LUMO energy levels of 2–7 are in the range of −4.88 to −5.57 eV and −3.37 to −3.48 eV respectively. Low-lying LUMO energy levels of 2–7 are comparable to well-known electron transporter materials and make them potential candidates as n-type semiconducting materials.

Triarylamines containing 9 H−Xanthen −9−one core and aromatic units such as phenyl, naphthyl and p −methoxyphenyl were synthesized by employing palladium catalyzed C −N bond forming amination reaction in good yields. The photophysical studies revealed that the absorption and emission spectra are influenced by the nature of the peripheral amines. The photoemission spectra can be readily tuned in the range 483–532 nm (solution) and 525–576 nm (film) displaying green or yellow emission (film) depending on the nature of the amine segment with optical band gaps in the range 2.52–2.75 eV (film). The ionization potential and electron affinity were found to be in the range 5.332–5.686 eV and 2.705–2.776 eV, respectively. Thermal studies revealed that the synthesized compounds have good thermal stability with 5% and 10% weight loss at temperature ranging from 260–330∘C and 340–370∘C, respectively.

A series of five new donor–acceptor molecules based on imidazo-anthraquinone-amines have been synthesized and characterized. The structure-property relationship in these molecules is systematically examined by absorption-emission spectroscopy, cyclic voltammetry and theoretical studies. Optical properties of these molecules have been studied in solvents of varying polarity as well as in neat solid film and found to be affected by the nature of triarylamine substituent with broad absorption windows, strong charge transfer transitions (425–502 nm), high molar extinction coefficients and emission in green light (500–568 nm). Electrochemical data indicated that the dyes possess relatively low-lying LUMO values ( $$-3.18$$ to $$-3.42$$ eV) while TGA studies revealed good thermal stability. The donor-acceptor architecture and HOMO–LUMO energies were further rationalized using DFT calculations. Experimental studies along with theoretical calculations suggest that these compounds have potential to be used as n-type materials in optoelectronic devices. Imidazoanthraquinone–amine derivatives with donor–acceptor molecular architecture were synthesized using Buchwald–Hartwig amination reaction featuring ICT absorption and low lying LUMO energy level ( $$-3.18$$ to $$-3.42$$ eV). These are comparable with well-known n-type materials for their applications in organic electronics.

In this work, we present the electrochemical polymerisation process of triarylamine-xanthone derivatives and behaviour of the formed polymers using various potentiodynamic techniques. The formed electropolymers have limited conjugation but show very promising electrochromic behaviour. Furthermore, by coupling the electrochemical analysis with each polymer's spectroscopic output, we were able to evaluate doping processes and the type of charge carriers formed. Through careful analysis, we were able to describe the electropolymerisation process and formed triarylamine-based polyxanthone derivatives. The polymers were found to exhibit good stability and good colouration efficiency to suggesting that they have potential application in electrochromic devices.

Novel low-cost bark-based magnetic iron oxide particles (BMIOPs) were synthesized and investigated for the removal of As(III) in drinking water. The synthesized BMIOP had a saturation magnetization value of 38.62 emug−1 which was found to be enough for the magnetic separation of exhausted BMIOP after As(III) adsorption. Parameters like agitation speed, adsorbent dosage, contact time, pH, temperature, and initial concentration were thoroughly investigated. Langmuir, Freundlich, and Dubinin–Radushkevich isotherms were used for the modeling of experiments and observed a maximum adsorption (19.61 mg g−1) of As(III) by Langmuir isotherm. Kinetics of As(III) sorption were well correlated with the coefficients in pseudo-first-order than the pseudo-second-order rate equation. Thermodynamic parameter investigation revealed that As(III) sorption process is endothermic, feasible, and spontaneous. BMIOP emerged as less expensive adsorbent for the abatement of arsenic ion from the drinking water. BMIOP showed 13.58 mg g−1 adsorption capacity when As(V) alone is present, while it is 9.43 and 7.04 mg g−1 for As(V) and As(III), respectively, when present together in the water.

A series of novel dipolar and nonplanar compounds featuring electron acceptor benzo[g]quinoxaline and various electron donor triarylamine units have been synthesized in good yields and fully characterized. The photophysical, electrochemical and thermal properties of the synthesized compounds are described. The photoluminescence properties of the synthesized molecules are influenced by peripheral amines. The derivatives have high Stokes shifts, low band gap and the Commission Internationale de l’Eclairage (CIE) coordinates are positioned in the green–yellow region of the chromaticity diagram. The ionization potentials and electron affinity were found to be in the range of 5.11–5.60 eV and 2.77–2.93 eV and are comparable to the commonly used hole transporters. Thermal studies also reveal that these synthesized molecules have good thermal stability with 5% and 10% weight loss temperature ranging from 200 to 355°C and 268 to 442°C, respectively.

Mesoporous MCM-41 has been synthesized by sol–gel method at room temperature possessing good thermal stability, high surface area as well as retention of surface area at high temperature. The MCM-41 neutral framework has been modified and put to practical use by incorporating Al3+ in the siliceous MCM-41 framework and supporting 12-TPA (12-tungstophosphoric acid) onto MCM-41 by process of anchoring and calcination to induce Bronsted acidity in MCM-41 to yield Al-MCM-41 and 12TPA-MCM-41, respectively. The synthesized materials have been characterized for elemental analysis by ICP-AES, XRD, SEM, TEM, EDX, FT–IR and TGA. Surface area has been determined by BET method and pore size and pore size distribution determined by BJH method. Surface acidity has been evaluated by NH3-TPD method. The potential use of Al-MCM-41 and 12TPA-MCM-41 as solid acid catalysts has been explored and compared by studying esterification as a model reaction wherein monoesters such as ethyl acetate (EA), propyl acetate (PA), butyl acetate (BA) and benzyl acetate (BzA) have been synthesized, optimizing several parameters such as catalyst amount, reaction time, reaction temperature and mole ratio of reagents.

T cells play critical roles in both protective and pathogenic adaptive immune responses. The release of cytokines by T cells is critical for their development, differentiation, and effector functions. However, significant gaps remain in our understanding of the fundamental cellular and molecular pathways that are critical for T cell cytokine release. Coat Protein Complex II (COPII) enables protein transport from the endoplasmic reticulum (ER) to the Golgi apparatus. It consists of an outer layer that facilitates the budding of vesicles from the ER membrane, and an inner layer responsible for selecting cargo proteins that comprises the protein SEC23B. The critical ER-Golgi pathway in T cell cytokine release is not known. Therefore, to explore the role of COPII secretory pathways, we generated novel Sec23bfl/-Cd4Cre mice that will lack Sec23b in T cells. We hypothesized that SEC23B-mediated COPII deficiency will lead to abnormalities in T cell development given the critical roles of T cell-derived cytokines in their ontogeny. Contrary to our hypothesis, SEC23B-deficient T cells developed normally, and were present in similar numbers in the thymus (p=0.20), lymph nodes (p=0.69), and spleen (p=0.10) as WT T cells. They also showed normal levels of surface phenotypic markers (TCR, CD25, CD44, CD62L, CD28). To rule out potential Cre-recombinase driven artifacts we next generated Sec23bfl/-Vav1Cre mice and found that T cell development was not affected. We explored the functions of mature fully developed T cells by stimulating them with aCD3/aCD28 for 3 days. Compared to WT T cells, SEC23B-deficient T cells demonstrated decreased release of cytokines such as IL-2, IL-7, and IFNg (all p We therefore hypothesized that SEC23B-deficient T cells were able to produce cytokines, but unable to release them selectively. To test this, we used Brefeldin A (BFA), an inhibitor of anterograde transport from the ER to the Golgi apparatus. In the presence of BFA, intracellular levels of IL-2 and IL-17 were similar in WT and SEC23B-deficient T cells (p=0.86). Collectively, these data suggest SEC23B-deficient T cells exhibit secretory defects of select cytokines upon stimulation compared to WT T cells. We next explored the in vivo relevance of SEC23B-dependent COPII vesicle formation in two clinically relevant models. We first tested the impact of disrupting Sec23b on in vivo protective functions of T cells in a model of viral immunity by utilizing the well-characterized LCMV Armstrong model of acute infection. Sec23b WTor Sec23bfl/-Cd4Cre mice were infected with 2x105 p.f.u. of LCMV Armstrong i.p., and T cells were analyzed on day 8 post-infection. In contrast to WT mice, Sec23bfl/-Cd4Cre mice demonstrated impaired ability to clear the virus by day 8 (9.1x107 p.f.u/gm vs N.D., p=0.0008), reduced expansion of viral antigen-specific cells (p=0.0001 for gp33, gp66, p=0.0006 for gp276), and reduced numbers of IFNg (p=0.0004) and TNFa (p=0.0003) producing T cells on day 8 post-infection. We next determined the pathogenic capacity of SEC23B-deficient T cells by utilizing a well-established MHC-mismatched C57BL/6->BALB/c model of Graft-versus-Host Disease (GVHD). BALB/c and C57BL/6 recipients were lethally irradiated (8.5 Gy) and transplanted with 5x106 allogeneic C57BL/6 WT bone marrow cells, and either 2x106 C57BL/6 WT or SEC23B-deficient T cells. All syngeneic recipients survived. By contrast, 100% of the recipients of allogeneic WT T cells died by day 61 due to GVHD. However, only 6% of allogeneic recipients of SEC23B-deficient T cells died (n=18/group, p Collectively, our data demonstrate a heretofore unrecognized but critical role for SEC23B-dependent COPII in T cell protective and pathogenic effector functions and thus provide fundamental insights into T cell-mediated immunity. Disclosures Ginsburg: Portola pharmaceuticals: Membership on an entity's Board of Directors or advisory committees; Shire plc: Membership on an entity's Board of Directors or advisory committees, Patents & Royalties.

Synthesis of series of (benzo-(5,6-e)-1,3-diphenyl-2-arylimino-(1,3)-diazepine)-4,7-dione hydrochlorides have been achieved by the interaction of N,N-diphenyl phthalamide with N-aryl isocyanodichlorides by irradiation in a domestic microwave oven for specified time using little chloroform as a solvent along with potassium carbonate. The hydrochlorides were then basified with dilute ammonium hydroxide solution. The parent compound N,N-diphenyl phthalamide was obtained by refluxing the mixture of phthalic anhydride and aniline in toluene. The structures of synthesized compounds were established on the basis of chemical transformation, elemental analysis, IR, 1 H NMR and Mass spectral studies. The synthesized compounds have been assayed for their antimicrobial activity against gram-positive as well as gram-negative microorganisms.

A simple, isocratic, rapid and accurate reversed phase high performance liquid chromatography method was developed for the quantitative determination of paracetamol and tramadol in commercial medicinal tablets. The chromatographic separation was achieved on an Intersil C18(250 mm x 4.6 mm, 5μm) column using water pH 3.4 with orthophosphoric acid: methanol (60:40, v/v) as a mobile phase, and UV detection at 228 nm. The chromatographic resolutions between paracetamol and tramadol were found greater than five. The linear range for paracetamol and tramadol were 20.8–39.0 μg/ml and 2.4–4.5 μg/ ml was obtained with correlation coefficients ≥0.999 for each analyte. The retention time were found to be 2.1 and 3.9 min for tramadol and paracetamol respectively. Paracetamol and tramadol was subjected to stress conditions (hydrolysis (acid, base) oxidation, photolysis and thermal degradation) and the stressed samples were analyzed by use of the method. The major degradation was observed in acid and minor in base, thermal, oxidation and photolysis. The forced degradation studies prove the stability indicating power of the method.

A rapid assembly of the tetracyclic core of marine diterpenoids related to puupehenone and kampanols featuring a Lewis acid catalyzed [4+2] cycloaddition reaction of 1,3,3-trimethyl-2-vinyl-1-cyclohexene and chromone dienophiles is described.

A rapid assembly of the tetracyclic core of marine diterpenoids related to puupehenone and kampanols by DielsAlder reaction of 2-ethenyl-1,3,3-trimethylcyclohexene with 4H-chromen-4-one (¼ 4H-1-benzopyran-4-one) dienophiles is described. Introduction. -T heDielsAlder reactions of 2-ethenyl-1,3,3-trimethylcyclohexene with dienophiles like dimethyl acetylenedicarboxylate (1), unsymmetrical 1,4-benzo- quinones (2), 1,4-benzoquinone (3), substituted 1,4-benzoquinones (4), 2-(methoxy- carbonyl)-4,4-dimethylcyclohex-2-enone (5), 3-((E)-(methoxycarbonyl)prop-2-eno- yl)-1,3-oxazolidin-2-one (6), acetylenedicarbaldehyde (7), (S)-5-(tert-Butyl)-3-hy- droxy-2-isopropyl-1,4-benzoquinone (8), and conjugated ketones (9) have been reported. There are very few reports on (4 þ 2) cycloaddition reactions using 4H- chromen-4-ones (¼ 4H-1-benzopyran-4-ones) as dienophiles, and in all these cases an activating functionality likeCHO, � COR, � COOR, � CN, � Ar, etc. at C(3) have been utilized (10). Only one DielsAlder reaction of 2-ethenyl-1,3,3-trimethylcyclohexene with 6-bromo-3-cyano-4H-chromen-4-one has been reported (10a).

A reversed phase HPLC method that allows the separation and simultaneous determination of the preservatives methyl paraben (M.P.) and propyl paraben (P.P.) is described. The separations were effected by using an initial mobile phase of water: acetonitrile (50:50) on Inertsil C18 to elute P.P. and M.P. The detector wavelength was set at 205 nm. Under these conditions, separation of the two components was achieved in less than 10 min. Analytical characteristics of the separation such as precision, specificity, linear range and reproducibility were evaluated. The developed method was applied for the determination of preservative M.P. and P.P. at concentration of 0.01 mg/mL and 0.1 mg/mL respectively. The method was successfully used for determining both compounds in sucralfate suspension.

A rapid assembly of the tetracyclic core of marine diterpenoids related to puupehenone and kampanols by a Diels–Alder reaction of 1,3,3-trimethyl-2-vinyl-1-cyclohexene with chromones under microwave irradiation with or without TiCl4 is described.

A mild, efficient method utilizing a copper-diamine catalyst at room temperature is reported for the coupling of hindered imidazoles with unsubstituted, ortho-substituted, and bis-ortho-substituted boronic acids in good to excellent yields. Aryl halides do not reaction under these conditions permitting sequential N-arylation reactions.

The main objective of this study was to assess the severity of iodine deficiency disorders (IDD) in the adult populations of the Baroda and Dang districts from Gujarat, western India using biochemical prevalence indicators of IDD. The other aim of this study was to establish a biochemical baseline for adequate iodine intake as a result of program evolution in the face of multiple confounding factors, like malnutrition and goitrogens responsible for goiter. A total of 959 adults (16-85 years) were studied from two districts (Baroda and Dang) and data was collected on dietary habits, anthropometric and biochemical parameters such as height, weight, urinary iodine (UI) and blood thyroid stimulating hormone (TSH). Drinking water and cooking salt were analyzed for iodine content. All subjects, irrespective of sex and district, showed median UI = 73 microg/L and mean blood TSH +/- SD = 1.59+/-2.4 mU/L. Seven per cent of the studied population had blood TSH values > 5 mU/L. Females in Baroda and males from Dang district were more affected by iodine deficiency as shown by a lower median UI. Mean TSH was significantly higher in women from both districts as compared to men (P = 0.001). The blood spots TSH values > 5 mU/L were seen in 20% of women from Dang. The normative accepted WHO values for UI and TSH for the severity of IDD as a significant health problem are not available for target population of adults. Urinary iodine normative limits and cut-offs are established for school-aged children. Blood spot TSH upper limit and cut-off values are available for neonate populations. The IDD has not been eliminated so far, as more than 20% of both male and female subjects had UI < 50 microg/L. Males were more malnourished than females in both districts (P < 0.05). Pearl millet from Baroda contained flavonoids like apigenin, vitexin and glycosyl-vitexin. Dang district water lacked in iodine content. Iodine deficiency disorder is a public health problem in Gujarat, with the Baroda district a new pocket of IDD. High amounts of dietary flavonoids in Baroda and Dang, malnutrition and an additional lack of iodine in Dang water account for IDD.

Aromatic electrophilic substitution reactions such as alkylation, acylation, benzoylation, and sulfonylation were studied in the presence of a catalytic amount of Cu(OTf) 2 and Sn(OTf) 2 . Cu(OTf) 2 was very efficient for alkylation, acylation, and benzoylation reactions. However, in case of sulfonylation reactions, Sn(OTf) 2 gave better results.

N-Aryl-β-amino acetates, obtained by opening epoxides with aromatic amines followed by acetylation of the hydroxyl group, were resolved using crude pig liver esterase (PLE) enzyme in DMSO in high enantiomeric excess.

The partitioning of alcohol dehydrogenase glucose-6-phosphate dehydrogenase and hexokinase from pressed bakers' yeast was studied in polyethylene glycol (PEG)/potassium phosphate aqueous two-phase system using unbound reactive triazine dyes as affinity ligands. The various parameters investigated were ligand type and concentration, pH of the system, phase composition of the system, and molecular weight of PEG. It was found that the best ligands gave an increase in partition coefficient of 2 to 3 times over that in the absence of the ligand.

The kinetics of release of nitroglycerin from adhesive matrix type patches was studied. At a high drug to adhesive ratio the patch consisted of nitroglycerin in part dispersed as droplets in the adhesive and in part dissolved in the adhesive. This patch showed instant release of a major fraction of nitroglycerin in the patch and thereafter release kinetics similar to that which may be expected for a solution system. The rate of skin permeation of nitroglycerin was influenced by the drug to adhesive ratio; first increasing with increase in drug to adhesive ratio and then showing no significant change at a high drug to adhesive ratio at which the system was apparently an emulsion of nitroglycerin in the adhesive.

Free radicals induce numerous diseases by lipid peroxidation, protein peroxidation and DNA damage. It has been reported that numerous plant extracts have antioxidant activities to scavenge free radicals. In the present study, the antioxidant properties of crude extract ofHibiscus rosasinensis were examined, using different in vitro analytical methodologies, such as total antioxidant activity determination by ferric thiocyanate, hydrogen peroxide scavenging, 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH) scavenging, 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS+ radical cation) radical cation scavenging activity and superoxide anion radical scavenging by riboflavin-methionine-illuminate system. Butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and α-tocopherol were used as the reference antioxidant radical scavenger compounds. The crude extract inhibited 94.58% peroxidation of linoleic acid emulsion at 20 μg/ml concentration, while the standard antioxidants BHA, BHT and α-tocopherol indicated an inhibition of 93.75, 96.66 and 83.33% at 60 μg/ml concentration, respectively. The hydrogen peroxide radical, DPPH radical, ABTS+ radical cation(s) and superoxide anion radical scavenging activities of crude extract were also compared to BHA, BHT and α-tocopherol as references antioxidant compounds. The present study shows that the crude extract is an effective natural antioxidant component. Key words: Hibiscus rosasinensis, antioxidant activity, free radical scavenging activity.