Double Click Research Articles

Click Chemistry Applied in the Synthesis of Symmetrical Triphenylene-Based Discotic Liquid-Crystalline Dimers

Symmetrical triphenylene dimers connected by a bis-triazole moiety have been synthesized and characterized. The bis-triazole part is formed as final step utilizing a straightforward double click reaction (CuAAC) allowing further structural variations of the linker. The 1,3-bis(triazol-1-yl)propyltriphenylene-based dimer display columnar mesophase over a wide range of temperatures starting at ambient temperature.

Sulfur-containing hyperbranched polymeric photoinitiator end-capped with benzophenone and tertiary amine moieties prepared via simultaneous double thiol-ene click reactions used for UV curing coatings

A series of sulfur-containing hyperbranched polymeric photoinitiators end-capped with benzophenone (BP) and tertiary amine moieties (B/A-HPIs) were synthesized via the simultaneous double thiol-ene click reactions of thiolated hyperbranched polymer with both dimethylaminoethyl acrylate and 3-(4-benzoylphenoxy)propyl acrylate. The molecular structures were characterized by 1H NMR and FT-IR spectroscopy. From the UV–vis spectra, B/A-HPIs showed the stronger n-π* absorption at ∼340 nm with a higher molar extinction coefficients of 371 L mol −1 cm −1 than 148 L mol −1 cm −1 of BP, and an obvious red shift of π–π* absorption from ∼250 nm of BP to ∼280 nm. According to the photo-DSC study, the photopolymerization rate of 1,6-hexanediol diacrylate initiated by 5 wt% B/A-HPI was twice higher than that by BP. The DMTA results showed the good miscibility of B/A-HPIs with acrylate resins and high crosslinking density of cured films.

Synthesis of Terpolymers by Click Reactions

Well-defined polymeric structures were easily generated through living polymerization systems, in particular, living radical polymerizations. The polymeric precursors with orthogonal functionalities were subsequently clicked together with single or double (combinatorial) click reactions, such as the copper-catalyzed azide-alkyne cycloadditions (CuAAC) and Diels-Alder reactions, to create a wide variety of linear and nonlinear terpolymers.

Sequential double polymer click reactions for the preparation of regular graft copolymers

AbstractIn this study, graft copolymers with regular graft points containing polystyrene (PS) backbone and poly(methyl methacrylate) (PMMA), poly(tert‐butyl acrylate) (PtBA), or poly (ethylene glycol) (PEG) side chains were simply achieved by a sequential double polymer click reactions. The linear α‐alkyne‐ω‐azide PS with an anthracene pendant unit per chain was produced via atom transfer radical polymerization of styrene initiated by anthracen‐9‐ylmethyl 2‐((2‐bromo‐2‐methylpropanoyloxy)methyl)‐2‐methyl‐3‐oxo‐3‐(prop‐2‐ynyloxy) propyl succinate. Subsequently, the azide–alkyne click coupling of this PS to create the linear multiblock PS chain with pendant anthracene sites per PS block, followed by Diels–Alder click reaction with maleimide end‐functionalized PMMA, PtBA, or PEG yielded final PS‐g‐PMMA, PS‐g‐PtBA or PS‐g‐PEG copolymers with regular grafts, respectively. Well‐defined polymers were characterized by 1H NMR, gel permeation chromatography (GPC) and triple detection GPC. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Block‐brush copolymers via ROMP and sequential double click reaction strategy

AbstractWe report an efficient way, sequential double click reactions, for the preparation of brush copolymers with AB block‐brush architectures containing polyoxanorbornene (poly (ONB)) backbone and poly(ε‐caprolactone) (PCL), poly(methyl methacrylate) (PMMA) or poly(tert‐butyl acrylate) (PtBA) side chains: poly(ONB‐g‐PMMA)‐b‐poly(ONB‐g‐PCL) and poly(ONB‐g‐PtBA)‐b‐poly(ONB‐g‐PCL). The living ROMP of ONB affords the synthesis of well‐defined poly(ONB‐anthracene)20‐b‐poly (ONB‐azide)5 block copolymer with anthryl and azide pendant groups. Subsequently, well‐defined linear alkyne end‐functionalized PCL (PCL‐alkyne), maleimide end‐functionalized PMMA (PMMA‐MI) and PtBA‐MI were introduced onto the block copolymer via sequential azide‐alkyne and Diels‐Alder click reactions, thus yielding block‐brush copolymers. The molecular weight of block‐brush copolymers was measured via triple detection GPC (TD‐GPC) introducing the experimentally calculated dn/dc values to the software. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Cyclic homo and block copolymers through sequential double click reactions

AbstractWell‐defined linear α‐anthracene‐ω‐maleimide functionalized polystyrene (l‐Anth‐PS‐MI) and linear α‐alkyne‐ω‐maleimide functionalized poly(tert‐butyl acrylate) (l‐alkyne‐PtBA‐MI) homopolymers, and linear α‐anthracene‐ω‐maleimide functionalized PS‐b‐PtBA (l‐Anth‐PS‐b‐PtBA‐MI) and linear α‐anthracene‐ω‐maleimide functionalized PS‐b‐poly(ε‐caprolactone) (PCL) (l‐Anth‐PS‐b‐PCL‐MI) block copolymers were obtained via combination of atom transfer radical polymerization (ATRP)/ring opening polymerization (ROP) and azide‐alkyne click reaction strategy. Subsequently, these linear homo and block copolymers were efficiently clicked via Diels‐Alder reaction to give their corresponding cyclic homo and block copolymers at reflux temperature of toluene for 48 h under 7–4 × 10−5 M conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

The pressure profile test is more sensitive and specific than Palmer's test in predicting correct placement of the Veress needle

Objectives Although the majority of laparoscopic complications result from improper Veress needle placement, the safety tests commonly used to determine correct placement are not always reliable. A prospective observational study (Canadian Task Force Classification II-2) was set up to determine the reliability of Palmer's and pressure profile tests in predicting the correct intraperitoneal placement of the Veress needle prior to insufflation. Study design One hundred consecutive women undergoing gynaecological laparoscopic surgery between September 2006 and June 2007 were recruited. The operating surgeons conducted Palmer's and pressure profile tests in all 100 cases and recorded the ease with which these tests were performed and whether or not they felt that the needle placement was correct. They were also asked to comment on the saline drop test and double click acoustic test if appropriate. Results The overall sensitivity of Palmer's test was 0.92 while its specificity was 0.5. The overall sensitivity and specificity of the pressure profile test were 0.99 and 0.75, respectively, making this a more reliable test for predicting intraperitoneal placement of the Veress needle. Conclusions The pressure profile test was a more reliable guide to confirming the correct placement of the Veress needle as a negative test is more likely to indicate failure to achieve intraperitoneal placement.

MEG does not reveal impaired sensory gating in first-episode schizophrenia

Objective The inability to adequately suppress the second of two identical stimuli is called sensory gating deficit and can be studied by recording evoked potentials to auditory stimuli, e.g. the P50 and the N100. It has been considered the physiological correlate of schizophrenia patients' perception of being flooded by sensory impressions. According to the notion that the gating deficit constitutes a genetic trait, we expected to demonstrate the phenomenon in first-episode schizophrenia patients by using Magnetencephalography (MEG). Methods Eighteen inpatients in remission of their first psychotic episode and 24 healthy, age- and sex-matched control subjects participated in the study. Diagnoses, psychopathology, and handedness were assessed with established instruments. Stimulation was performed with the double click paradigm (ISI 500 ms, ITI 9–10 s). MEG recordings of 15 patients and 18 controls entered further analyses with the software BESA for spatio-temporal source analyses and statistical analyses with MATLAB. Results Neither P50 nor N100 responses differed statistically between the groups, which means that gating was not impaired in this sample of first-episode schizophrenia patients. Conclusions These results are not in line with the majority of studies on sensory gating in schizophrenia, however, studies on first-episode patients are scarce. The most likely reasons for not observing a gating deficit in our study are patients' first-episode status and atypical antipsychotic medication.

Synthesis and ‘double click’ density functionalization of 8-aza-7-deazaguanine DNA bearing branched side chains with terminal triple bonds

The 7-[di(prop-2-ynl)amino]prop-1-ynyl derivative of 8-aza-7-deaza-2′-deoxyguanosine ( 1) was synthesized from 7-iodo-8-aza-7-deaza-2′-deoxyguanosine ( 7) by Sonogashira cross-coupling and converted into the phosphoramidite building block 10. Oligonucleotides bearing branched side chains with terminal triple bonds were prepared by solid-phase synthesis containing single or multiple residues of 1 as 2′-deoxyguanosine surrogates. T m measurements demonstrate that compound 1 has a positive effect on duplex stability, which is comparable to the stabilizing effect of the octa-1,7-diynylated non-branched nucleoside 2. Nucleoside 1 and corresponding oligonucleotides were functionalized by the Cu(I)-mediated 1,3-dipolar cycloaddition ‘double click’ reaction with diverse ligands (AZT 3, benzyl azide 4, 11-azidoundecanol 5 and m-dPEG™ 4-azide 6). The conjugation reactions were carried out in solution and on solid support. Nucleoside 1 allowed ‘double’ functionalization of a single residue with two reporter groups. The ‘double click’ reaction proceeded smoothly even when two residues of nucleoside 1 were arranged in proximal positions. Hybridization with complementary strands led to a stable oligonucleotide duplex. Molecular modeling indicates that inspite of the crowded steric situation with four AZT ligands within closest proximal positions, all ligands are well accommodated in the major groove not disturbing the DNA helix.

Multiarm star triblock terpolymers via sequential double click reactions

AbstractMultiarm star triblock terpolymers were obtained by using two different click reactions sequentially: Cu(I) catalyzed azide–alkyne and Diels–Alder. The synthetic strategy is described as follows: (poly(methyl methacrylate))n‐(polystyrene)m‐poly(divinyl benzene)) ((PMMA)n‐(PS)m‐polyDVB) multiarm star diblock copolymer was first obtained from an azide–alkyne click reaction of (alkyne‐PS)m‐polyDVB multiarm star polymer with α‐anthracene‐ω‐azide PMMA (anth‐PMMA‐N3), followed by a Diels–Alder click reaction of the anthracene groups at the star periphery with α‐maleimide poly (tert‐butyl acrylate) (PtBA‐MI) or α‐maleimide poly(ethylene glycol) (PEG‐MI) leading to target (PtBA)k‐(PMMA)n‐(PS)m‐polyDVB and (PEG)p‐(PMMA)n‐(PS)m‐polyDVB multiarm star triblock terpolymers. The hydrodynamic diameter of individual multiarm star triblock terpolymers were measured by dynamic light scattering (DLS) to be ∼24–27 nm in consistent with the atomic force microscopy (AFM) images on silicon substrates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1557–1564, 2010

Genetic Code of Electrical Operational Procedures: Lock-Out Systems, Simulators, and Training

In electrical installations, each working zone and each source node present a kit of operating instructions as a logic gene. Previous papers have introduced a new approach and a language of a ternary code for operational procedures (Parise program). This paper deals with some comments on definitions and the syntax of the operational language. The same status of switching defines working zones or nodes by double operating value, free value, and packed value, thereby discriminating between decision and execution, and executed act from verification. The recommended command is a double click. The instructions have to be assembled like in a genetic cryptogram in the context of an electrical power system and of its architecture and constitution. They describe the complete and reversible evolution of the operational procedures for safe transition from a one set of switching configuration to another ( <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">waves of safe sets</i> ). Transitions maps are introduced to assist in the elaboration of operational procedures and to help the training of operators, their competence, and performance. These maps are specialized for the operational procedures more than the Karnaugh maps of digital electronics. On the basis of the logic gates, the basic equivalent mechanical connectives are defined to guide the operational procedures. A switching simulator based on electronic gates can be very useful for verifying the effects of any set of switching operations, adopting for commands the double click.

Sequential double click reactions: a highly efficient post-functionalization method for optoelectronic polymers

A new post-functionalization method based on the Huisgen's 1,3-dipolar cycloaddition between azides and alkynes, followed by the atom-economic addition reaction between electron-rich alkynes and tetracyanoethylene (TCNE) was developed to introduce the donor–acceptor chromophores into polystyrene derivatives in remarkably high yields.

An easy way to the preparation of multi-miktoarm star block copolymers via sequential double click reactions

As a new synthetic route, we here employed sequential double click reactions involving azide–alkyne and Diels–Alder reactions for the preparation of multi-miktoarm star block copolymers by using the arm-first approach.

Glycosyl-nucleoside fluorinated amphiphiles as components of nanostructured hydrogels

Abstract The synthesis of two novel glycosyl-nucleoside fluorinated amphiphiles (GNFs) derived from the 2H,2H,3H,3H-perfluoro-undecanoyl hydrophobic chain is described. The GNF amphiphiles, which feature either β- d -glucopyranosyl or β- d -lactopyranosyl moieties linked to a thymine base via a 1,2,3 triazole linker, were prepared using a ‘double click’ chemistry route. Surface tension measurements, gelation properties, and TEM studies show that GNFs spontaneously assemble into supramolecular structures. Similarly to their hydrocarbon analogues (GNLs), the GNFs have unique gelation properties in water. A minimum hydrogelation concentration of 0.1% (w/w), was determined in the case of the β- d -glucopyranosyl derivative. Cell viability studies indicate that fluorocarbon GNF 5 was not toxic for human cells (Huh7), whereas hydrocarbon analogue GNL is toxic above 100 μm.

“Double Click” Reaction on 7-Deazaguanine DNA: Synthesis and Excimer Fluorescence of Nucleosides and Oligonucleotides with Branched Side Chains Decorated with Proximal Pyrenes

The 7-tripropargylamine-7-deaza-2'-deoxyguanosine (2) containing two terminal triple bonds in the side chain was synthesized by the Sonogashira cross-coupling reaction from the corresponding 7-iodo nucleoside 1b. This was protected at the 2-amino group with an iso-butyryl residue, affording the protected intermediate 5. Then, compound 5 was converted to the 5'-O-DMT derivative 6, which on phosphitylation afforded the phosphoramidite 7. This was employed in solid-phase synthesis of a series of oligonucleotides. T(m) measurements demonstrate that a covalently attached tripropargylamine side chain increases duplex stability. Both terminal triple bonds of nucleoside 2 and corresponding oligonucleotides were functionalized by the Cu(I)-mediated 1,3-dipolar cycloaddition "double click reaction" with 1-azidomethyl pyrene 3, decorating the side chain with two proximal pyrenes. While the monomeric tripropargylamine nucleoside with two proximal pyrenes (4) shows strong excimer fluorescence, the ss-oligonucleotide containing 4 does not. This was also observed for ds-oligonucleotides when the complementary strand was unmodified. However, duplex DNA bearing pyrene residues in both strands exhibits strong excimer fluorescence when each strand contains two pyrene residues linked to the tripropargylamine moiety. This pyrene-pyrene interstrand interaction occurs when the pyrene modification sites of the duplex are separated by two base pairs which bring the fluorescent dyes in a proximal position. Molecular modeling indicates that only two out of four pyrene residues are interacting forming the exciplex while the other two do not communicate.

A one-pot approach to dendritic star polymers via double click reactions

A class of well-defined dendritic star polymers with poly (e-caprolactone) (PCLs) on the periphery has been prepared via one-pot double click reactions (Cu-catalyzed azide/alkyne click chemistry, i.e., CuAAC and Diels–Alder [4+2] cycloaddition reactions). The predecessors for Diels–Alder reaction, maleimide end-functionalized PCLs were produced by ring-opening polymerization (ROP). Obtained dendritic star polymers were characterized by 1H NMR, size exclusion chromatography (SEC), UV/vis, and fluorescence spectroscopy.

Sensory gating P50 in schizophrenic patients with and without homicide

To investigate the change of sensory gating P50 in schizophrenic patients with and without homicide. The auditory evoked potentials P50 were recorded from 26 schizophrenic patients with homicide (Sch group), 27 schizophrenic patients without homicide (non-Sch group) and 32 normal controls (NC) using conditioning/testing paradigm presented with auditory double click stimuli by EGI 256 dense array. And the same time, their clinical symptoms were evaluated by positive and negative symptom scale (PANSS). (1) Compared with NC, two Sch groups showed no significant difference in amplitude and latency of S1-P50 [amplitude: NC, Sch group, non-Sch group at Fz: (2.4 + or - 1.6) microV, (2.5 + or - 1.5) microV, (3.4 + or - 2.7) microV; latency: NC, Sch group, non-Sch group at Fz: (68 + or - 19) ms, (67 + or - 20) ms, (61 + or - 19) ms; respectively], but a higher amplitude and delayed latency of S2-P50 [amplitude: NC, Sch group, non-Sch group at Fz: (0.8 + or - 0.7) microV, (2.5 + or - 1.6) microV, (3.3 + or - 2.2) microV; latency: NC, Sch group, non-Sch group at Fz: (50 + or - 26) ms, (75 + or - 19) ms and (70 + or - 24) ms respectively] (P < 0.01), and no significant difference in amplitude and latency of S2-P50 between two Sch groups. (2) Compared with NC, two Sch groups showed a higher S2/S1 ratio [NC, Sch group, non-Sch group at Fz: 35 + or - 26, 153 + or - 137, 125 + or - 85, respectively], lower S2-S1 [NC, Sch group, non Sch group at Fz: 1.69 + or - 1.55, 0.08 + or - 2.41 and 0.17 + or - 2.30, respectively] and 100 (1-S2/S1) [NC, Sch group, non-Sch group at Fz: 65 + or - 26, -53 + or - 137 and -25 + or - 85 respectively] (P < 0.01). And there was no significant difference in S2/S1 ratio, S2-S1 and 100 (1-S2/S1) between two Sch groups. (3) Two Sch groups showed no significant difference in PANSS total, P scale, N scale, and G scale [Sch group: (110 + or - 27), (26 + or - 10), (29 + or - 7), (55 + or - 12); non Sch group: (105 + or - 27), (24 + or - 8), (28 + or - 10) and (53 + or - 12) respectively] (P > 0.05), and no significant correlation with S2/S1 ratio, S2-S1 and 100(1-S2/S1) (P > 0.05). Sensory gating deficit exists in schizophrenic patients with and without homicide. And it can be quantified by measuring auditory evoked potential P50, but sensory gating P50 has no difference between schizophrenic patients with and without homicide.

Probing the Activity of Matrix Metalloproteinase II with a Sequentially Click‐Labeled Silica Nanoparticle FRET Probe

Selective double click labeling: The determination of nanomolar concentrations of matrix metalloproteinase II is made possible through the use of a nanoprobe that consists of fluorescently doped silica nanoparticles to which a FRET-based enzyme substrate has been conjugated through sequential click reactions.

One‐pot double click reactions for the preparation of H‐shaped ABCDE‐type quintopolymer

AbstractWe employed for the first time double click reactions: Cu(I) catalyzed azide‐alkyne 1,3‐dipolar cycloaddition and Diels–Alder (4 + 2) reactions for the preparation of H‐shaped polymer possessing pentablocks with different chemical nature (H‐shaped quintopolymer) using one‐pot technique. H‐shaped quintopolymer consists of poly(ethylene glycol) (PEG)‐poly(methylmethacrylate) (PMMA) and poly(ε‐caprolactone) (PCL)‐polystyrene (PS) blocks as side chains and poly (tert‐butylacrylate) (PtBA) as a main chain. For the preparation of H‐shaped quintopolymer, PEG‐b‐PMMA and PCL‐b‐PS copolymers with maleimide and alkyne functional groups at their centers, respectively, were synthesized and simply reacted in one‐pot with PtBA with α‐anthracene‐ω‐azide end functionalities in N,N‐dimethylformamide (DMF) using CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as catalyst at 120 °C for 48 h. The precursors and the target H‐shaped quintopolymer were characterized comprehensively by 1H NMR, UV, FTIR, GPC, and triple detection GPC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3409–3418, 2009

Glycosyl-Nucleoside Lipids as Low-Molecular-Weight Gelators

A family of new glycosyl-nucleoside lipids (GNLs) that were prepared using a convenient "double click" chemistry route is described. Physicochemical studies (surface tension measurements, gelation properties, and transmission electron microscopy) indicate that these amphiphiles spontaneously assemble into supramolecular structures including fibers, vesicles, hydrogels, and organogels. GNLs possess unique gelation properties both in water and chloroform. A very low minimum gelation concentration of 0.1% (w/w) was observed in the case of the amide-saturated derivative in water.