Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

• this single compound. 6.2. Switchable catenanes in ordered arrays Besides ordered arrays on surfaces, on nanoparticles or in Langmuir–Blodgett films, a possibility to arrange bistable catenanes in an ordered fashion is to incorporate them into the rigid scaffold of a metal-organic framework (MOF) [107

Synthesis of new p-tert-butylcalix[4]arene-based polyammonium triazolyl amphiphiles and their binding with nucleoside phosphates

• Vladimir A. Burilov,
• Guzaliya A. Fatikhova,
• Mariya N. Dokuchaeva,
• Ramil I. Nugmanov,
• Diana A. Mironova,
• Pavel V. Dorovatovskii,
• Victor N. Khrustalev,
• Svetlana E. Solovieva and
• Igor S. Antipin

Beilstein J. Org. Chem. 2018, 14, 1980–1993, doi:10.3762/bjoc.14.173

• (DLS) and electrophoretic (ELS) light scattering methods and the obtained results are collected in Table 2. Both di- and tetrasubstituted macrocycles do form nanoparticles in aqueous solution with hydrodynamic diameters within the range of 150–200 nm. The electrokinetic potential of the aggregates

Water-soluble SNS cationic palladium(II) complexes and their Suzuki–Miyaura cross-coupling reactions in aqueous medium

• Alphonse Fiebor,
• Richard Tia,
• Banothile C. E. Makhubela and
• Henok H. Kinfe

Beilstein J. Org. Chem. 2018, 14, 1859–1870, doi:10.3762/bjoc.14.160

• mixture turned black in the presence of TBAB, we were under the impression that the reaction could have proceeded via formation of palladium nanoparticles as it is common with most palladium catalysed coupling reactions. However, mercury drop experiments provided comparable yields (Table 2, entry 29 and

• 30) under the same reaction conditions ruling out the possibility of a coupling reaction catalysed by palladium nanoparticles [37]. The fact that the reaction mixture remained yellowish in the absence of TBAB and the mercury drop experiments did not lead to an appreciable decrease in yield, the

• reaction was proposed to proceed via a Pd(II) to Pd(IV) mechanism contrary to the previously reported SNS pincer Pd(II) complexes which proceeded via formation of Pd nanoparticles [35] (Pd(II) to Pd(0) type of mechanism). Literature suggestions on a Pd(II) to Pd(IV) mechanism are known for biscarbene (CNC

Graphitic carbon nitride prepared from urea as a photocatalyst for visible-light carbon dioxide reduction with the aid of a mononuclear ruthenium(II) complex

• Kazuhiko Maeda,
• Daehyeon An,
• Ryo Kuriki,
• Daling Lu and
• Osamu Ishitani

Beilstein J. Org. Chem. 2018, 14, 1806–1812, doi:10.3762/bjoc.14.153

• nanoparticles, were capable of reducing CO2 into formate under visible light (λ > 400 nm) in the presence of triethanolamine as an electron donor, with the aid of a molecular Ru(II) cocatalyst (RuP). The CO2 reduction activity was improved by increasing the synthesis temperature of g-C3N4, with the maximum

• -derived g-C3N4 exhibited an enhanced activity for CO2 reduction compared to mpg-C3N4, when modified with Ag nanoparticles and a binuclear Ru(II) complex [14]. Thermal heating of urea results in decomposition and formation of g-C3N4, whose physicochemical properties should be dependent on the heating

• in this study. Ag nanoparticles loaded on mpg-C3N4 serves as a promoter of electron transfer from mpg-C3N4 to RuP, as discussed in our previous work [13]. TEM observation indicated that the loaded Ag is in the form of nanoparticles of 5–10 nm in size (Figure 5). Without Ag (i.e., RuP/g-C3N4), formate

Synthesis and photophysical studies of a multivalent photoreactive Ru^II-calix[4]arene complex bearing RGD-containing cyclopentapeptides

• Sofia Kajouj,
• Lionel Marcelis,
• Alice Mattiuzzi,
• Adrien Grassin,
• Damien Dufour,
• Pierre Van Antwerpen,
• Didier Boturyn,
• Eric Defrancq,
• Mathieu Surin,
• Julien De Winter,
• Pascal Gerbaux,
• Ivan Jabin and
• Cécile Moucheron

Beilstein J. Org. Chem. 2018, 14, 1758–1768, doi:10.3762/bjoc.14.150

• reported in the field of calixarene chemistry [66][73][74][75][76][77][78]. Unfortunately, this methodology led to poor yields and a lack of reproducibility in the case of calixarene 7 and c-[RGDfK]-alkyne 8, even when a microwave heating was used. We then evaluated the use of copper nanoparticles (CuNPs

Design, synthesis and structure of novel G-2 melamine-based dendrimers incorporating 4-(n-octyloxy)aniline as a peripheral unit

• Cristina Morar,
• Pedro Lameiras,
• Attila Bende,
• Gabriel Katona,
• Emese Gál and
• Mircea Darabantu

Beilstein J. Org. Chem. 2018, 14, 1704–1722, doi:10.3762/bjoc.14.145

• previously reported nanosystems as polymeric nanoparticles. In covalent series, G-1 dendron D-N

  NH itself (as unexpected reference) self-assembled into nanospheres with a high D value (694 nm). We ascribed this packing ability to three basic π stacking interactions [72] associating stratified parallel

Cobalt–metalloid alloys for electrochemical oxidation of 5-hydroxymethylfurfural as an alternative anode reaction in lieu of oxygen evolution during water splitting

• Jonas Weidner,
• Stefan Barwe,
• Kirill Sliozberg,
• Stefan Piontek,
• Justus Masa,
• Ulf-Peter Apfel and
• Wolfgang Schuhmann

Beilstein J. Org. Chem. 2018, 14, 1436–1445, doi:10.3762/bjoc.14.121

• agglomerates of CoB nanoparticles after the spray-coating process (Figure 3c,d; Supporting Information File 1, Figure S4). The current density (normalized to the geometric area of NF) at 1.45 V vs RHE reached 55 mA cm−2 during the oxidation of HMF, while a 180 mV more anodic potential was necessary to achieve

Spectroelectrochemical studies on the effect of cations in the alkaline glycerol oxidation reaction over carbon nanotube-supported Pd nanoparticles

• Dennis Hiltrop,
• Steffen Cychy,
• Karina Elumeeva,
• Wolfgang Schuhmann and
• Martin Muhler

Beilstein J. Org. Chem. 2018, 14, 1428–1435, doi:10.3762/bjoc.14.120

• , 44780 Bochum, Germany 10.3762/bjoc.14.120 Abstract The effects of the alkali cations Na+ and K+ were investigated in the alkaline electrochemical oxidation of glycerol over Pd nanoparticles (NPs) deposited on functionalized carbon nanotubes (CNTs). The electrocatalytic activity was assessed by cyclic

• fine chemicals it is important to extend the knowledge about this effect. In this study we used Pd nanoparticles (NPs) deposited on functionalized carbon nanotubes (Pd/xCNT, x = N or O) for catalyzing the glycerol oxidation reaction (GOR). Pd/NCNT has been investigated recently in the ethanol

• . Conclusion The effects of the alkali cations Na+ and K+ on the electrochemical oxidation of glycerol were investigated over Pd nanoparticles supported on carbon nanotubes. The CNTs used as support for the Pd NPs were either oxygen- or nitrogen-functionalized. Cyclic voltammetry showed that the achieved

Recent applications of chiral calixarenes in asymmetric catalysis

• Mustafa Durmaz,
• Erkan Halay and
• Selahattin Bozkurt

Beilstein J. Org. Chem. 2018, 14, 1389–1412, doi:10.3762/bjoc.14.117

• converted to the the carboxylic acid analogue 82 by treatment with sodium hydroxide in MeOH at ambient temperature. Finally, deprotection of Boc groups under standard conditions afforded the targeted organocatalyst 83. Magnetic nanoparticles (MNPs) due to their high surface area have been widely used as

• calixarene derivative functionalized with two proline units on the lower rim was supported onto well defined (15 ± 3 nm) magnetic Fe3O4 nanoparticles by Yilmaz et al. [64]. Reaction of compound 84 with [3-(2,3-epoxypropoxy)propyl]trimethoxysilane-modified Fe3O4 nanoparticles (EPPTMS-MN) 85 in the presence of

• sodium hydride in tetrahydrofuran and subsequent deprotection of Boc groups afforded L-proline immobilized calix[4]arene magnetic nanoparticles (Calix-Pro-MN) 86 (Scheme 23). In 2016, three new lower rim functionalized calix[4]arene-based L-proline catalysts 87–89 containing ester, amide and acid units

Design and biological characterization of novel cell-penetrating peptides preferentially targeting cell nuclei and subnuclear regions

• Anja Gronewold,
• Mareike Horn and
• Ines Neundorf

Beilstein J. Org. Chem. 2018, 14, 1378–1388, doi:10.3762/bjoc.14.116

• or basic character. During the last 25–30 years, many different CPPs have been described and used for manifold applications like the delivery of nucleic acids, proteins, peptides, nanoparticles, small organic drugs, and others [10]. CPP conjugates can be generated by covalent conjugation between

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

• variety of areas in organic chemistry [56][57]. Recently, Shaabani’s group synthesized and characterized palladium nanoparticles supported on ethylenediamine-functionalized cellulose (PdNPs@EDACs) as a novel bio-supported catalyst for Heck and Sonogashira couplings in water [58]. Shaabani’s group reported

On the design principles of peptide–drug conjugates for targeted drug delivery to the malignant tumor site

• Eirinaios I. Vrettos,
• Gábor Mező and
• Andreas G. Tzakos

Beilstein J. Org. Chem. 2018, 14, 930–954, doi:10.3762/bjoc.14.80

• vehicles and formulates like nanoparticles [24] and calixarenes or cyclodextrins [25][26], where the cytotoxic drug is loaded and can be released at the malignant tumor site; b) installation of labile chemical groups to the tumor microenvironment (i.e., low pH) able to mask the cytotoxic drug and form a

Nanoreactors for green catalysis

• M. Teresa De Martino,
• Loai K. E. A. Abdelmohsen,
• Floris P. J. T. Rutjes and
• Jan C. M. van Hest

Beilstein J. Org. Chem. 2018, 14, 716–733, doi:10.3762/bjoc.14.61

• nanoparticles (DSN) have been shown to be highly efficient in the catalysis of olefin hydrogenation and in Suzuki coupling reactions [98][99]. Ornelas et al. entrapped a palladium catalyst with dendrimers containing triazole groups (DSN) (Figure 6) [100]. The aim here was to provide a platform to perform

• colloidal stable particle in water but also can be prepared form a wide range of components and in many different sizes and shapes. They have been used for the templated synthesis of metal nanoparticles, via which the shape and size of the nanogel directed the formation of the corresponding particle with

• similar morphology [56][112]. The metal nanoparticle core is covered by polymeric brushes, the length and the grafting are important factors which can affect the reaction, as discussed in the following paragraph, and the easy manufacturing of metal nanoparticles makes the preparation of these core-brushes

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry

• Katharina Hiebler,
• Georg J. Lichtenegger,
• Manuel C. Maier,
• Eun Sung Park,
• Renie Gonzales-Groom,
• Bernard P. Binks and
• Heidrun Gruber-Woelfler

Beilstein J. Org. Chem. 2018, 14, 648–658, doi:10.3762/bjoc.14.52

• palladium by ligands which are covalently bound to the support material [12]. One example of such a catalyst was reported by our group using a bis(oxazoline) ligand bonded to 3-mercaptopropyl-functionalised silica [20]. Alternatively, the use of unsupported Pd nanoparticles or encapsulated Pd complexes are

• interface populated by catalyst particles. They deposited metallic Pd onto carbon nanotube–inorganic oxide hybrid nanoparticles and used them in emulsions for the hydrodeoxygenation of a phenolic compound and the hydrogenation and etherification of an aldehyde. The advantages of such a system include a high

Synthesis of a sucrose-based macrocycle with unsymmetrical monosaccharides "arms"

• Karolina Tiara,
• Mykhaylo A. Potopnyk and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2018, 14, 634–641, doi:10.3762/bjoc.14.50

• ] and aza-crown [17][18] derivatives, macrocyclic dilactams [19][20], and ureas [21], were prepared in our laboratory. Sucrose was also used by other groups as a precursor for the preparation of biodegradable polymers [22][23][24] and polymeric nanoparticles [25]. On the other hand, sucrose derivatives

Mannich base-connected syntheses mediated by ortho-quinone methides

• Petra Barta,
• Ferenc Fülöp and
• István Szatmári

Beilstein J. Org. Chem. 2018, 14, 560–575, doi:10.3762/bjoc.14.43

• acid nanoparticles (ASA NPs) proved to be efficient under neat conditions for the synthesis of 1-amidoalkyl-2-naphthols [19]. Zali et al. carried out this synthesis applying nano-sulfated zirconia [20], Borhade et al. used PbS nanoparticles [21], while Safari et al. applied magnetic-nanoparticle

• 5, the catalyst gave remarkable results at room temperature in short reactions (5–30 minutes) in 90–96% yields. Comparing these results with those achieved by the application of tin dioxide nanoparticles (nano SnO2, Table 1, entry 6), molten salt catalysis affording higher yields in shorter

• (CFBILs) [27] proved to be efficient in the reaction (Table 1, entries 8–10). Safari et al. combined the benefits of using magnetic nanoparticles and ionic liquids by the application of magnetic Fe3O4 nanoparticles functionalized with 1-methyl-3-(3-trimethoxysilylpropyl)-1H-imidazol-3-ium acetate (MNP-IL

An alternative to hydrogenation processes. Electrocatalytic hydrogenation of benzophenone

• Cristina Mozo Mulero,
• Alfonso Sáez,
• Jesús Iniesta and
• Vicente Montiel

Beilstein J. Org. Chem. 2018, 14, 537–546, doi:10.3762/bjoc.14.40

• a polymer electrolyte membrane electrochemical reactor (PEMER). Palladium (Pd) nanoparticles were synthesised and supported on a carbonaceous matrix (Pd/C) with a 28 wt % of Pd with respect to carbon material. Pd/C was characterised by transmission electron microscopy (TEM), and thermogravimetric

• ; electrocatalytic hydrogenation; palladium nanoparticles; polymer electrolyte membrane; Introduction Hydrogenation is a common procedure applied in organic chemistry industry based on the use of an external hydrogen source, generally carried out under moderate experimental conditions of high temperature (until 673

• electrocatalytic hydrogenation of benzophenone has not been accomplished using a PEMER yet. This work aims at exploring the electrocatalytic hydrogenation of benzophenone over palladium nanoparticles supported on carbon black based electrode using a PEMER. A nanoparticulate platinum gas diffusion electrode is used

Carbohydrate inhibitors of cholera toxin

• Vajinder Kumar and
• W. Bruce Turnbull

Beilstein J. Org. Chem. 2018, 14, 484–498, doi:10.3762/bjoc.14.34

• restricted to organic polymers. Gold nanoparticles coated in galactosyl ligands have been shown to be effective multivalent ligands for cholera toxin [73] and E. coli heat-labile toxin [74]. In these cases the objective of the studies was not to invoke inhibition, but rather to exploit the colour changes

• induced upon crosslinking the gold nanoparticles with CTB or LTB as a strategy for detecting the bacterial toxins. Conclusion Cholera and related diseases caused by other bacterial toxins remain a substantial threat to society. This challenge, and a molecular understanding of the basis of toxin action

Stimuli-responsive oligonucleotides in prodrug-based approaches for gene silencing

• Françoise Debart,
• Christelle Dupouy and
• Jean-Jacques Vasseur

Beilstein J. Org. Chem. 2018, 14, 436–469, doi:10.3762/bjoc.14.32

Fluorogenic PNA probes

• Tirayut Vilaivan

Beilstein J. Org. Chem. 2018, 14, 253–281, doi:10.3762/bjoc.14.17

• been successfully employed in one case [111]. A PNA-based strand displacement probe was delivered into mammalian cells by employing cationic shell cross-linked nanoparticles, whereupon its application in the imaging of cellular mRNA expression was demonstrated [112]. Related to the concept of strand

5-Aminopyrazole as precursor in design and synthesis of fused pyrazoloazines

• Ranjana Aggarwal and
• Suresh Kumar

Beilstein J. Org. Chem. 2018, 14, 203–242, doi:10.3762/bjoc.14.15

• ). Bhaumik et al. [59] carried out a similar reaction of 5-aminopyrazole (R = H, R1 = Me, 16), isatin 54 and cyclic-1,3-diones 58 in aqueous ethanol using aluminosilicate nanoparticles catalyst to yield pyrazolo[3,4-b]pyridines 61 (Scheme 13). Dandia et al. [60] carried out the multicomponent synthesis of

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• sulfoxide. Different aryl thiols were reacted with aliphatic and aromatic alkenes, showing a reasonable functional group tolerance. In 2015, the group of Greaney substituted the transition metal photocatalysts by titanium dioxide (TiO2) nanoparticles (Scheme 7) [37]. Photoexcitation of electrons to the

Recent applications of click chemistry for the functionalization of gold nanoparticles and their conversion to glyco-gold nanoparticles

• Vivek Poonthiyil,
• Thisbe K. Lindhorst,
• Vladimir B. Golovko and
• Antony J. Fairbanks

Beilstein J. Org. Chem. 2018, 14, 11–24, doi:10.3762/bjoc.14.2

• unravel the causes of, potential new detection methods for, and novel therapeutic strategies against, many disease states. In the last two decades, glyco-gold nanoparticles have emerged as one of several potential new tools for glycoscientists. Glyco-gold nanoparticles consist of the unique structural

• combination of a gold nanoparticle core and an outer-shell comprising multivalent presentation of carbohydrates. The combination of the distinctive physicochemical properties of the gold core and the biological function/activity of the carbohydrates makes glyco-gold nanoparticles a valuable tool in

• glycoscience. In this review we present recent advances made in the use of one type of click chemistry, namely the azide–alkyne Huisgen cycloaddition, for the functionalization of gold nanoparticles and their conversion to glyco-gold nanoparticles. Keywords: azide–alkyne Huisgen cycloaddition; carbohydrates

Binding abilities of polyaminocyclodextrins: polarimetric investigations and biological assays

• Marco Russo,
• Daniele La Corte,
• Annalisa Pisciotta,
• Serena Riela,
• Rosa Alduina and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2017, 13, 2751–2763, doi:10.3762/bjoc.13.271

• synthesis of noble metal nanoparticles, and systems for the complexation and cell transfection of genetic material [17][18][19][20][21][22]. In particular, the complexation and transfection of polynucleotides also have been successfully accomplished by means of polycationic cyclodextrin or calixarene

Solvent-free copper-catalyzed click chemistry for the synthesis of N-heterocyclic hybrids based on quinoline and 1,2,3-triazole

• Martina Tireli,
• Silvija Maračić,
• Stipe Lukin,
• Marina Juribašić Kulcsár,
• Dijana Žilić,
• Mario Cetina,
• Ivan Halasz,
• Silvana Raić-Malić and
• Krunoslav Užarević

Beilstein J. Org. Chem. 2017, 13, 2352–2363, doi:10.3762/bjoc.13.232

• [20], nanoparticles [15][21], and with a wide application in the synthesis of pharmaceutical solids [22]. Furthermore, medicinal mechanochemistry, a new research discipline that provides an access to the active pharmaceutical ingredients, is anticipated to have a strong impact on the future