Social Protection and Child Protection: Two Sides of the Same Coin?

There is widespread recognition that children are a particularly vulnerable group; they have different basic needs than adults do, they are dependent on others for the fulfilment of their needs and the denial of those needs can have far-reaching and long-term adverse consequences (Roelen and Sabates-Wheeler 2012, White, Leavy, and Masters 2003, Sabates-Wheeler, Devereux, and Hodges 2009). The policy areas of social protection and child protection are part and parcel of the response to children and their vulnerabilities. Nevertheless, both policy areas have largely developed in silos (Roelen, Long, and Edstrom 2012). This holds in both academic and policy terms. Whilst issues of child protection are mostly dealt with in disciplines of child psychology and childhood studies, social protection is largely appropriated by economists and social scientists. Similarly, national governments, international organisations and NGOs often deal with issues of child protection and social protection in different departments and through distinct sectoral policies. It is increasingly recognised that this dichotomy is artificial (Shibuya and Taylor 2013), and that it compromises the effectiveness of the response to the wide set of needs of vulnerable children

pH and Auxiliary Ligand Influence on the Structural Variations of 5­(2′-Carboxylphenyl) Nicotate Coordination Polymers

A ligand 5-(2′-carboxylphenyl) nicotic acid (H₂cpna) has been successfully applied to construct a series of coordination complexes {[Cd­(Hcpna)₂(H₂O)₂]·3H₂O}_<i>n</i> (<b>1</b>), [Cd­(cpna)­(H₂O)]_<i>n</i> (<b>2</b>), [M­(cpna)­(2,2′-bipy)­(H₂O)]_<i>n</i> (M = Cd (<b>3</b>), Co (<b>4</b>), and Mn (<b>5</b>)), [Co­(cpna)­(phen)­(H₂O)]_<i>n</i> (<b>6</b>), [Mn­(cpna)­(phen)­(H₂O)]_<i>n</i> (<b>7</b>), {[Nd­(Hcpna)­(cpna)­(H₂O)₂]·3H₂O}_<i>n</i> (<b>8</b>), and {[Ln­(Hcpna)­(cpna)­(phen)]·2H₂O}_<i>n</i> (Ln = Pr (<b>9</b>), Nd (<b>10</b>), Eu (<b>11</b>), and Gd (<b>12</b>), 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline) under hydrothermal conditions. By adjusting the reaction pH, H₂cpna ligand is partially deprotonated to form Hcpna^– in <b>1</b> and completely deprotonated to create cpna^2– in <b>2</b>–<b>7</b>, and both forms are observed in <b>8</b>–<b>12</b>. Complexes <b>1</b>–<b>5</b> and <b>8</b> possess two-dimensional (2D) layered structures, which are further extended into 3D metal–organic supramolecular frameworks by C–H···O hydrogen bond and/or π–π stacking interactions. Complexes <b>6</b>, <b>7</b>, and <b>9</b>–<b>12</b> exhibit one-dimensional (1D) chain structures, which further build three-dimensional (3D) supramolecular architecture via C–H···O hydrogen-bonding and/or π–π stacking interactions. The results revealed that the pH value of the reaction system and auxiliary ligand play an important role in determining the structures of the complexes. Magnetic susceptibility measurements indicate that compounds <b>4</b>–<b>10</b> and <b>12</b> have dominating antiferromagnetic couplings between metal centers. Furthermore, thermal stabilities for <b>1</b>–<b>12</b> and luminescent properties for <b>1</b>–<b>3</b>, and <b>11</b> are also discussed in detail

pH and Auxiliary Ligand Influence on the Structural Variations of 5­(2′-Carboxylphenyl) Nicotate Coordination Polymers

A ligand 5-(2′-carboxylphenyl) nicotic acid (H₂cpna) has been successfully applied to construct a series of coordination complexes {[Cd­(Hcpna)₂(H₂O)₂]·3H₂O}_<i>n</i> (<b>1</b>), [Cd­(cpna)­(H₂O)]_<i>n</i> (<b>2</b>), [M­(cpna)­(2,2′-bipy)­(H₂O)]_<i>n</i> (M = Cd (<b>3</b>), Co (<b>4</b>), and Mn (<b>5</b>)), [Co­(cpna)­(phen)­(H₂O)]_<i>n</i> (<b>6</b>), [Mn­(cpna)­(phen)­(H₂O)]_<i>n</i> (<b>7</b>), {[Nd­(Hcpna)­(cpna)­(H₂O)₂]·3H₂O}_<i>n</i> (<b>8</b>), and {[Ln­(Hcpna)­(cpna)­(phen)]·2H₂O}_<i>n</i> (Ln = Pr (<b>9</b>), Nd (<b>10</b>), Eu (<b>11</b>), and Gd (<b>12</b>), 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline) under hydrothermal conditions. By adjusting the reaction pH, H₂cpna ligand is partially deprotonated to form Hcpna^– in <b>1</b> and completely deprotonated to create cpna^2– in <b>2</b>–<b>7</b>, and both forms are observed in <b>8</b>–<b>12</b>. Complexes <b>1</b>–<b>5</b> and <b>8</b> possess two-dimensional (2D) layered structures, which are further extended into 3D metal–organic supramolecular frameworks by C–H···O hydrogen bond and/or π–π stacking interactions. Complexes <b>6</b>, <b>7</b>, and <b>9</b>–<b>12</b> exhibit one-dimensional (1D) chain structures, which further build three-dimensional (3D) supramolecular architecture via C–H···O hydrogen-bonding and/or π–π stacking interactions. The results revealed that the pH value of the reaction system and auxiliary ligand play an important role in determining the structures of the complexes. Magnetic susceptibility measurements indicate that compounds <b>4</b>–<b>10</b> and <b>12</b> have dominating antiferromagnetic couplings between metal centers. Furthermore, thermal stabilities for <b>1</b>–<b>12</b> and luminescent properties for <b>1</b>–<b>3</b>, and <b>11</b> are also discussed in detail

Total Syntheses of (±)-Rhodonoids A and B and C12-<i>epi</i>-Rhodonoid B

Total syntheses of (±)-rhodonoids A and B and C12-<i>epi</i>-rhodonoid B are described here. A unified strategy employed in these syntheses is an intramolecular <i>oxa</i>-[3 + 3] annulation for accessing the chromene unit. A Fe­(OTf)₃-promoted diastereoselective cationic [2 + 2] cycloaddition and a photochemical [2 + 2] cycloaddition were featured to construct the cyclobutane core of (±)-rhodonoids A and B and C12-<i>epi</i>-rhodonoid B, respectively. Fe­(OTf)₃ also leads to an interesting bridged tetracycle, which was unambiguously confirmed by single crystal X-ray analysis

Total Syntheses of (±)-Rhodonoids C, D, E, F, and G and Ranhuadujuanine B

Here we describe the divergent, biosynthetically inspired syntheses of (±)-rhodonoids C–G and (±)-ranhuadujuanine B. The key steps of the syntheses include the construction of the chromene unit through a formal oxa-[3 + 3] annulation and a biomimetic acid-catalyzed ring cyclization. Cationic [2 + 2] cycloaddition is accomplished to form the cyclobutane core of (±)-rhodonoids E and F

Transition Metal-Free Visible Light-Driven Photoredox Oxidative Annulation of Arylamidines

A fast catalytic synthesis of multisubstituted quinazolines from readily available amidines via visible light-mediated oxidative C­(sp³)-C­(sp²) bond formation has been established. This reaction is a metal-free oxidative coupling catalyzed by a photoredox organocatalyst. The protocol features low catalyst loading (1 mol %)

Capillary-Driven Boiling Heat Transfer on Superwetting Microgrooves

Boiling can transfer a vast amount of heat and thereby is widely used for cooling advanced systems with high power density. However, the capillary force of most existing wicks is insufficient to surpass the liquid replenishing resistance for high-efficient boiling. Herein, we report a new microgroove wick on high-conductive copper substrates that was constructed via ultraviolet nanosecond pulsed laser milling. The phase explosion, combined with melting and resolidification effects of laser milling induces dense microcavities with sizes around several micrometers on the microgroove surface. The hierarchical microstructures significantly improve the wettability of the microgroove wicks to obtain strong capillary and meanwhile provide abundant effective nucleation sites. The boiling heat transfer in a visualized flat heat pipe shows that the new wicks enable sustainable liquid replenishing even under antigravity conditions, thus resulting in maximum 33-fold improvement of equivalent thermal conductivity when compared with the copper base. This research provides both scientific and technical bases for the design and manufacture of high-performance phase change cooling devices

Continuous Modification of Perovskite Film by a Eu Complex to Fabricate the Thermal and UV-Light-Stable Solar Cells

Perovskite solar cells (PSCs) with simple and low-cost processability have shown promising photovoltaic performances. However, internal defects, external UV light, and heat sensitivity are principal obstacles on their way toward commercialization. Herein, we prepare an Eu complex and directly dope it into the perovskite precursor as a UV filter to decrease the photodegradation of PSCs. The formation of hydrogen bonds between the organic cation of perovskite and the −CF3 in the Eu complex could restrain the escape of organic cations under heating. The Eu complex acts as a redox shuttle to reduce metallic lead (Pb0) and iodine (I0) defects when the PSCs have a long-time operation. Additionally, the ligand-containing aromatic rings could reduce the trace amount of I0 existing as electronic defects in perovskites and together with the long alkyl chain retard the moisture immersion into the PSCs. The best efficiency of PSCs modified by the Eu complex improves up to 20.9%. The excellent thermal stability and UV-light resistance are also realized. This strategy provides a method to design a passivator which continuously modifies the imperfections and inhibits the chemical chain reactions in perovskite film, thereby enhancing the performance and stability of PSCs

Mechanistic Insights into the Gold(I)-Catalyzed Activation of Glycosyl <i>ortho</i>-Alkynylbenzoates for Glycosidation

Anomerization, which involves cleavage and formation of the anomeric C–O bond, is of fundamental importance in the carbohydrate chemistry. Herein, the unexpected gold­(I)-catalyzed anomerization of glycosyl <i>ortho</i>-alkynylbenzoates has been studied in detail. Especially, crossover experiments in the presence of an exogenous isochromen-4-yl gold­(I) complex confirm that the anomerization proceeds via the exocleavage mechanism, involving (surprisingly) the addition of the isochromen-4-yl gold­(I) complex onto a sugar oxocarbenium (or dioxolenium) and an elimination of LAu⁺ from the vinyl gold­(I) complex. The inhibitory effect of the exogenous isochromen-4-yl gold­(I) complex when in stoichiometric amount on the anomerization has guided us to disclose an isochromen-4-yl <i>gem</i>-gold­(I) complex, which is inactive in catalysis but in equilibrium with the monogold­(I) complex and the LAu⁺ catalyst. The proposed key intermediate in the anomerization, a transient glycosyloxypyrylium species, is successfully trapped via a cycloaddition reaction with <i>n</i>-butyl vinyl ether as a dienophile. S_N2-like substitution of the initially formed glycosyloxypyrylium intermediate has then been achieved to a large extent via charging with acceptors in an excess amount to lead to the corresponding glycosides in a stereoselective manner

Total Syntheses of Cannabicyclol, Clusiacyclol A and B, Iso-Eriobrucinol A and B, and Eriobrucinol

Total syntheses of a series of chromane natural products that contain a cyclobutane ring are described. A unified theme in the strategy employed for all these syntheses is an <i>oxa</i>-[3 + 3] annulation for constructing the chromane nucleus and a stepwise cationic [2 + 2] cycloaddition for the cyclobutane formation. More importantly, the two reactions could be rendered in tandem, thereby providing an expeditious approach to this family of natural products