The Role of Polymer-AuNP Interaction in the Stimuli-Response Properties of PPA-AuNP Nanocomposites.

The helical sense control of dynamic helical polymers such as poly(phenylacetylene)s (PPAs) is greatly affected when they are conjugated to AuNPs through a strong thiol-Au connection, which restricts conformational changes at the polymer. Thus, the classical thiol-MNP bonds must be replaced by weaker ones, such as supramolecular amide-Au interactions. A straightforward preparation of the PPA-Au nanocomposite by reduction of a preformed PPA-Au3+ complex cannot be used due to a redox reaction between the two components of the complex which degrades the polymer. To avoid the interaction between the PPA and the Au3+ ions before the reduction takes place, the metal ions are added to the polymer solution capped as a TOAB complex, which keeps the PPA stable due to the lack of PPA-Au3+ interactions. Ulterior reduction of the Au3+ ions by NaBH4 affords the desired nanocomposite, where the AuNPs are stabilized by supramolecular anilide-AuNPs interactions. By using this approach, 3.7 nm gold nanoparticles are generated and aligned along the polymer chain with a regular distance between particles of 6 nm that corresponds to two helical pitches. These nanocomposites show stimuli-responsive properties and are also able to form macroscopically chiral nanospheres with tunable size.

Photochemical Electrocyclization of Poly(phenylacetylene)s: Unwinding Helices to Elucidate their 3D Structure in Solution.

Photochemical electrocyclization of poly(phenylacetylene)s (PPAs) is used for the structural elucidation of a polyene backbone. This method not only allows classification of PPAs in cis-cisoidal (ω1 <90°) or cis-transoidal structures (ω1 >90°), but also approximating ω1 . A PPA solution is illuminated with visible light and monitoring the photochemical electrocyclization of the PPA helix by measuring the ECD spectra at different times. PPAs with a cis-cisoidal structure show a reduction of the ECD signal of at least 50 % before 30 min of irradiation, while cis-transoidal helices need much longer time because the transoidal bond must be isomerized. The different cis-cisoidal and cis-transoidal helices require different times to decrease their ECD signal by 50 % (t1/2 ), depending on the degree of compression or stretching of the helix, establishing a relationship between the secondary structure adopted by PPA (ω1 ) and the time required to lose the ECD vinylic signal by light irradiation.

From Sergeants and Soldiers to Chiral Conflict Effects in Helical Polymers by Acting on the Conformational Composition of the Comonomers.

Different communication mechanisms can be switched within a copolymer by acting on the conformational composition of the components and their chirality. Thus, a sergeant and soldiers effect is produced in two diastereomeric copolymer series, poly[(S)-1r -co-(S)-2(1-r) ] and poly[(R)-1r -co-(S)-2(1-r) ], owing to the presence in chloroform of a preferred conformation in (S)-2, and a conformational equilibrium in 1, where a P helix is induced independently of the absolute configuration of the soldier. In THF, the presence of a conformational equilibrium at the pendants of the two components produces a reciprocal chiral enhancement effect by copolymerization of the two monomers, while in DMF, a third chiral to chiral communication switch is produced due to the presence of a single conformer at the pendant group of the two components. In such a case, a chiral conflict or chiral accord effect is produced depending if the two components induce the same or the opposite helical sense.

A Stimuli-Responsive Macromolecular Gear: Interlocking Dynamic Helical Polymers with Foldamers.

Herein, macromolecular gears composed of helical poly(phenylacetylenes) (PPAs) bearing short oligopeptides as pendant groups are described, in which the two structural motifs (framework and substituents) are combined. These gears are obtained by polymerization of the acetylene groups introduced at the C-terminus of short oligopeptides formed by achiral (Aib)n units (n=1-3) derivatized at the N-terminus by a single enantiomer (R or S) of α-methoxy-α-trifluoromethylphenylacetic acid (MTPA, Mosher's reagent). The chiral information of the MTPA is transmitted to the achiral Aib fragments and, through either chiral tele-induction and/or chiral harvesting mechanisms, is further transferred to the polyene backbones, which adopt preferentially P or M helical senses. Moreover, these materials also show dynamic behavior and respond to the action of external stimuli by either inverting the P/M sense and/or modifying the elongation in fully reversible processes.

Chiral Overpass Induction in Dynamic Helical Polymers Bearing Pendant Groups with Two Chiral Centers.

The dynamic behavior of helical polymers bearing pendant groups with two chiral centers was studied. Controlled conformational changes at the chiral units placed either closer to or further away from the main chain promote different helical structures. Although the first residue is usually responsible for determining a specific helicity (P or M), we now found that the second chiral center is also able to induce a preferred helical sense when it is located closer in space to the main chain, thereby cancelling the order from the first chiral moiety. This result was achieved through proper coordination with a metal cation. As proof of concept, poly(phenylacetylene)s (PPAs) that bear one and two chiral amino acid units of different sizes and configuration combinations (l/d-alanine and l/d-phenylalanine) as pendants were evaluated. In total, ten polymers were studied. This constitutes the first report of axial control from a remote stereocenter in polymers bearing complex chiral pendants.

Stimuli-Directed Colorimetric Interconversion of Helical Polymers Accompanied by a Tunable Self-Assembly Process.

Interconversion between extended and bent structures at the pendant groups of a chiral polyene framework [poly(phenylacetylene) with (R)-(2-methoxy-2-phenylacetyl)glycine residues linked to 4-vinylanilines] allows the reversible colorimetric transformation from stretched to compressed helical cis-transoid polyenic structures through manipulation of the flexible spacer. This transformation generates either organogels (stretched helical form) or nanoparticles (compressed helical form) under the control of polar/low polar stimuli respectively and opens the way to the development of new sensors and stimuli-sensitive materials based on these concepts.

Chiral Conflict as a Method to Create Stimuli-Responsive Materials Based on Dynamic Helical Polymers.

A new multi-sensor material based on helical copolymers showing the chiral conflict effect have been prepared. It can successfully detect and identify diverse metal cations in solution. The design of this material has taken into account not only the opposite helical senses induced by the two chiral monomers in the copolymer, but also their dynamic behavior. The induced helical sense can thus be enhanced, diminished, or inverted by interaction with different stimuli (that is, metal ions). Thus, depending on both the copolymer compositions (such as monomer ratios and absolute configurations) and the nature of the metal ion, the response of these dynamic helical copolymers to adopt a single-handed P or M helix is unique, making it possible not only to detect their presence, but also to identify them individually. New multi-sensors materials based and inspired on this effect should arise in the future choosing appropriate monomers and stimuli.

Chiral-to-Chiral Communication in Polymers: A Unique Approach To Control Both Helical Sense and Chirality at the Periphery.

A novel approach to the classical Sergeants and Soldiers effect, using chiral Sergeants and chiral Soldiers, allows control over both helical and external chirality in helical polymers. In the systems reported here, it is possible to induce the same helical sense ( M or P) from either of the two enantiomers of a chiral pendant group ["chiral Soldier", major component; i.e., ( R)- or ( S)-1] when it faces a single enantiomer of an appropriate "chiral Sergeant" [minor component; i.e., ( S)-2]. For instance, the copolymer series poly[( R)-1 r- co-( S)-2(1- r)], poly[( S)-1 r- co-( S)-2(1- r)], and poly[( rac)-1 r- co-( S)-2(1- r)] adopt the same P helix even though the major component shows the opposite absolute configuration. This chiral-to-chiral communication effect is transmitted by the stabilization of different conformations in each enantiomeric form of the Soldier. As a result, this groundbreaking approximation to the Sergeants and Soldiers effect allows the preparation of a single-handed helix-which depends only on the Sergeant's configuration-with different chiralities on the helix periphery. Thus, a P helix can be decorated with the R isomer, S isomer, or even a racemic mixture of the chiral Soldier. A change in the absolute configuration of the Sergeant affords the opposite M helix, which can also be decorated with the R isomer, S isomer, or racemic mixture of the chiral Soldier.

Chiral Coalition in Helical Sense Enhancement of Copolymers: The Role of the Absolute Configuration of Comonomers.

Both the role of the absolute configuration and the tendency of a chiral monomer to promote a certain helical scaffold in a poly(phenylacetylene) (PPA) have been evaluated to study the communication between two chiral monomers within a copolymer chain. Nineteen different PPA copolymer series-47 helical copolymers altogether-were prepared to explore the existence of a chiral-to-chiral communication mechanism. From the data obtained, we found that communication between two different chiral monomers emerges when both exhibit two special features: (a) a different conformational composition-one must exist in a single low-energy conformation ("chiral Sergeant") and the other must present two conformers ("chiral Soldier")-and (b) the induction of a similar scaffold in the PPA, either cis-cisoidal or cis-transoidal. In the selected systems, the chiral Soldier includes the 4-ethynylanilide (para position) of either (R)- or (S)-2-methoxy-2-phenylacetic acid pendants characterized by their conformational flexibility (equilibrium between synperiplanar and antiperiplanar conformations). The chiral Sergeant contains the same chiral groups but linked to the backbone in meta position [3-ethynylanilide of (R)- or (S)-2-methoxy-2-phenylacetic acid] and is selected on the basis of its restricted antiperiplanar conformation. Incorporation of a very small amount (1%) of the Sergeant into a chain composed of just the Soldier transforms the originally axially racemic chain into a helix with strong sense preference (either M or P) that is determined by the absolute configuration of the Soldier.

Filtering the NMR Spectra of Complex Mixtures through Polymer-Mediated Paramagnetic Spin Relaxation.

A polymer-mediated paramagnetic spin relaxation (PSR) filter is presented for the selective suppression of signals from polymer-interacting species in the 1D and 2D NMR spectra of mixtures. The combined use of Gd3+ and a polymer with a high transverse relaxation enhancement (R2p , which gives a measure of the Gd3+ -complexing ability) results in the suppression of signals from any polymer-interacting component in mixtures, irrespective of their R2p . By using poly(acrylic acid) (PAA) as a model system, we demonstrate selective filtering of the signals of typical low-R2p species (insensitive to Gd3+ ), such as molecular/polymeric cations and non-ionic polymers, which, through PAA recognition (electrostatic/hydrogen-bonding interactions), become exposed to the paramagnetic effect of Gd3+ , while leaving non-PAA-interacting species unaffected. Typical suppression conditions involve PAA (approximately equimolar amount with respect to the species to be filtered) accompanied by sub-mm concentrations of Gd3+ and T2 -filters ≤100 ms. Overall, by exploiting the PSR principles and the recognition properties of polymers, selective NMR filtrations that are not attainable by diffusion, relaxation, or direct PSR filters, can be achieved.

Predicting the Helical Sense of Poly(phenylacetylene)s from their Electron Circular Dichroism Spectra.

The calculated ECD spectrum (time-dependent density functional theory TD-DFT) for small oligomers of polyphenylacetylenes (PPAs) show a very good match with the experimental spectra of the PPA polymers, particularly with the first Cotton band associated to the helical sense of the internal polyenic backbone. This has been proven with a series of PPAs representative of cis-cisoidal, cis-transoidal, compressed and stretched polyene backbones, with identical or opposite internal/external rotational senses and allows the prediction of the helical sense of the internal helix of a PPA directly from its CD spectra.

Tuning the Size of Nanoassembles: A Hierarchical Transfer of Information from Dendrimers to Polyion Complexes.

The generation of dendrimers is a powerful tool in the control of the size and biodistribution of polyion complexes (PIC). Using a combinatorial screening of six dendrimers (18-243 terminal groups) and five oppositely charged PEGylated copolymers, a dendrimer-to-PIC hierarchical transfer of structural information was revealed with PIC diameters that increased from 80 to 500 nm on decreasing the dendrimer generation. This rise in size, which was also accompanied by a micelle-to-vesicle transition, is interpreted according to a cone- to rod-shaped progression in the architecture of the unit PIC (uPIC). This precise size tuning enabled dendritic PICs to act as nanorulers for controlled biodistribution. Overall, a domino-like control of the size and biological properties of PIC that is not attainable with linear polymers is feasible through dendrimer generation.

Simultaneous Adjustment of Size and Helical Sense of Chiral Nanospheres and Nanotubes Derived from an Axially Racemic Poly(phenylacetylene).

Nanospheres and nanotubes with full control of their size and helical sense are obtained in chloroform from the axially racemic chiral poly(phenylacetylene) poly-(R)-1 using either Ag+ as both chiral inducer and cross-linking agent or Na+ as chiral inducer and Ag+ as cross-linking agent. The size is tuned by the polymer/ion ratio while the helical sense is modulated by the polymer/cosolvent (i.e., MeCN) ratio. In this way, the helicity and the size of the nanoparticles can be easily interconverted by very simple experimental changes.

Architecture of Chiral Poly(phenylacetylene)s: From Compressed/Highly Dynamic to Stretched/Quasi-Static Helices.

The remarkable consequences in elongation, dynamic character, response to external stimuli (e.g., solvent effects, metal cations), and aggregation observed in helical poly(phenylacetylene)s (PPAs) when either the type of linkage with the pendant groups (i.e., anilide, benzamide) or the aromatic substitution pattern (i.e., ortho, meta, para) of the parent phenylacetylene monomer undergo modification are analyzed in depth. Two series of PPAs substituted at the phenyl ring in ortho, meta, and para with either (S)-α-methoxy-α-phenylacetic acid (MPA) or (S)-phenylglycine methyl ester (PGME) linked through anilide or benzamide bonds were prepared (i.e., o-, m-, p-poly-1 and poly-2 series) and characterized both in solution and in the solid state (CD, UV-vis, Raman, NMR, DSC, TGA, X-ray, AFM, SEM). Para-substituted polymers (p-poly-1 and p-poly-2) present the most compressed and dynamic helices, which respond easily to external stimuli. Meta-substituted PPAs (m-poly-1 and m-poly-2) exist as a mixture in equilibrium of two different helices (compressed and stretched), both less dynamic than the para counterparts and with a weak response to external stimuli. Moreover, in the solid state, m-poly-1 and m-poly-2 show separate fields for the compressed and for the stretched helices. For its part, the ortho-substituted PPA (o-poly-1) presents a highly stretched, almost planar and practically rigid helical structure, inert to external stimuli and prone to aggregate. These structural changes (elongation/dynamic behavior) are rationalized on the basis of the increasing difficulties imposed by the meta- and ortho-substitution on the accommodation of the pendants within the helical structure.

Joint NMR and Solid-Phase Microextraction-Gas Chromatography Chemometric Approach for Very Complex Mixtures: Grape and Zone Identification in Wines.

In very complex mixtures, classification by chemometric methods may be limited by the difficulties to extract from the NMR or gas chromatography/mass spectrometry (GC/MS) experimental data information useful for a reliable classification. The joint analysis of both data has showed its superiority in the biomedical field but is scarcely used in foodstuffs and never in wine in spite of the complexity of their spectra and classification. In this article we show that univariate and multivariate principal component analysis-discriminant analysis (PCA-DA) statistics applied to the combined (1)H NMR and solid-phase microextraction-gas chromatography (SPME-GC) data of a collection of 270 wines from Galicia (northwest Spain) allows a discrimination and classification not attainable from the separate data, distinguishing wines from autochthonous and nonautochthonous grapes, mono- from the plurivarietals, and identifying, in part, the geographical subzone of origin of the albariño wines. A general and automatable protocol, based on the signal integration of selected ROIs (regions of interest), is proposed that allows the fast and reliable identification of the grape in Galician wines.

Chiral Nanostructures from Helical Copolymer-Metal Complexes: Tunable Cation-π Interactions and Sergeants and Soldiers Effect.

Poly(phenylacetylene) (PPA) copolymers containing (R)- or (S)-MPA as minor chiral pendant can be forced to selectively adopt the right- o left-handed helix, in the presence of small amounts of Na(+) or Ag(+) ("Sergeants and Soldiers Effect") by addition of a donor cosolvent. The helical sense depends exclusively on the chiral monomer/donor cosolvent ratio, and this allows a perfect on/off tuning of the helicity of the copolymer. When the amount of the donor cosolvent is low, the metal ion complex is stabilized by a cation-π interaction, which is selectively cleaved when the amount of cosolvent is higher. Macroscopically chiral nanospheres and nanotubes composed by helical copolymers with P or M helical sense are also described. Our results demonstrate that it is possible to obtain the two enantiomeric helical structures (P and M helicities) and the corresponding nanospheres and nanotubes from a single helical copolymer, by controlled activation/deactivation of the Sergeant and Soldiers Effect with a donor cosolvent.

Predicting PSR filters by transverse relaxation enhancements.

The paramagnetic spin relaxation (PSR) filter allows the suppression of the NMR resonances of individual components in mixtures according to their Gd(3+)-complexing ability. The difficulty in predicting this property hampers, however, the widespread application of this filter. Herein we describe that the PSR filter is dominated by the transverse relaxation enhancement (R(2p)) experienced by nuclei in the presence of Gd(3+), so that R(2p) represents a reliable predictive tool of suppression in the 1D and 2D PSR filter of complex mixtures. The robustness of R(2p) as a predictive tool in PSR filters has been demonstrated at different magnetic fields and for the (1)H, (13)C, COSY, and HMQC filtering of commercial multicomponent compositions, including beverages and drugs.

Nanospheres, nanotubes, toroids, and gels with controlled macroscopic chirality.

The interaction of a highly dynamic poly(aryl acetylene) (poly-1) with Li(+), Na(+), and Ag(+) leads to macroscopically chiral supramolecular nanospheres, nanotubes, toroids, and gels. With Ag(+), nanospheres with M helicity and tunable sizes are generated, which complement those obtained from the same polymer with divalent cations. With Li(+) or Na(+), poly-1 yields chiral nanotubes, gels, or toroids with encapsulating properties and M helicity. Right-handed supramolecular structures can be obtained by using the enantiomeric polymer. The interaction of poly-1 with Na(+) produces nanostructures whose helicity is highly dependent on the solvation state of the cation. Therefore, structures with either of the two helicities can be prepared from the same polymer by manipulation of the cosolvent. Such chiral nanotubes, toroids, and gels have previously not been obtained from helical polymer-metal complexes. Chiral nanospheres made of poly(aryl acetylene) that were previously assembled with metal(II) species can now be obtained with metal(I) species.

Stepwise filtering of the internal layers of dendrimers by transverse-relaxation-edited NMR.

The characteristic distribution of transverse relaxation times (T2) within dendrimers (shorter values at the core than the periphery) can be exploited in T2-edited 1D and 2D NMR experiments for the stepwise filtering of internal nuclei according to their topology within the dendritic structure. The resulting filtered spectra, which can be conceived as corresponding to virtual hollow dendrimers, benefit from reduced signal overlap, thus facilitating signal assignment and characterization. The generality of the method as a powerful tool in structural and end-group analysis has been confirmed with various dendritic families and nuclei ((1)H, (13)C, (31)P).

Real-time evaluation of binding mechanisms in multivalent interactions: a surface plasmon resonance kinetic approach.

Multivalency is a key, ubiquitous phenomenon in nature characterized by a complex combination of binding mechanisms, with special relevance in carbohydrate-lectin recognition. Herein we introduce an original surface plasmon resonance kinetic approach to analyze multivalent interactions that has been validated with dendrimers as monodisperse multivalent analytes binding to lectin clusters. The method, based on the analysis of early association and late dissociation phases of the sensorgrams provides robust information of the glycoconjugate binding efficiency and real-time structural data of the binding events under the complex scenario of the glyco-cluster effect. Notably, it reveals the dynamic nature of the interaction and offers experimental evidence on the contribution of binding mechanisms.