Traditional methods of drug delivery present several drawbacks, mainly due to off-target effects that may originate severe side and toxic effect to healthy tissues. Parallel to the development of novel more effective drugs, particular effort has been dedicated to develop and optimize drug delivery vehicles capable of specifically targeting the required tissue/organ and to deliver the cargo only where and when it is needed. New drug delivery systems based on nanoscale devices showing new and improved pharmacokinetic and pharmacodynamics properties like enhanced bioavailability, high drug loading or systemic stability have surged in the past decade as promising solutions to the required therapeutic efficacy. Amongst these nanoscale vectors, nanoparticles for drug delivery, such as polymeric, lipidbased, ceramic or metallic nanoparticles, have been at the forefront of pharmaceutical development. The interest in nanomedicine for treatment and diagnosis is clearly reflected on the increasing number of publications and issued patents every year. Here, we provide a broad overview of novel nanoparticle based drug delivery systems, ranging from polymeric systems to metal nanoparticles, while simultaneously listing the most relevant related patents.

Nanotechnology has emerged as a {"}disruptive technology{"} that may provide researchers with new and innovative ways to diagnose, treat and monitor cancer. In fact, nanomedicine approaches have delivered several strategies, such as new imaging agents, real-time assessments of therapeutic and surgical efficacy, multifunctional, targeted devices capable of bypassing biological barriers to target and silence specific pathways in tumours. Of particular interest, has been the increased capability to deliver multiple therapeutic agents directly to bulk cancer cells and cancer stem cells that play a critical role in cancer growth and metastasis. These multifunctional targeted nanoconjugates are also capable of avoiding cancer resistance and monitor predictive molecular changes that open the path for preventive action against pre-cancerous cells, minimizing costs and incidence of relapses. A myriad of nanoconjugates with effective silencing and site-targeting moieties can be developed by incorporating a diverse selection of targeting, diagnostic, and therapeutic components. A discussion of the integrative effort of nanotechnology systems with recent developments of biomolecular interactions in cancer progression is clearly required. Here, we will update the state of the art related to the development and applications of nanoscale platforms and novel biomolecular players in cancer diagnosis, imaging and treatment.

The preferential binding of anions and cations in aqueous solutions of the ionic liquids (ILs) 1-butyl- 3-methylimidazolium ([C₄mim]⁺) and 1-ethyl-3-methylimidazolium ([C₂mim]⁺) chloride and dicyanamide (dca^-) with the small alpha-helical protein Im7 was investigated using a combination of differential scanning calorimetry, NMR spectroscopy and molecular dynamics (MD) simulations. Our results show that direct ion interactions are crucial to understand the effects of ILs on the stability of proteins and that an anion effect is dominant. We show that the binding of weakly hydrated anions to positively charged or polar residues leads to the partial dehydration of the backbone groups, and is critical to control stability, explaining why dca^- is more denaturing than Cl^-. Direct cation–protein interactions also mediate stability; cation size and hydrophobicity are relevant to account for destabilisation as shown by the effect of [C₄mim]⁺ compared to [C₂mim]⁺. The specificity in the interaction of IL ions with protein residues established by weak favourable interactions is confirmed by NMR chemical shift perturbation, amide hydrogen exchange data and MD simulations. Differences in specificity are due to the balance of interaction established between ion pairs and ion-solvent that determine the type of residues affected. When the interaction of both cation and anion with the protein is strong the net result is similar to a non-specific interaction, leading ultimately to unfolding. Since the nature of the ions is a determinant of the level of interaction with the protein towards denaturation or stabilisation, ILs offer a unique possibility to modulate protein stabilisation or even folding events.

The use of a vacuum double crystal spectrometer, coupled to an electron-cyclotron resonance ion source (ECRIS), allows to measure low-energy x-ray transitions energies in highly-charged ions with accuracies of the order of a few parts per million. We have used this installation to measure the 1s2p 1 P1 - 1s2 1 S0 diagram line and the 1s2s 3 S1 - 1s2 1 S0 forbidden M1 transition energies in helium-like argon, the 1s2s2p 2 P j 1s2 2s 2 S1/2 transitions in lithium-like argon and the 1s2s2 2p 1 P1 - 1s2 2s2 1 S0 transition in beryllium-like argon. These transition measurements have accuracies between 2 and 4 ppm depending on the line intensity. Thanks to the excellent agreement between the simulations and the measurements, we were also able to measure the transition width of all the allowed transitions. The results are compared to recent QED and relativistic many-body calculations.

We present relaxivities measurements for both the longitudinal and transverse relaxations of two types of liposomes loaded with ultra small superparamagnetic iron oxide nanoparticles. The magnetoliposome systems presented are soybean phosphatidylcholine liposomes, with and without cholesterol, in the phospholipid bilayer with different molar ratios lipid:cholesterol. In fact, cholesterol is needed to obtain stable liposomes for intravenous administration. The longitudinal and transverse relaxivities were measured with a NMR spectrometer in a 7T magnetic field. For the studied concentrations, the liposomes show a negligible effect on the longitudinal relaxation time T1 of the medium, but they are very efficient on decreasing the transverse relaxation time T2, the behaviour one expects for a negative CA. We observed a lower transverse relaxivity for the magnetoliposome nanosystem with cholesterol, which strongly decreases with the cholesterol content in the liposome bilayer.

The use of agar-based biomaterials for the development of emerging areas, such as tissue engineering or ‘smart materials’ production has recently gained great interest. Understanding how these gel-forming polysaccharides self-organise in aqueous media and how these associations can be tuned to meet the specific needs of each application is thus of great relevance. As an extension of previous pioneering research concerning the application of the microwave-assisted extraction (MAE) technique in the recovery of native (NA) and alkali-modified (AA) agars, this article focuses on the different molecular assemblies assumed by these novel NA and AA when using different MAE routes. The molecular architectures in dilute (5, 10, 50 and 100 mg mL
1) and concentrated (1.5% (w/w)) aqueous media were imaged by AFM and cryoSEM, respectively. Relevant structural and physicochemical properties were investigated to support the microscopic data. Different extraction routes led to polysaccharides with unique properties, which in turn resulted in different molecular assemblies. Even at 5 mg mL
1, AFM images included individual fibers, cyclic segments, aggregates and local networks. At higher polymer concentrations, the structures further aggregated forming multilayer polymeric networks for AA. The more compact and denser 3D networks of AA, imaged by cryoSEM, and their higher resistance to large deformations matched the 2D-shapes observed by AFM. Depending on the nature of the AA chains, homogeneous or heterogeneous growth of assemblies was seen during network formation. The obtained results support well the view of double helix formation followed by intensive double helix association proposed for agar gelation.

Non-catalytic cellulosomal carbohydrate-binding modules (CBMs) are responsible for increasing the catalytic efficiency of cellulosic enzymes by selectively putting the substrate (a wide range of poly- and oligosaccharides) and enzyme into close contact. In the present work we carried out an atomistic rationalization of the molecular determinants of ligand specificity of a family 11 CBM from thermophilic C. thermocellum (CtCBM11), based on a NMR and molecular modeling approach. We have determined the NMR solution structure of CtCBM11 at 25 and 50 ºC and derived information on the residues of the protein involved in ligand recognition and on the influence of the length of the saccharide chain on binding. We obtained models of the CtCBM11/cellohexaose and CtCBM11/cellotetraose complexes by docking in accordance with the NMR experimental data. Specific ligand/protein CH-π and Van der Waals interactions were found to be determinant for the stability of the complexes and for defining specificity. Using the order parameters derived from backbone dynamics analysis in the presence and absence of ligand and at 25 and 50 ºC, we determined that the protein’s backbone conformational entropy is slightly positive. This data in combination with the negative binding entropy calculated from ITC studies supports a selection mechanism where a rigid protein selects a defined oligosaccharide conformation.

Where is CO2 ? The intermolecular interactions of [C4 mim]BF4 and [C4 mim]PF6 ionic liquids and CO2 have been determined by high-pressure NMR spectroscopy in combination with molecular dynamic simulations. The anion and the cation are both engaged in interactions with CO2 . A detailed picture of CO2 solvation in these ILs is provided. CO2 solubility is essentially determined by the microscopic structure of the IL.