Lighting the Path: Light Delivery Strategies to Activate Photoresponsive Biomaterials In Vivo

Photoresponsive biomaterials are experiencing a transition from in vitro models to in vivo demonstrations that point toward clinical translation. Dynamic hydrogels for cell encapsulation, light-responsive carriers for controlled drug delivery, and nanomaterials containing photosensitizers for photodynamic therapy are relevant examples. Nonetheless, the step to the clinic largely depends on their combination with technologies to bring light into the body. This review highlights the challenge of photoactivation in vivo, and presents strategies for light management that can be adopted for this purpose. The authors’ focus is on technologies that are materials-driven, particularly upconversion nanoparticles that assist in “direct path” light delivery through tissue, and optical waveguides that “clear the path” between external light source and in vivo target. The authors’ intention is to assist the photoresponsive biomaterials community transition toward medical technologies by presenting light delivery concepts that can be integrated with the photoresponsive targets. The authors also aim to stimulate further innovation in materials-based light delivery platforms by highlighting needs and opportunities for in vivo photoactivation of biomaterials.     

Intramolecular Hydroamination of Selenoalkynes to 2-Selenylindoles in the Absence of Catalyst

In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles.     

Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes

The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.     

Herstellung von substituierten 2-Aminooxazol-4-carbonitrilen

Preparation of Substituted 2-Aminooxazole-4-carbonitriles During our synthetic programme to convert 4-isoxazolylthioureas 3 into the corresponding carbodiimides 5 , a side reaction leading to the hitherto unknown 2-aminooxazole-4-carbonitriles 6 was observed. By selecting appropriate reaction conditions, it was possible to improve the yields of the carbodiimides 5 as well as of the novel oxazole-carbonitriles 6 at will, thus allowing the synthesis of 6 to be conducted in very good yields. To overcome the difficulty of isolating unstable carbodiimides, the synthesis of 6 is best carried out in a one-pot procedure. A limited mechanistic study showed that the formation of 6 proceeds via 5 as the only intermediate. The stability of the N?C?N bonds against base attack (depending strongly on both sterical hindrance and electronic-density factors) forms the only limitation of this new synthetic pathway to oxazole-4-carbonitriles.     

Finitely additive integration and local integration with respect to upper integrals

Summary We study the integration theory for general integral metrics when restricted to upper integrals q, finding improvements in the relation between the classes of the q-integrable and the q_l-integrable functions. We give new results and notions which lead to the desirable characterizations of q-integrable functions as q_l-integrable f with q(|f|) < ∞, and of q_l-integrable functions via the integrability of their upper truncations, under natural conditions which are fulfilled in most finitely additive integration theories.     

Static light scattering,ultraviolet–visible,and fluorescence spectroscopy from fluorescent methyl methacrylate/benzazole dye copolymers displaying an intramolecular proton‐transfer mechanism in the electronically excited state

The solution behavior of new copolymers of methyl methacrylate and benzazole dyes emitting fluorescence because of an intramolecular proton‐transfer mechanism in the electronically excited state has been investigated by static light scattering, fluorescence spectroscopy, ultraviolet–visible, and gel permeation chromatography. In the dilute regime, with tetrahydrofuran (THF) and chloroform as solvents, the copolymers behave as typical polydisperse linear chains in good solvents. The analysis of the osmotic modulus for concentrated solutions in THF (c ≥ 60 g L^?1) indicates the existence of an interchain association mechanism. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 341–350, 2003     

Use of the Apparent Content Curves for the spectrophotometric identification of substances: identification of amphetamines

The possibility of identification of substances which have similar spectral behaviour by means of Apparent Content Curves has been studied. This study is carried out with absorption, excitation and emission spectra of several amphetamines of widespread pharmaceutical use. Results obtained show that amphetamine, phenylpropanolamine, pseudoephedrine, phenylephrine, epinephrine, dopamine and methoxyamphetamine can be identified with a probability of >95%.     

Adaptive two-loop Voltage-mode control of DC-DC switching converters

A new two-loop control scheme for voltage-mode control (VMC) of dc-dc switching converters is presented. The proposed method adds a high-gain robust loop with two controllers to the conventional VMC loop, achieving an analog "adaptive" loop in which the "equivalent voltage regulator" varies with the changing power stage parameters given as follows: 1) input voltage; 2) load; and 3) component tolerances. The loop significantly improves the disturbance rejection of the control system, i.e., closed-loop output impedance and audiosusceptibility while preserving the stability and the loop gain crossover frequency to a significant extent. Both the small-signal analysis and the experimental results carried out on a buck converter demonstrate the superiority of the proposed scheme with respect to the conventional single loop.     

Reaction of SbPO4 with lithium in non-aqueous electrochemical cells: preliminary study and evaluation of its electrochemical performance in anodes for lithium ion batteries

SbPO₄, a phosphate with a layered structure, was tested as an electrode material for lithium cells spanning the 3.0-0.0 V range. Two main electrochemical processes were detected as extensive plateaus at ca. 1.6 and 0.7 V in galvanostatic measurements. The first process was found to be irreversible, thus excluding a potential intercalation-like mechanism for the reaction and being better interpreted as a decomposition reaction leading to the formation of elemental Sb. This precludes the use of this compound as a cathodic material for lithium cells. By contrast, the process at 0.7 V is reversible and can be ascribed to the formation of lithium-antimony alloys. The best electrochemical response was obtained by cycling the cell at a C/20 discharge rate over the voltage range 1.25-0.25 V. Under these conditions, the cell delivers an average capacity of 165 Ah/kg—a value greater than those reported for other phosphates—upon successive cycling.