"Space—the final frontier." This preamble to a well-known television series captures the challenge encountered not only in space travel adventures, but also in the field of porous materials, which aims to control the size, shape and uniformity of the porous space and the atoms and molecules that define it. The past decade has seen significant advances in the ability to fabricate new porous solids with ordered structures from a wide range of different materials. This has resulted in materials with unusual properties and broadened their application range beyond the traditional use as catalysts and adsorbents. In fact, porous materials now seem set to contribute to developments in areas ranging from microelectronics to medical diagnosis.

Ordered porous materials for emerging applications

Photodynamic therapy involves administration of a tumor-localizing photosensitizing agent, which may require metabolic synthesis (i.e., a prodrug), followed by activation of the agent by light of a specific wavelength. This therapy results in a sequence of photochemical and photobiologic processes that cause irreversible photodamage to tumor tissues. Results from preclinical and clinical studies conducted worldwide over a 25-year period have established photodynamic therapy as a useful treatment approach for some cancers. Since 1993, regulatory approval for photodynamic therapy involving use of a partially purified, commercially available hematoporphyrin derivative compound (Photofrin) in patients with early and advanced stage cancer of the lung, digestive tract, and genitourinary tract has been obtained in Canada, The Netherlands, France, Germany, Japan, and the United States. We have attempted to conduct and present a comprehensive review of this rapidly expanding field. Mechanisms of subcellular and tumor localization of photosensitizing agents, as well as of molecular, cellular, and tumor responses associated with photodynamic therapy, are discussed. Technical issues regarding light dosimetry are also considered.

Photodynamic Therapy

Metal–organic frameworks (MOFs) display a wide range of luminescent behaviors resulting from the multifaceted nature of their structure. In this critical review we discuss the origins of MOF luminosity, which include the linker, the coordinated metal ions, antenna effects, excimer and exciplex formation, and guest molecules. The literature describing these effects is comprehensively surveyed, including a categorization of each report according to the type of luminescence observed. Finally, we discuss potential applications of luminescent MOFs. This review will be of interest to researchers and synthetic chemists attempting to design luminescent MOFs, and those engaged in the extension of MOFs to applications such as chemical, biological, and radiation detection, medical imaging, and electro-optical devices (141 references).

Luminescent Metal–Organic Frameworks

A. Water Exchange 2326 B. Proton Exchange 2327 C. Electronic Relaxation 2327 D. Relaxivity 2331 E. Outerand Second-Sphere Relaxivity 2334 F. Methods of Improving Relaxivity 2336 V. Macromolecular Conjugates 2336 A. Introduction 2336 B. General Conjugation Methods 2336 C. Synthetic Linear Polymers 2336 D. Synthetic Dendrimer-Based Agents 2338 E. Naturally Occurring Polymers (Proteins, Polysaccharides, and Nucleic Acids) 2339

https://mriquestions.com/uploads/3/4/5/7/34572113/lauffer_1999_review.pdf

Gadolinium(III) Chelates as MRI Contrast Agents: Structure, Dynamics, and Applications

Metal Organic Frameworks in Biomedicine Patricia Horcajada,* Ruxandra Gref, Tarek Baati, Phoebe K. Allan, Guillaume Maurin, Patrick Couvreur, G erard F erey, Russell E. Morris, and Christian Serre* Institut Lavoisier, UMR CNRS 8180, Universit e de Versailles St-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France Facult e de Pharmacie, UMR CNRS 8612, Universit e Paris-Sud, 92296 Châtenay-Malabry Cedex, France Institut Charles Gerhardt Montpellier, UMR CNRS 5253, Universit e Montpellier 2, 34095 Montpellier cedex 05, France EaStChem School of Chemistry, University of St. Andrews Purdie Building, St Andrews, KY16 9ST U.K.

Metal-organic frameworks in biomedicine.

1H NMR studies of porcine uteroferrin. Magnetic interactions and active site structure.

Bovine immunoglobulins (IgG) and bovine serum albumin (BSA) were multiply labeled with multidentate ligands, either ethylenediaminetetraacetic acid (EDTA) or diethylene lriaminepentaacetic acid (DTPA), and metal ions were inserted to form the ternary protein ligand-ion conjugates. The NMRD profiles (the magnetic field dependence of 1/T1) of solutions of the ternary conjugates differ greatly from those of the corresponding binary ligand-metal-ion complexes, both in magnitude and functional form, exhibiting 5-to 10 fold greater relaxivities and prominent peaks near 20 MHz. The inference is that the protein-bound chelates are relatively rigidly attached to the macromolecules. The structure and metal ion affinities of these novel conjugates, as well as the relevance to contrast enhancement in NMR imaging, is discussed. © 1986 Academic Press, Inc.

1/T1 NMRD profiles of solutions of Mn2+ and Gd3+ protein-chelate conjugates.

The present invention relates to contrast agents for diagnostic imaging with prolonged blood retention. In particular, this invention relates to novel compounds that are characterized by an image enhancing moiety (IEM); a protein plasma binding moiety (PPBM); and a blood half-life extending moiety (BHEM). This invention also relates to pharmaceutical compositions comprising these compounds and to methods of using the compounds and compositions for blood half-life extension and contrast enhancement of diagnostic imaging.

Diagnostic imaging contrast agents with extended blood retention

The solution structure and dynamics of lanthanide(III) complexes of diethylenetriaminepentaacetate (DTPA) have been investigated by {sup 1}H NMR. Two-dimensional (2D) exchange spectroscopy (EXSY) enables the determination of solution dynamics. At low temperatures (0-25{degree}C) the complexes Pr(DTPA){sup 2{minus}}, Eu(DTPA){sup 2{minus}}, and Yb(DTPA){sup 2{minus}} are in slow exchange on the NMR time scale, and all 18 proton chemical shifts are resolved. Raising the temperature causes the number of resonances to decrease from 18 to 9, consistent with exchange between two enantiomers. The rates of exchange of the complexes follow the order Pr(III) < Eu(III) < Yb(III). Utilization of 2D correlation spectroscopy (COSY) along with EXSY data as constraints enables assignments of the chemical shifts via calculations of the dipolar shifts. These calculations afford many reasonable solutions with low R factors, and only through the use of the 2D COSY and EXSY data can certain solutions be rejected. The calculations also confirm that the previously published crystal structure of Nd(DTPA){sup 2{minus}} can quite satisfactorily explain the solution structure. In addition , these data indicate that the central acetate moiety is coordinated to the metal in solution.

Solution structure and dynamics of lanthanide(III) complexes of diethylenetriaminepentaacetate: a two-dimensional NMR analysis

The ability of a blood pool contrast agent to enhance MR coronary angiography was defined. The proximal coronary vessels of pigs were imaged before and after administration of Gd-DTPA bound covalently to bovine serum albumin (0.2 mmol/kg). The contrast agent resulted in a reduction of the blood T1 value to 33 ± 5 msec, as determined in vivo with a Look-Locker technique. Both 2D and 3D imaging techniques were performed. An inversion pulse suppressed the signal of nonblood tissue postcontrast. After contrast agent administration, in the 3D data set the signal-to-noise ratio (SNR) of blood and contrast-to-noise ratio (CNR) of blood to myocardium were improved by factors of 2.0 ± 0.2 and 15 ± 8, respectively (P < 0.05). Postcontrast, the 3D acquisition was superior to the 2D technique in terms of spatial resolution, SNR of blood, and CNR of blood to myocardium. The high contrast of the 3D data set allowed for direct and rapid display of coronary arteries using a “closest vessel projection.”Magn Reson Med 41:360–367, 1999. © 1999 Wiley-Liss, Inc.

Randall B. Lauffer

Papers

1H NMR studies of porcine uteroferrin. Magnetic interactions and active site structure.

1/T1 NMRD profiles of solutions of Mn2+ and Gd3+ protein-chelate conjugates.

Diagnostic imaging contrast agents with extended blood retention

Solution structure and dynamics of lanthanide(III) complexes of diethylenetriaminepentaacetate: a two-dimensional NMR analysis

Blood pool agent strongly improves 3D magnetic resonance coronary angiography using an inversion pre-pulse