@article{chen_sun_fan_taniguchi_mcdowell_yang_diers_bocian_holten_lindsey_2012, title={Synthesis and Physicochemical Properties of Metallobacteriochlorins}, volume={51}, ISSN={["1520-510X"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84865712494&partnerID=MN8TOARS}, DOI={10.1021/ic301262k}, abstractNote={Access to metallobacteriochlorins is essential for investigation of a wide variety of fundamental photochemical processes, yet relatively few synthetic metallobacteriochlorins have been prepared. Members of a set of synthetic bacteriochlorins bearing 0-4 carbonyl groups (1, 2, or 4 carboethoxy substituents, or an annulated imide moiety) were examined under two conditions: (i) standard conditions for zincation of porphyrins [Zn(OAc)(2)·2H(2)O in N,N-dimethylformamide (DMF) at 60-80 °C], and (ii) treatment in tetrahydrofuran (THF) with a strong base [e.g., NaH or lithium diisopropylamide (LDA)] followed by a metal reagent MX(n). Zincation of bacteriochlorins that bear 2-4 carbonyl groups proceeded under the former method whereas those with 0-2 carbonyl groups proceeded with NaH or LDA/THF followed by Zn(OTf)(2). The scope of metalation (via NaH or LDA in THF) is as follows: (a) for bacteriochlorins that bear two electron-releasing aryl groups, M = Cu, Zn, Pd, and InCl (but not Mg, Al, Ni, Sn, or Au); (b) for bacteriochlorins that bear two carboethoxy groups, M = Ni, Cu, Zn, Pd, Cd, InCl, and Sn (but not Mg, Al, or Au); and (c) a bacteriochlorin with four carboethoxy groups was metalated with Mg (other metals were not examined). Altogether, 15 metallobacteriochlorins were isolated and characterized. Single-crystal X-ray analysis of 8,8,18,18-tetramethylbacteriochlorin reveals the core geometry provided by the four nitrogen atoms is rectangular; the difference in length of the two sides is ∼0.08 Å. Electronic characteristics of (metal-free) bacteriochlorins were probed through electrochemical measurements along with density functional theory calculation of the energies of the frontier molecular orbitals. The photophysical properties (fluorescence yields, triplet yields, singlet and triplet excited-state lifetimes) of the zinc bacteriochlorins are generally similar to those of the metal-free analogues, and to those of the native chromophores bacteriochlorophyll a and bacteriopheophytin a. The availability of diverse metallobacteriochlorins should prove useful in a variety of fundamental photochemical studies and applications.}, number={17}, journal={INORGANIC CHEMISTRY}, publisher={American Chemical Society (ACS)}, author={Chen, Chih-Yuan and Sun, Erjun and Fan, Dazhong and Taniguchi, Masahiko and McDowell, Brian E. and Yang, Eunkyung and Diers, James R. and Bocian, David F. and Holten, Dewey and Lindsey, Jonathan S.}, year={2012}, month={Sep}, pages={9443–9464} }
 @article{krayer_ptaszek_kim_meneely_fan_secor_lindsey_2010, title={Expanded Scope of Synthetic Bacteriochlorins via Improved Acid Catalysis Conditions and Diverse Dihydrodipyrrin-Acetals}, volume={75}, ISSN={["0022-3263"]}, DOI={10.1021/jo9025572}, abstractNote={Bacteriochlorins are attractive candidates for a wide variety of photochemical studies owing to their strong absorption in the near-infrared spectral region. The prior acid-catalysis conditions [BF(3) x O(Et)(2) in CH(3)CN at room temperature] for self-condensation of a dihydrodipyrrin-acetal (bearing a geminal dimethyl group in the pyrroline ring) typically afforded a mixture of three macrocycles: the expected 5-methoxybacteriochlorin (MeOBC-type), a 5-unsubstituted bacteriochlorin (HBC-type), and a free base B,D-tetradehydrocorrin (TDC-type). Here, a broad survey of >20 acids identified four promising acid catalysis conditions of which TMSOTf/2,6-di-tert-butylpyridine in CH(2)Cl(2) at room temperature was most attractive owing to formation of the 5-methoxybacteriochlorin as the sole macrocycle regardless of the pyrrolic substituents in the dihydrodipyrrin-acetal (electron-withdrawing, electron-donating, or no substituent). Eleven new dihydrodipyrrin-acetals were prepared following standard routes. Application of the new acid catalysis conditions has afforded diverse bacteriochlorins (e.g., bearing alkyl/ester, aryl/ester, diester, and no substituents) in a few days from commercially available starting materials. Consideration of the synthetic steps and yields for formation of the dihydrodipyrrin-acetal and bacteriochlorin underpins evaluation of synthetic plans for early installation of bacteriochlorin substituents via the dihydrodipyrrin-acetal versus late installation via derivatization of beta-bromobacteriochlorins. Treatment of the 5-methoxybacteriochlorins with NBS gave regioselective 15-bromination when no pyrrolic substituents were present or when each pyrrole contained two substituents; on the other hand, the presence of a beta-ethoxycarbonyl group caused loss of regioselectivity. The 15 new bacteriochlorins prepared herein exhibit a long-wavelength absorption band in the range 707-759 nm, providing tunable access to the near-infrared region. Taken together, this study expands the scope of available bacteriochlorins for fundamental studies and diverse applications.}, number={4}, journal={JOURNAL OF ORGANIC CHEMISTRY}, author={Krayer, Michael and Ptaszek, Marcin and Kim, Han-Je and Meneely, Kelly R. and Fan, Dazhong and Secor, Kristen and Lindsey, Jonathan S.}, year={2010}, month={Feb}, pages={1016–1039} }
 @article{huang_mroz_zhiyentayev_sharma_balasubramanian_ruzie_krayer_fan_borbas_yang_et al._2010, title={In Vitro Photodynamic Therapy and Quantitative Structure-Activity Relationship Studies with Stable Synthetic Near-Infrared-Absorbing Bacteriochlorin Photosensitizers}, volume={53}, ISSN={["1520-4804"]}, DOI={10.1021/jm901908s}, abstractNote={Photodynamic therapy (PDT) is a rapidly developing approach to treating cancer that combines harmless visible and near-infrared light with a nontoxic photoactivatable dye, which upon encounter with molecular oxygen generates the reactive oxygen species that are toxic to cancer cells. Bacteriochlorins are tetrapyrrole compounds with two reduced pyrrole rings in the macrocycle. These molecules are characterized by strong absorption features from 700 to >800 nm, which enable deep penetration into tissue. This report describes testing of 12 new stable synthetic bacteriochlorins for PDT activity. The 12 compounds possess a variety of peripheral substituents and are very potent in killing cancer cells in vitro after illumination. Quantitative structure-activity relationships were derived, and subcellular localization was determined. The most active compounds have both low dark toxicity and high phototoxicity. This combination together with near-infrared absorption gives these bacteriochlorins great potential as photosensitizers for treatment of cancer.}, number={10}, journal={JOURNAL OF MEDICINAL CHEMISTRY}, author={Huang, Ying-Ying and Mroz, Pawel and Zhiyentayev, Timur and Sharma, Sulbha K. and Balasubramanian, Thiagarajan and Ruzie, Christian and Krayer, Michael and Fan, Dazhong and Borbas, K. Eszter and Yang, Eunkyung and et al.}, year={2010}, month={May}, pages={4018–4027} }
 @article{mroz_huang_szokalska_zhiyentayev_janjua_nifli_sherwood_ruzie_borbas_fan_et al._2010, title={Stable synthetic bacteriochlorins overcome the resistance of melanoma to photodynamic therapy}, volume={24}, ISSN={["0892-6638"]}, DOI={10.1096/fj.09-152587}, abstractNote={Cutaneous malignant melanoma remains a therapeutic challenge, and patients with advanced disease have limited survival. Photodynamic therapy (PDT) has been successfully used to treat many malignancies, and it may show promise as an antimelanoma modality. However, high melanin levels in melanomas can adversely affect PDT effectiveness. Herein the extent of melanin contribution to melanoma resistance to PDT was investigated in a set of melanoma cell lines that markedly differ in the levels of pigmentation;3 new bacteriochlorins successfully overcame the resistance. Cell killing studies determined that bacteriochlorins are superior at (LD50≈0.1 µM) when compared with controls such as the FDA‐approved Photofrin (LD50≈10 µM) and clinically tested LuTex (LD50≈=1 µM). The melanin content affects PDT effectiveness, but the degree of reduction is significantly lower for bacteriochlorins than for Photofrin. Microscopy reveals that the least effective bacteriochlorin localizes predominantly in lysosomes, while the most effective one preferentially accumulates in mitochondria. Interestingly all bacteriochlorins accumulate in melanosomes, and subsequent illumination leads to melanosomal damage shown by electron microscopy. Fluorescent probes show that the most effective bacteriochlorin produces significantly higher levels of hydroxyl radicals, and this is consistent with the redox properties suggested by molecular‐orbital calculations. The best in vitro performing bacteriochlorin was tested in vivo in a mouse melanoma model using spectrally resolved fluorescence imaging and provided significant survival advantage with 20% of cures (P<0.01).—Mroz, P., Huang, Y.‐Y., Szokalska, A., Zhiyentayev, T., Janjua, S., Nifli, A.‐P., Sherwood, M. E., Ruzié, C., Borbas, K. E., Fan, D., Krayer, M., Balasubramanian, T., Yang, E., Kee, H. L., Kirmaier, C., Diers, J. R., Bocian, D. F., Holten, D., Lindsey, J. S., Hamblin, M. R. Stable synthetic bacteriochlorins overcome the resistance of melanoma to photodynamic therapy. FASEB J. 24, 3160–3170 (2010). www.fasebj.org}, number={9}, journal={FASEB JOURNAL}, author={Mroz, Pawel and Huang, Ying-Ying and Szokalska, Angelika and Zhiyentayev, Timur and Janjua, Sahar and Nifli, Artemissia-Phoebe and Sherwood, Margaret E. and Ruzie, Christian and Borbas, K. Eszter and Fan, Dazhong and et al.}, year={2010}, month={Sep}, pages={3160–3170} }
 @article{kee_diers_ptaszek_muthiah_fan_lindsey_bocian_holten_2009, title={Chlorin-Bacteriochlorin Energy-transfer Dyads as Prototypes for Near-infrared Molecular Imaging Probes: Controlling Charge-transfer and Fluorescence Properties in Polar Media}, volume={85}, ISSN={["1751-1097"]}, DOI={10.1111/j.1751-1097.2008.00532.x}, abstractNote={Abstract}, number={4}, journal={PHOTOCHEMISTRY AND PHOTOBIOLOGY}, author={Kee, Hooi Ling and Diers, James R. and Ptaszek, Marcin and Muthiah, Chinnasamy and Fan, Dazhong and Lindsey, Jonathan S. and Bocian, David F. and Holten, Dewey}, year={2009}, pages={909–920} }
 @misc{lindsey_taniguchi_balakumar_fan_2009, title={Methods and intermediates for the synthesis of porphyrins}, volume={7,582,751}, number={2009 Sep. 1}, author={Lindsey, J. S. and Taniguchi, M. and Balakumar, A. and Fan, D.}, year={2009} }
 @misc{lindsey_chinnasamy_fan_2009, title={Self-assembled photosynthesis-inspired light harvesting material and solar cells containing the same}, volume={7,633,007}, number={1999 Dec. 15}, author={Lindsey, J. S. and Chinnasamy, M. and Fan, D.}, year={2009} }
 @article{kee_nothdurft_muthiah_diers_fan_ptaszek_bocian_lindsey_culver_holten_2008, title={Examination of chlorin-bacteriochlorin energy-transfer dyads as prototypes for near-infrared molecular imaging probes}, volume={84}, ISSN={["1751-1097"]}, DOI={10.1111/j.1751-1097.2008.00409.x}, abstractNote={Abstract}, number={5}, journal={PHOTOCHEMISTRY AND PHOTOBIOLOGY}, author={Kee, Hooi Ling and Nothdurft, Ralph and Muthiah, Chinnasamy and Diers, James R. and Fan, Dazhong and Ptaszek, Marcin and Bocian, David F. and Lindsey, Jonathan S. and Culver, Joseph P. and Holten, Dewey}, year={2008}, pages={1061–1072} }
 @article{muthiah_kee_diers_fan_ptaszek_bocian_holten_lindsey_2008, title={Synthesis and excited-state photodynamics of a chlorin-bacteriochlorin dyad-through-space versus through-bond energy transfer in tetrapyrrole arrays}, volume={84}, ISSN={["1751-1097"]}, DOI={10.1111/j.1751-1097.2007.00258.x}, abstractNote={Abstract}, number={3}, journal={PHOTOCHEMISTRY AND PHOTOBIOLOGY}, author={Muthiah, Chinnasamy and Kee, Hooi Ling and Diers, James R. and Fan, Dazhong and Ptaszek, Marcin and Bocian, David F. and Holten, Dewey and Lindsey, Jonathan S.}, year={2008}, pages={786–801} }
 @article{fan_taniguchi_lindsey_2007, title={Regioselective 15-bromination and functionalization of a stable synthetic bacteriochlorin}, volume={72}, ISSN={["0022-3263"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-34447323851&partnerID=MN8TOARS}, DOI={10.1021/jo070785s}, abstractNote={5-Methoxy-8,8,18,18-tetramethyl-2,12-di-p-tolylbacteriochlorin (MeO-BC) undergoes regioselective electrophilic bromination with NBS to give the 15-bromo analogue (MeO-BC-Br15) in 85% yield. By contrast, the bacteriochlorin lacking the 5-methoxy group (8,8,18,18-tetramethyl-2,12-di-p-tolylbacteriochlorin, H-BC) gives a mixture of two monobromo- and two dibromobacteriochlorins. Deuterium exchange of both bacteriochlorins (H-BC and MeO-BC) in acidic media (TFA-d) occurs preferentially at the beta-pyrrole positions (3, 13) > unhindered meso-positions (5, 15 for H-BC; 15 for MeO-BC) > hindered meso-positions (10, 20). The 15-bromo-5-methoxybacteriochlorin MeO-BC-Br15 was subjected to three types of Pd-mediated coupling reactions (Suzuki, Sonogashira, Hartwig-Buchwald) to give six bacteriochlorins bearing functional groups at the 15-position (49% to 85% yield). The groups include 4-(tert-butoxycarbonylmethoxy)phenyl, 4-pyridyl, 3,5-diformylphenyl, phenylethynyl, TIPS-ethynyl, and N-benzamido. The presence of the 15-ethynyl moiety shifts the position of the long-wavelength Qy band from 732 nm to approximately 753 nm. The ability to introduce a range of groups at a specific site enables synthetic bacteriochlorins to be tailored for a variety of applications.}, number={14}, journal={JOURNAL OF ORGANIC CHEMISTRY}, publisher={American Chemical Society (ACS)}, author={Fan, Dazhong and Taniguchi, Masahiko and Lindsey, Jonathan S.}, year={2007}, month={Jul}, pages={5350–5357} }
 @article{fan_taniguchi_yao_dhanalekshmi_lindsey_2005, title={1,9-bis(N,N-dimethylaminomethyl)dipyrromethanes in the synthesis of porphyrins bearing one or two meso substituents}, volume={61}, ISSN={["0040-4020"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-25144489698&partnerID=MN8TOARS}, DOI={10.1016/j.tet.2005.08.028}, abstractNote={A synthesis of 5,15-disubstituted zinc-porphyrins has been developed that employs condensation of a 1,9-bis(N,N-dimethylaminomethyl)dipyrromethane+a dipyrromethane in refluxing ethanol containing zinc acetate followed by oxidation with DDQ. The N,N-dimethylaminomethylation of the dipyrromethane was achieved via Eschenmoser's reagent (N,N-dimethylmethyleneammonium iodide) in CH2Cl2 at room temperature. The synthesis is compatible with diverse substituents (e.g., alkyl, aryl, ester, acetal) and enables rapid synthesis of trans-AB-, A2-, and A-porphyrins. The synthesis of >40 zinc porphyrins has been surveyed; 13 zinc porphyrins were isolated in yields of 5–20% without detectable scrambling.}, number={43}, journal={TETRAHEDRON}, publisher={Elsevier BV}, author={Fan, DZ and Taniguchi, M and Yao, Z and Dhanalekshmi, S and Lindsey, JS}, year={2005}, month={Oct}, pages={10291–10302} }
 @article{taniguchi_balakumar_fan_mcdowell_lindsey_2005, title={Imine-substituted dipyrromethanes in the synthesis of porphyrins bearing one or two meso substituents}, volume={9}, ISSN={["1099-1409"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-33244492173&partnerID=MN8TOARS}, DOI={10.1142/S1088424605000678}, abstractNote={ 5,15-substituted porphyrins are valuable compounds in bioorganic and materials chemistry. A new synthesis has been developed that employs 1,9-diformylation of a dipyrromethane, conversion of the diformyldipyrromethane to the bis(imino) derivative, and reaction of the bis(imino)dipyrromethane + a dipyrromethane to give the zinc-porphyrin bearing trans-AB-substituents. 1,9-diformylation was achieved via Vilsmeier reaction. Imination was achieved by treatment of the 1,9-diformyldipyrromethane with excess amine under neat conditions at room temperature. The porphyrin-forming reaction was carried out over 2 h in refluxing ethanol containing zinc acetate exposed to air. Oxidation of the intermediate porphyrinogen occurs aerobically. A complex composed of two bis(imino)dipyrromethanes and two zinc atoms was observed to form reversibly during the course of the reaction. A set of zinc-porphyrins with trans-AB-, A 2-, or A-substituents has been prepared in yields of ~30% (without detectable scrambling) with straightforward purification. The reaction is applicable to A/B substituent combinations of aryl/aryl, aryl/alkyl, and aryl/H. }, number={8}, journal={JOURNAL OF PORPHYRINS AND PHTHALOCYANINES}, publisher={World Scientific Pub Co Pte Lt}, author={Taniguchi, M and Balakumar, A and Fan, DZ and McDowell, BE and Lindsey, JS}, year={2005}, pages={554–574} }