The non-stereospecific α-haloalkanoic acid dehalogenase DehE from Rhizobium sp. RC1 catalyzes the removal of the halide from α-haloalkanoic acid D,L-stereoisomers and, by doing so, converts them into hydroxyalkanoic acid L,D-stereoisomers, respectively. DehE has been extensively studied to determine its potential to act as a bioremediation agent, but its structure/function relationship has not been characterized. For this study, we explored the functional relevance of several putative active-site amino acids by site-specific mutagenesis. Ten active-site residues were mutated individually, and the dehalogenase activity of each of the 10 resulting mutants in soluble cell lysates against D- and L-2-chloropropionic acid was assessed. Interestingly, the mutants W34→A,F37→A, and S188→A had diminished activity, suggesting that these residues are functionally relevant. Notably, the D189→N mutant had no activity, which strongly implies that it is a catalytically important residue. Given our data, we propose a dehalogenation mechanism for DehE, which is the same as that suggested for other non-stereospecific α-haloalkanoic acid dehalogenases. To the best of our knowledge, this is the first report detailing a functional aspect for DehE, and our results could help pave the way for the bioengineering of haloalkanoic acid dehalogenases with improved catalytic properties.
Kajian yang dijalankan ini bertujuan untuk menilai indeks kualiti air di sekitar kawasan lombong di Sungai Pelepah Kanan, Kota Tinggi, Johor. Sebanyak enam stesen pensampelan telah dipilih dari bahagian hulu ke hilir sungai ini untuk menilai indeks kualiti air di sepanjang sungai tersebut. Tiga replikasi sampel telah diambil daripada setiap stesen pensampelan. Pengambilan sampel dilakukan pada dua musim yang berbeza iaitu musim kering (Julai) dan musim hujan (Disember) 2007. Parameter in-situ yang ditentukan dalam kajian ini ialah suhu, pH, oksigen terlarut (DO) dan konduktiviti. Parameter ex-situ yang dianalisis dalam makmal ialah turbiditi air, jumlah pepejal terampai (TSS), keperluan oksigen biokimia (BOD), keperluan oksigen kimia (COD) dan ammonia nitrogen (NH3-N). Berdasarkan Piawaian Interim Kualiti Air Kebangsaan Malaysia (INWQS) hasil kajian yang diperolehi menunjukkan semua stesen pensampelan di Sungai Pelepah Kanan pada bulan Julai berada dalam kelas I kecuali oksigen terlarut dan pH berada dalam kelas II. Selain itu, hasil kajian pada bulan Disember juga menunjukkan semua parameter fiziko-kimia berada dalam kelas I-II kecuali pH berada dalam kelas III. Ujian korelasi menunjukkan terdapat hubungan bererti antara parameter-parameter fiziko-kimia yang di tertentukan. Analisis Indeks Kualiti Air (IKA) menunjukkan nilai purata IKA pada bulan Julai adalah 96.88 (kelas I) manakala pada bulan Disember telah merosot ke 84.03 (kelas II). Berdasarkan kepada nilai IKA dan perbandingan dengan INWQS, indeks kualiti air Sungai Pelepah Kanan adalah berada pada tahap yang bersih dan kurang mengalami pencemaran yang serius daripada aktiviti antropogenik mahupun pencemaran secara semula jadi.
Halogenated compounds are recalcitrant environmental pollutants prevalent in agricultural fields, waste waters and industrial by-products, but they can be degraded by dehalogenase-containing microbes. Notably, 2-haloalkanoic acid dehalogenases are employed to resolve optically active chloropropionates, as exemplified by the d-specific dehalogenase from Rhizobium sp. RCI (DehD), which acts on d-2-chloropropionate but not on its l-enantiomer. The catalytic residues of this dehalogenase responsible for its affinity toward d-2-chloropropionate have not been experimentally determined, although its three-dimensional crystal structure has been solved. For this study, we performed in silico docking and molecular dynamic simulations of complexes formed by this dehalogenase and d- or l-2-chloropropionate. Arg134 of the enzyme plays the key role in the stereospecific binding and Arg16 is in a position that would allow it to activate a water molecule for hydrolytic attack on the d-2-chloropropionate chiral carbon for release of the halide ion to yield l-2-hydroxypropionate. We propose that within the DehD active site, the NH group of Arg134 can form a hydrogen bond with the carboxylate of d-2-chloropropionate with a strength of ∼4 kcal/mol that may act as an acid-base catalyst, whereas, when l-2-chloropropionate is present, this bond cannot be formed. The significance of the present work is vital for rational design of this dehalogenase in order to confirm the involvement of Arg16 and Arg134 residues implicated in hydrolysis and binding of d-2-chloropropionate in the active site of d-specific dehalogenase from Rhizobium sp. RC1.
The D-2-haloacid dehalogenase of D-specific dehalogenase (DehD) from Rhizobium sp. RC1 catalyses the hydrolytic dehalogenation of D-haloalkanoic acids, inverting the substrate-product configuration and thereby forming the corresponding L-hydroxyalkanoic acids. Our investigations were focused on DehD mutants: R134A and Y135A. We examined the possible interactions between these mutants with haloalkanoic acids and characterized the key catalytic residues in the wild-type dehalogenase, to design dehalogenase enzyme(s) with improved potential for dehalogenation of a wider range of substrates. Three natural substrates of wild-type DehD, specifically, monochloroacetate, monobromoacetate and D,L-2,3-dichloropropionate, and eight other non-natural haloalkanoic acids substrates of DehD, namely, L-2-chloropropionate; L-2-bromopropionate; 2,2-dichloropropionate; dichloroacetate; dibromoacetate; trichloroacetate; tribromoacetate; and 3-chloropropionate, were docked into the active site of the DehD mutants R134A and Y135A, which produced altered catalytic functions. The mutants interacted strongly with substrates that wild-type DehD does not interact with or degrade. The interaction was particularly enhanced with 3-chloropropionate, in addition to monobromoacetate, monochloroacetate and D,L-2,3-dichloropropionate. In summary, DehD variants R134A and Y135A demonstrated increased propensity for binding haloalkanoic acid and were non-stereospecific towards halogenated substrates. The improved characteristics in these mutants suggest that their functionality could be further exploited and harnessed in bioremediations and biotechnological applications.
Artikel ini bertujuan mengkaji keberkesanan program SHIELDS daripada perspektif pelajar dan urusetia yang telah turut terlibat. Program SHIELDS adalah satu bentuk program campbased yang diperkenalkan hasil kerjasama antara Kementerian Pendidikan dan Pihak Agensi Anti Dadah Kebangsaan (AADK). Nama SHEILDS ini adalah akronim yang bermaksud Sayangi Hidup, Elak Derita Selamanya. Sehubungan itu, program ini bertujuan meningkatkan kesedaran dan mengupayakan ketahanan diri murid (lingkungan umur 13 hingga 18 tahun) yang dikenalpasti berisiko dalam penyalahgunaan dadah. Kajian kuantitatif ini melibatkan dua fasa iaitu fasa pertama adalah mengedarkan soal selidik sebelum dan selepas program SHIELDS dijalankan. Manakala, fasa kedua pula adalah sesi follow up selepas 3 bulan terhadap 50 pelajar yang telah terlibat dengan program SHIELDS terlebih dahulu. Hasil kajian menunjukkan secara keseluruhan perspektif pelajar seramai 559 orang yang terlibat dengan program SHIELDS ini adalah baik dengan min=4.48. Kesimpulannya, dapatan ini menunjukkan bahawa program SHIELDS ini sewajarnya diteruskan dengan beberapa penambahbaikan untuk kelangsungan program dan kebaikan semua pihak yang terlibat.
Suatu kajian untuk menilai kesan gabungan aktiviti guna tanah dan perubahan musim terhadap kualiti sumber air telah dijalankan di Terusan Utara, Kedah. Kajian ini dijalankan di lima stesen terpilih selama 12 bulan berdasarkan Indeks Kualiti Air (WQI) dan Piawaian Interim Kualiti Air Kebangsaan (INWQS). Kajian mendapati kualiti air di Terusan Utara berada pada Kelas III dan berlaku peningkatan kualiti air dari hulu ke hilir. Hampir semua stesen berpotensi sebagai punca pencemaran berdasarkan aktiviti guna tanah terutamanya di Pelubang, Jitra serta Tunjang. Kajian menunjukkan terdapat perbezaan yang signifikan ketika perubahan musim pada DO, TSS serta BOD, namun tidak pada ammonia, pH dan COD. Secara amnya, kombinasi aktiviti guna tanah dan perubahan musim boleh mempengaruhi atau memberi kesan terhadap kualiti sumber air. Oleh itu, tindakan segera perlu dilakukan untuk mengawal punca pencemaran bagi memastikan kualiti sumber air di Terusan Utara kekal terpelihara.
This study describes the development of a multimedia environmental fate and transport model of dichlorodiphenyltrichloroethane (DDT) at Sungai Sayong watershed. Based on the latest estimated DDT emission, the DDT concentrations in air, soil, water and sediment as well as the transfer processes were simulated under the equilibrium and steady-state assumption. Model predictions suggested that soil and sediment was the dominant sink of DDT. The results showed that the model predicted was generally good agreement with field data. Compared with degradation reaction, advection outflow was more important processes occurred in the model. Sensitivities of the model estimates to input parameters were tested. The result showed that vapour pressure (Ps) and organic carbon water partition coefficient (KOC) were the most influential parameters for the model output. The model output-concentrations of DDT in multimedia environment is very important as it can be used in future for human exposure and risk assessment of organochlorine pesticides (OCPs) at Sungai Sayong Basin.
During high-temperature refining of vegetable oils, 3-monochloropropanediol (3-MCPD) esters, possible carcinogens, are formed from acylglycerol in the presence of a chlorine source. To investigate organochlorine compounds in vegetable oils as possible precursors for 3-MCPD esters, we tested crude palm, soybean, rapeseed, sunflower, corn, coconut, and olive oils for the presence of organochlorine compounds. Having found them in all vegetable oils tested, we focused subsequent study on oil palm products. Analysis of the chlorine isotope mass pattern exhibited in high-resolution mass spectrometry enabled organochlorine compound identification in crude palm oils as constituents of wax esters, fatty acid, diacylglycerols, and sphingolipids, which are produced endogenously in oil palm mesocarp throughout ripening. Analysis of thermal decomposition and changes during refining suggested that these naturally present organochlorine compounds in palm oils and perhaps in other vegetable oils are precursors of 3-MCPD esters. Enrichment and dose-response showed a linear relationship to 3-MCPD ester formation and indicated that the sphingolipid-based organochlorine compounds are the most active precursors of 3-MCPD esters.
Magnetic solid phase extraction (MSPE) employing oil-palm fiber activated carbon (OPAC) modified with magnetite (Fe3O4) and polypyrrole (OPAC-Fe3O4-PPy) was successfully used for the determination of two organochlorine pesticides (OCPs), namely endosulfan and dieldrin in environmental water samples. Analysis was performed using gas chromatography with micro-electron capture detection (GC-μECD). The effects of three preparation variables, namely Fe3O4:OPAC ratio, amount of pyrrole monomer, and amount of FeCl3 oxidant were optimized using Box-Behnken design (BBD) (R2 < 0.99, p-value < 0.001%). The optimum conditions were as follows: Fe3O4:OPAC ratio of 2:1 w/w, 1 g of FeCl3 and 100 μL of pyrrole monomer. The experimental results obtained agreed satisfactorily with the model prediction (> 90% agreement). Optimized OPAC-Fe3O4-PPy composite was characterized using field emission scanning electron microscope, vibrating sample magnetometer and Fourier transform infrared spectroscopy. Four numerical parameters of MSPE procedure was optimized using BBD. The significance of the MSPE parameters were salt addition > sample solution pH > extraction time and desorption time. Under the optimized conditions (extraction time: 90 s, desorption time: 10 min, salt: 0%, and pH: 5.8), the method demonstrated good linearity (25-1000 ng L-1) with coefficients of determination, R2 > 0.991, and low detection limits for both endosulfan (7.3 ng L-1) and dieldrin (8.6 ng L-1). The method showed high analyte recoveries in the range of 98.6-103.5% for environmental water samples. The proposed OPAC-Fe3O4-PPy MSPE method offered good features such as sustainability, simplicity, and rapid extraction.
This study investigates the presence and distribution of organochlorine pesticides in streams and the lake in the Sembrong Lake Basin in Malaysia. The catchment of Sembrong Lake has been converted to agricultural areas over the past 30 years, with oil palm plantations and modern agricultural farming being the main land use. Surface water samples were collected from eight sites comprising the stream and lake and analysed for 19 organochlorine pesticides (OCPs). In situ measurement of temperature, dissolved oxygen, pH and conductivity were also undertaken at each site. Aldrin, endrin, δ-BHC, 4,4-DDT, methoxychlor and endosulfan were the main OCPs detected in the lake basin. The total OCP concentration ranged between 5.42 and 349.2 ng/L. The most frequently detected OCPs were δ-BHC, heptachlor and aldrin. The maximum values detected were 23.0, 43.2 and 50.4 ng/L respectively. The highest concentration of OCPs was attributed to 4,4-DDT, but such high residue was rare and only detected once. Other OCP residues were low. Significant differences in the mean values were observed between lake and stream for dichlorodiphenyldichloroethylene (DDE) and α-endosulfan concentration (p
Nineteen pairs of gaseous and surface seawater samples were collected along the cruise from Malaysia to the south of Bay of Bengal passing by Sri Lanka between April 12 and May 4, 2011 on the Chinese research vessel Shiyan I to investigate the latest OCP pollution status over the equatorial Indian Ocean. Significant decrease of α-HCH and γ-HCH was found in the air and dissolved water phase owing to global restriction for decades. Substantially high levels of p,p'-DDT, o,p'-DDT, trans-chlordane (TC), and cis-chlordane (CC) were observed in the water samples collected near Sri Lanka, indicating fresh continental riverine input of these compounds. Fugacity fractions suggest equilibrium of α-HCH at most sampling sites, while net volatilization for DDT isomers, TC and CC in most cases. Enantiomer fractions (EFs) of α-HCH and o,p'-DDT in the air and water samples were determined to trace the source of these compounds in the air. Racemic or close to racemic composition was found for atmospheric α-HCH and o,p'-DDT, while significant depletion of (+) enantiomer was found in the water phase, especially for o,p'-DDT (EFs = 0.310 ± 0.178). 24% of α-HCH in the lower air over the open sea of the equatorial Indian Ocean is estimated to be volatilized from local seawater, indicating that long-range transport is the main source.
The present study aims to investigate the susceptibility status of Aedes albopictus (Skuse) collected from residential areas in Sabah, Malaysia towards eight WHO-recommended dosages of larvicides representing the classes of organophosphates and organochlorines. Field and reference strains of Ae. albopictus larvae were bioassayed in accordance to WHO standard methods using diagnostic dosages of bromophos, malathion, fenthion, fenitrothion, temephos, chlorpyrifos, dichlorodiphenyltrichloroethane (DDT), and dieldrin. The results revealed that Ae. albopictus was resistant (mortality < 90%) towards malathion, temephos, and DDT. In addition, most of the Ae. albopictus strains exhibited a wide range of susceptibilities against bromophos, with mortality ranged from 49.33 to 93.33%. On the contrary, only dieldrin was able to induce 100% mortality against all strains of Ae. albopictus. Tolerance to fenitrothion, fenthion, and chlorpyrifos, with mortality ranging from 81.33 to 97.33%, was also observed in this study.
Chlorinated compounds such as sphingolipid-based organochlorine compounds are precursors for the formation of 3-monochlororopanediol (3-MCPD) esters in palm oil. This study evaluates the effects of several factors within the palm oil supply chain on the levels of sphingolipid-based organochlorine, which in turn may influence the formation of 3-MCPD esters during refining. These factors include application of inorganic chlorinated fertiliser in the oil palm plantation, bruising and degradation of oil palm fruits after harvest, recycling of steriliser condensate as water for dilution of crude oil during oil palm milling, water washing of palm oil and different refining conditions. It was observed that bruised and degraded oil palm fruits showed higher content of sphingolipid-based organochlorine than control. In addition, recycling steriliser condensate during milling resulted in elevated content of sphingolipid-based organochlorine in palm oil. However, the content of sphingolipid-based organochlorine compounds was reduced by neutralisation, degumming and bleaching steps during refining. Although water washing of crude palm oils (CPO) prior to refining did not reduce the content of sphingolipid-based organochlorine, it did reduce the formation of 3-MCPD esters through the removal of water-soluble chlorinated compounds. It was found that the use of inorganic chlorinated fertiliser in plantations did not increase the content of chlorinated compounds in oil palm fruits and extracted oil, and hence chlorinated fertiliser does not seem to play a role in the formation of 3-MCPD esters in palm oil. Overall, this study concluded that lack of freshness and damage to the fruits during transport to mills, combined with water and oil recycling in mills are the major contributors of chlorinated precursor for 3-MCPD esters formation in palm oil.
Pendidikan kemahiran resusitasi kardiopulmonari (CPR) kepada orang awam sangat penting dalam merendahkan kadar kematian serangan jantung. American Heart Association mencadangkan kemahiran tersebut harus dimasukkan ke dalam kurikulum sekolah. Pelatih rakan sebaya adalah kaedah yang berkos rendah dan berkesan dalam mencapai objektif ini. Objektif kajian terkawal 3 bulan ini adalah untuk membandingkan keberkesanan pengajaran kompresi CPR antara rakan sebaya dan jurulatih Basic Life Support (BLS) kepada pelajar sekolah menengah. Peningkatan pengetahuan dan kemahiran psikomotor pemampatan CPR adalah hasil utama yang dinilai. Dua belas pelatih rakan sebaya berusia 16 tahun dan dua belas pelatih BLS telah direkrut dalam kajian ini. Kompresi CPR diajarkan kepada 36 pelajar sekolah menengah secara rawak oleh pelatih rakan sebaya (Kumpulan P) atau pelatih BLS (Kumpulan B). Pra-ujian, pasca ujian serta ujian pengekalan 3 bulan mengenai pengetahuan dan kemahiran psikomotor telah dijalankan. Tidak terdapat perbezaan yang signifikan secara statistik dalam skor min pengetahuan dan psikomotor pada pra-ujian, pasca ujian serta ujian pengekalan 3 bulan antara Kumpulan P dan Kumpulan B. Terdapat peningkatan skor pengetahuan yang signifikan antara pra-ujian dan pasca ujian dalam Kumpulan P (perbezaan min 5.8+2.7, p
Dalam kajian ini, pendekatan pengelompokan kabur Gustafson-Kessel (Gx) telah digunakan untuk mengelaskan 35 stesen hujan di Semenanjung Malaysia ke dalam rantau homogen. Pertama, algoritma pengelompokan kabur GK digunakan untuk mengenal pasti rantau awal. Kemudian, diuji keserasian dan kehomogenan rantau berkenaan. Akhir sekali, penyesuaian rantau dilakukan untuk mendapatkan rantau homogen. Hasil kajian mendapati 35 stesen hujan kajian boleh dibahagikan kepada enam rantau yang homogen. Rantau 1 meliputi bahagian barat laut dan utara Semenanjung Malaysia, rantau 2, 3 dan 4 meliputi bahagian barat, rantau 5 meliputi bahagian barat daya dan rantau 6 meliputi bahagian timur. Hasil kajian ini juga memperlihatkan bahawa berdasarkan nilai purata Indeks Kerpasan Piawai (sPi) skala masa satu bulan, rantau 2 lebih sering mengalami keadaan kemarau melampau. Walau bagaimanapun, berdasarkan sPi skala masa satu bulan, peristiwa kemarau terjadi secara rawak dalam semua rantau yang dianalisis , bahkan semua rantau tersebut pernah mengalami kejadian kemarau melampau dalam tempoh masa setahun. Hasil kajian ini turut menunjukkan bahawa pendekatan pengelompokan kabur Gustafson-Kessel boleh digunakan untuk membina rantau homogen.
This study determined the concentrations of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides, and tris(4-chlorophenyl) methane (TCPMe) in human breast milk samples collected in 2003 from primipara mothers living in Penang, Malaysia. OCs were detected in all the samples analyzed with DDTs, hexachlorocyclohexane isomers (HCHs), and PCBs as the major contaminants followed by chlordane compounds (CHLs), hexachlorobenzene (HCB), and TCPMe. The residue levels of DDTs, HCHs, and CHLs were comparable to or higher than those in general populations of other countries, whereas PCBs and HCB were relatively low. In addition, dioxins and related compounds were also detected with a range of dioxin equivalent concentrations from 3.4 to 24 pg-TEQs/g lipid wt. Levels of toxic equivalents (TEQs) were slightly higher than those in other developing countries but still much lower than those of industrialized nations. One donor mother contained a high TEQs level, equal to the mean value in human breast milk from Japan, implying that some of the residents in Malaysia may be exposed to specific pollution sources of dioxins and related compounds. No association was observed between OCs concentrations and maternal characteristics, which might be related to a limited number of samples, narrow range of age of the donor mothers, and/or other external factors. The recently identified endocrine disrupter, TCPMe, was also detected in all human breast milk samples of this study. A significant positive correlation was observed between TCPMe and DDTs, suggesting that technical DDT might be a source of TCPMe in Malaysia. The present study provides a useful baseline for future studies on the accumulations of OCs in the general population of Malaysia.
Fenologi tumbuhan menggambarkan fasa kitaran hidup atau aktiviti tumbuhan dan adalah penting untuk memahami
interaksinya dengan iklim. Kajian dilakukan untuk mengenal pasti respons fenologi tumbuhan dan metrik fenologi
hutan dipterokarpa, kelapa sawit dan pokok getah menggunakan data indeks tumbuhan Enhanced Vegetation Index
(EVI) daripada MODIS-Aqua (produk MYD13Q1) dan purata hujan bulanan sepanjang tahun 2007 dan 2009 di negeri
Johor. Pola hujan pada tahun 2007 menunjukkan taburan hujan normal, manakala tahun 2009 mengalami kekurangan
hujan sepanjang tempoh sebelas tahun (2000-2010). Hasil mendapati tren EVI hutan dipterokarpa lebih bervariasi pada
2009 dengan nilai EVI antara 0.39-0.64 berbanding tren pada 2007 yang tekal dengan nilai EVI antara 0.33-0.57. Tren
fenologi kelapa sawit pada 2007 lebih kerap mengalami turun naik berbanding pada 2009, masing-masing dengan EVI
antara 0.45-0.71 dan 0.5-0.74. Corak fenologi pokok getah pada kedua-dua tahun kajian adalah sama dan julat EVI
pada 2009 adalah lebih kecil berbanding 2007, masing-masing dengan EVI antara 0.39-0.62 dan 0.30-0.73. Pengaruh
masa susulan ke atas tahap kehijauan tumbuhan telah dikesan, khususnya selepas peristiwa hujan lebat dalam dua
tahun tersebut dan sedikit sebanyak mempengaruhi nilai korelasi antara pemboleh ubah purata hujan bulanan dengan
EVI tumbuh-tumbuhan. Permulaan dan pengakhiran musim pertumbuhan hutan dipterokarpa bagi kedua-dua tahun
berlaku dalam bulan yang sama, iaitu Februari (permulaan musim) dan Disember (pengakhiran musim). Tidak wujud
perbezaan yang ketara antara panjang musim pertumbuhan kelapa sawit bagi kedua-dua tahun, iaitu hanya 32 hari
lebih panjang pada 2007 berbanding 2009. Musim pertumbuhan pokok getah pula adalah lebih panjang pada 2007 dan
lebih singkat pada 2009, masing-masing 176 hari dan 113 hari.
Since a few centuries ago, organochlorine compounds (OCs) become one of the threatened contaminants in the world. Due to the lipophilic and hydrophobic properties, OCs always discover in fat or lipid layers through bioaccumulation and biomagnification. The OCs are able to retain in soil, sediment and water for long time as it is volatile, OCs will evaporate from soil and condense in water easily and frequently, which pollute the shelter of aquatic life and it affects the function of organs and damage system in human body. Photocatalysis that employs the usage of semiconductor nanophotocatalyst and solar energy can be the possible alternative for current conventional water remediation technologies. With the benefits of utilizing renewable energy, no production of harmful by-products and easy operation, degradation of organic pollutants in rural water bodies can be established. Besides, nanophotocatalyst that is synthesized with nanotechnology outnumbered conventional catalyst with larger surface area to volume ratio, thus higher photocatalytic activity is observed. In contrast, disadvantages particularly no residual effect in water distribution network, requirement of post-treatment and easily affected by various factors accompanied with photocatalysis method cannot be ignored. These various factors constrained the photocatalytic efficiency via nanocatalysts which causes the full capacity of solar photocatalysis has yet to be put into practice. Therefore, further modifications and research are still required in nanophotocatalysts' synthesis to overcome limitations such as large band gaps and photodecontamination.