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Ghavidel, M., Shirazi Beheshtiha, S., Heravi, M. (2018). Cu(I) nanoparticles immobilized onto Poly (Vinylpyridine-N-N-Methylenebisacrylamide-Acrylicacid) as a new, efficient and recyclable catalyst for the regioselective synthesis of 1, 2, 3-Triazoles via click reaction in water. International Journal of Nano Dimension, 9(4), 408-420.
Mahdieh Ghavidel; Seyed Yahya Shirazi Beheshtiha; Majida Heravi. "Cu(I) nanoparticles immobilized onto Poly (Vinylpyridine-N-N-Methylenebisacrylamide-Acrylicacid) as a new, efficient and recyclable catalyst for the regioselective synthesis of 1, 2, 3-Triazoles via click reaction in water". International Journal of Nano Dimension, 9, 4, 2018, 408-420.
Ghavidel, M., Shirazi Beheshtiha, S., Heravi, M. (2018). 'Cu(I) nanoparticles immobilized onto Poly (Vinylpyridine-N-N-Methylenebisacrylamide-Acrylicacid) as a new, efficient and recyclable catalyst for the regioselective synthesis of 1, 2, 3-Triazoles via click reaction in water', International Journal of Nano Dimension, 9(4), pp. 408-420.
Ghavidel, M., Shirazi Beheshtiha, S., Heravi, M. Cu(I) nanoparticles immobilized onto Poly (Vinylpyridine-N-N-Methylenebisacrylamide-Acrylicacid) as a new, efficient and recyclable catalyst for the regioselective synthesis of 1, 2, 3-Triazoles via click reaction in water. International Journal of Nano Dimension, 2018; 9(4): 408-420.
Department of Chemistry, School of Sciences, Alzahra University, Vanak, Tehran, Iran.
Poly (vinylpyridine-N-N-methylenebisacrylamide-acrylicacid) (2-VP-MBAm-AA) was prepared from the reaction of TiO2-methacryloxypropyltrimethoxysilane (TiO2-MAPTMS) with 2-vinylpyridine, methylenbisacrylamide (MBAm) and tert-butyl acrylate (t-BuA). Subsequently (2-VP-MBAm-AA) was reacted with CuI to give the Cu(I) NPs supported onto the above polymer. These immobilized nano-particles were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), FT-IR and inductively coupled plasma optical emission spectrometry (ICP-OES). This well characterized composite was examined as effective and reusable heterogeneous catalyst in water for the regioselective synthesis of 1, 4-disubstituted 1, 2, 3-triazoles in excellent yields. The catalyst can be recovered by simple filtration and reused for at least five runs without losing its efficiency.
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Nowadays research in synthetic organic and medicinal chemistry, are focused on the synthesis of structurally complex molecules through a rational design. Importantly, if these molecules show any practical applications, the synthetic pathway should be both synthetically operational and economically feasible .
Due to their high accessible surface area and unique quantum effect, immobilized-metal nanoparticles are among the very interesting and effective catalytic components . Among different base-metal-NPs, copper nanoparticles (Cu NPs) show the particularly unique catalytic activity in a broad range of chemical transformation and energy related areas such as the Huisegn 1,3-dipolar cycloaddition of azide-alkyne [3, 4], hydrogenation , reduction [6, 7], oxidation  and cross-coupling reactions .
Utilization of metal-NPs in catalyzed organic transformations have attracted much attention of organic synthetic chemists due to their remarkable electronic, optical, and catalytic qualities and also their significant large surface area to volume ratio [10, 11].
Cu(I) and Cu(II)–catalyzed reactions in organic transformations are well-studied and appreciated . Based on the substantial kind of surface, size and quantum effects, use of nanoparticles (NPs), with the well-recognized unique properties are more favorable comparing with the use of their ordinary counter parts . NPs are more active under mild reaction conditions and at the same time the essential features of a heterogeneous catalysis are maintained .
In addition, the industrial catalysts often work on the surface of metals, thus metal-NPs, which has much surface area per unit volume or weight in comparison with virgin metal are considered as gifted catalysts .
Copper NPs can be provided via different procedures such as thermal decomposition of precursors, reduction from a solution by mild reducing agents as well as electrochemical methods [12, 15-19].
They can also be prepared by photoreduction, MWI, micro emulsion techniques and laser ablation [20-25]. In addition, using ultrasonic irradiation recently has attracted tremendous attention in the preparation of nanomaterials [26-28].
Cu-based nanocatalysts have exhibited several applications in the field of nanoscience and nanotechnology, including a wide range of catalyzed-organic reactions, electrocatalysis, and photocatalysis [29-37].
Immobilization of homogeneous catalysts on solid supports often presents advantages. These supported catalysts have attracted much attention in organic synthesis for different reasons [38, 39] including easy separation from the reaction mixture by simple filtration and sometimes providing high catalytic activity, stability, and selectivity in comparison to unsupported materials [40, 41].
The cycloaddition is the reaction of a dipolarophile with a 1,3-dipolar compound that leads to 5-membered heterocycles. The azide-alkyne Huisgen cycloaddition is a 1,3-dipolar cycloaddition between an azide and a terminal or internal alkyne to give 1,2,3-triazole ring. Rolf Huisgen was the first who understood the scope of this organic reaction. Regrettably, the thermal Huisgen 1,3-dipolar cycloaddition of alkynes to azides required elevated temperatures and often produced mixtures of the two regioisomers when asymmetric alkynes are used . In this respect, the classic 1,3-dipolar cycloaddition fails as an ideal reaction as well as requiring harsh reaction conditions .
However, the Cu(I)-catalyzed 1,3-dipolar Huisegn cycloaddition has circumvented these back draws.
In 2002, Sharpless et al.  reported that the use of catalytic amounts of Cu(I) resulted in the rapid and regioselective Huisegn azide-alkyne cycloadditions at ambient temperature. Latter they called this reaction as a cream crop of click reaction [45-47].
The role of Cu(I) as a coordinating agent in the mechanistic pathway of click reactions has now been well established. As a matter of fact the coordination of Cu(I) with terminal alkynes along with the activation of azide species to produce a copper-azide-acetylide complex were responsible for such advantages [48, 49]. Nowadays, it is well known that the ligand protects the Cu ion from undesired interactions leading to degradation and generation of side products and more importantly prevents the oxidation of the Cu(I) species to the Cu(II) [50, 51] Moreover, immobilization of Cu(I) nanoparticles on different kinds of supports compared to Cu(0) NPs is a useful method to make them heterogeneous, thus easily recoverable and reusable [52-54].
Thus, notable variant of the Huisgen 1,3-dipolar cycloaddition is the modified Cu(I)-catalyzed reaction is no longer a true concerted cycloaddition, in which organic azides and terminal alkynes are united to afford 1,4-regioisomers of 1,2,3-triazoles as the sole products.
The copper(I)-catalyzed variant was first reported in 2002 in independently Meldal at the Carlsberg Laboratory in Denmark  and then by K. Barry Sharpless at the Scripps Research Institute . Thus, at ambient and green conditions, 1,2,3-triazoles can be synthesized. They are a significant class of heterocyclic compound due to their usefulness as agrochemicals, dyes, corrosion inhibitors, photostabilizers, fluorescent whiteners and optical brightening agents  and photographic materials [57-61].
1,2,3-Triazoles exhibit a wide range of biological activity and even pharmaceutical properties such as antiviral, antifungal, antitubercular , antiepileptic antimalarial, antidiabetic, anticancer , antibacterial, antiallergic, anti-HIV activity and selective β3 adrenergic receptor agonist [64-68].
Nowadays, it has been found that N-substituted 1,2,3-triazoles have more potential uses than simple 1,2,3-triazole derivatives . Nonetheless, for the synthesis of N-substituted 1,2,3-triazoles via Cu(I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC) , the starting materials, such as functional alkynes and organic azides were not easily accessible and those commercially available are expensive.
In addition, although the synthesis of N-substituted 1,2,3-triazoles proceed smoothly in the presence of Cu salts as homogeneous catalyst, their separation and recovery from the reaction mixture is usually difficult. Besides, it is possible that the obtained 1,2,3-triazoles were contaminated by the Cu metal in homogeneous catalysis. In order to overcome the above deficiencies and cumbersome, immobilizing the Cu salts as heterogeneous catalysts in CuAAC reaction is still in much demands.
Recently, polymer-supported reagents have attracted much attention as insoluble matrices in organic synthesis . A wide range of polymer-supported nanoparticles of Cu(I) as reusable catalyst in the click synthesis of 1,2,3-triazoles between azides and alkynes have been reported [72-74]. Polymeric supports bearing nitrogen as electron releasing atoms are of distinctive importance. One of such polymers is cross-linked. Poly(vinylpyridine) (PVPy) which is a functionalized polymer is able to coordinate with different transition metal ions. The complexation between PVPy and several transition metals have been prepared and employed as catalysts in several organic transformations [75-80].
Cross-linked PVPy, as insoluble polymer showing unique properties, nowadays they are frequently used as support for preparing heterogeneous catalysts. It shows extraordinary properties such as: (a) it can undergo easy functionalization, (b) it has several accessible functional groups, (c) it is not hygroscopic, (d) it can be provided easily and even some of them are commercially available, (e) it can be easily filtered, and (f) it can be swelled in conventional organic solvents . Noticeably, PVPy has two market purchasable isomers so-called poly(4-vinylpyridine) (P4VPy), and poly(2-vinylpyridine) (P2VPy) . Some differences in the performance and properties between some derivatives of P4VPy and P2VPy have been recognized and previously reported [82-86]. P2VPy can be made with different strategies exhibiting fascinating physical and chemical properties .
Poly (2-VP-MBAm-AA) is a copolymer that has been prepared from 2-vinyl pyridine and tert-butyl acrylate (t-BuA) as a monomer and N,N-methylenbisacrylamide (MBAm) as a crosslinker to acquire a three-dimensional skeleton .
We are interested in heterocyclic chemistry [87-95] via MCR [73, 74, 96, 97] under green conditions  and heterogeneous catalysis, applied in a wide range of organic transformations . We have also recently had successful attempts for the synthesis of 1,2,3-triazoles, via click reaction under heterogeneous catalysis [73-75, 100-104] including their theoretical studies.
Worthy to emphasize that the Poly (2-VP-MBAm-AA) nanocomposite has never been examined as catalyst in organic transformation but used as a colorimetric sensor based on dithizone-anchored poly (vinyl pyridine-N,N-methylenebisacrylamide-acrylic acid) (poly (2-VP-MBAm-AA)) nanocomposite for detection of mercury and lead ions trace levels from aqueous media .
In this study, we have investigated the reaction of TiO2-MAPTMS with 2-vinylpyridine, methylenbisacrylamide and tert‐butyl acrylate to obtain the poly (vinyl pyridine-N,N-methylenebisacrylamide-acrylic acid) (poly (2-VP-MBAm-AA))  and used it as a support of immobilization of nano-Cu(I) for the preparation of a novel heterogeneous catalyst so called TiO2/poly (2-VP-MBAm-AA)-CuI.
For preventing the agglomeration tendency of NPs, Cu(I) NPs were prepared in situ  and supported on the polymer surface to afford the immobilized heterogeneous catalyst. This novel nanocatalyst was examined in a one-pot three-component click synthesis of 1,4-disubstituted-1H-1,2,3-triazoles involving α-haloketones or benzyl halides, sodium azide, and terminal alkynes via click reaction in water as a greenest and most abundant solvent.
Thoroughly Cu-NPs were prepared via a facile and effective methodology. By using the above-mentioned novel catalyst, the regioselective products could be separated by a simple filtration, thus, avoiding time-consuming and problematic separation steps. High yields, short reaction times, regioselectivity, mild reaction conditions and five repeated runs, with very low leaching of the immobilized catalyst, make this strategy very simple and useful for the synthesis of wide range of 1,4-disubstituted 1,2,3-triazoles.
Furthermore, using water as green reaction medium and experimental simplicity are other advantages of using this catalyst in the synthesis of triazoles via click reaction.
CuI nanoparticles has less cytotoxicity of the traditional Cu(I) reagents. Hence, we think our catalyst is worthwhile to be examined to other copper-catalyzed organic transformations.
N,N-Dimethylformamide (DMF) and acetonitrile were distilled and stored over 4 A° molecular sieve before use; other reagents were used as received from Aldrich and Merck Chemical Companies with high-grade quality. Copper content was measured by SPECTRO ARCOS ICP-OES analyzer. Scanning electron micrographs were recorded using Tescan Vega-3 LMU SEM instruments. FT-IR spectra were recorded on FT-IR Bruker Tensor 27 instrument using KBr disks in the 500–4,000 cm-1 region.
Initially TiO2 NPs were provided in accordance to the procedure reported, previously . Accordingly, aqueous solution of ammonium sulfate (1.5 mol L-1) and titanium (IV) chloride (0.75 mol L-1) were mixed to react. This reaction proceeded at 75 °C and completed in 90 min. Upon completion of this reaction, NH4OH (2.5 mol L-1) was gradually added under vigorous stirring until the pH of mixture was reached to 7. Then, the obtained solid was filtered off, washed with water/ethanol and dried at 60 °C. Then calcination of NPs was achieved at 350 °C for 4 h which allowed to cool down to room temperature .
For preparation of TiO2-MAPTMS NPs, we followed our previously reported method . Accordingly, TiO2 NPs (1g) were dispersed in dry toluene (30 ml) using ultrasonic bath for 15 min. Then, MAPTMS (2 ml) was added as a coupling agent, drop wise to the mixture and the solution was kept under N2atmosphere at ambient temperature for 48 h with vigorous stirring. The final product was separated by centrifugation and washed with toluene twice. Then modified TiO2 NPs were dried under vacuum at 60 ◦C for 24 h.
To provide hydrogel in 1:0.2:1 mole ratios, 2-VP, MBAm and t-BuA, TiO2-MAPTMS (0.5 g) were dissolved in DMSO (15 ml) and dispersed using ultrasonic bath for 15 min, under stirring and N2 purging for the same time, 2-Vp, (3 ml), t-BuA (4.1 ml) and MBAm (0.9 g) were added to the reaction mixture and stirred for 2 h. Ultimately, the resulting solution was heated up to 80 °C with subsequent addition of AIBN (0.08 g). The polymerization was occurred in 2 h. The obtained hydrogel was washed several times with EtOH for the removal of unreacted monomers and then dried at 50 °C. To hydrolyze the obtained hydrogel, the dried hydrogel (1g) was poured into the reaction vessel contained CH2Cl2 (40 ml) and TFA (5 ml). Upon stirring the mixture in 24 h, the hydrolyzed hydrogel was washed with EtOH/H2O and dried at 60 °C .
CuI (0.247 g) was dissolved in dry CH3CN (2 ml) under ultrasonic and stirred for a while to obtain a transparent light yellow solution. Then DMF (20 ml) was added at ambient temperature to obtain CuI NPs [102-105]. It was then transferred into a 100 ml round-bottom flask containing dry polymer-supported (1 g). Then the mixture was magnetically stirred at reflux temperature for 5 h under a nitrogen atmosphere. The TiO2/poly (2-VP-MBAm-AA)-CuI as a heterogeneous catalyst was filtrated and washed with CH3CN (2×20 ml) and dried under vacuum at 60 ◦C for 24 h.
In a round-bottom flask, an appropriate α-halogenoketone (1 mmol) or benzyl halide (1 mmol) (5a–e), a suitable alkyne (1 mmol) (6a-6c), sodium azide (1.1 mmol), and water (10 ml) were placed. Then, TiO2/poly (2-VP-MBAm-AA)-CuI catalyst 4 (0.02 g) was added (Fig. 1), and the suspension was magnetically stirred under reflux for the appropriate time. The progress of the reaction was monitored by TLC (using n-hexane: ethyl acetate; 7:3 as eluent). Upon the completion of the reaction, the resin was filtered off and washed with hot EtOH. The recovered catalyst was washed with acetone, dried under reduced pressure at 70 ºC for 3 h and stored for being employed in another reaction. Upon evaporation of the solvent of the filtrate, a solid was obtained which was recrystallized from hot EtOH to give the pure products in high yields. All the obtained triazoles (8a–h) were known and their physical data were compared with those of authentic samples and were found being identical [84-86, 106-110].
The TiO2 nanoparticles were initially provided in accordance with the procedure reported in the literature, previously  followed by modification using MAPTMS. Then, TiO2-MAPTMS react with 2-vinylpyridine, methylenbisacrylamide (MBAm) and tert-butyl acrylate (t-BuA) to form TiO2/poly (2-VP-MBAm-AA) for being examined as a polymeric support (Fig. 2) The structure of product of each step was confirmed by FT-IR spectroscopy, X-ray diffraction, SEM images and thermogravimetry analysis .
Poly(vinyl pyridine) was known as a reactive species due to its high nucleophilicity but weakly basic due to ring nitrogen. Then, CuI NPs were supported to the synthesized above mentioned polymer support. In order to prevent agglomeration of the nanoparticles, Cu(I) NPs were synthesized in situ and then refluxed with polymer support under N2 atmosphere in DMF . In this way, Cu(I) NPs were immobilized onto polymer support to obtain polymer-supported CuI nanoparticle catalyst (Fig. 2). As expected, the TiO2/poly (2-VP-MBAm-AA)-CuI NPs were insoluble in all common organic solvents thus, its structural characterization was limited to obtain their SEM, EDX, and ICP analysis.
The SEM of the TiO2/poly (2-VP-MBAm-AA)-CuI NPs (Fig. 3) vividly illustrated that the Cu(I) nanoparticles were homogeneously supported on the prepared polymer surface. The average size of Cu(I) NPs was estimated to be 43.85-75.24 nm.
Energy dispersive spectroscopy analysis (EDX) data for the TiO2/poly (2-VP-MBAm-AA)-CuI nanocatalyst is illustrated given in Fig. 4. The EDX data confirms that polymer matrix is containing Cu(I) NPs onto its surface. This data along with other aforementioned data such as SEM and FT‐IR approved the attachment of Cu(I) NPs onto TiO2/poly (2-VP-MBAm-AA).
The FT-IR spectrum of our sample was found identical to the already reported for TiO2 nanoparticles, TiO2-MAPTMS, TiO2/poly (2-VPMBAm-t-BuA) nanocomposite  is shown in Fig. 5. As it can be seen clearly in Fig. 5a, the absorption broad bands below 800 cm-1 and the broad peak in ۳۰۳۸ cm-1 can be assigned to the Ti-O bond vibration and hydroxyl groups of TiO2 nanoparticles, respectively . On the other hand, the peaks in 956 cm-1, 1639 cm-1, 1712 cm-1 and ۲۸۷۹-۲۹۱۹ cm-1 can be assigned to the Ti-O-Si, C=C and C=O moieties, respectively (Fig. 5b) [113-115]. In conclusion, the preparation and modification TiO2-MAPTMS has been approved.
The fruitful polymerization can be realized and approved by the appearing and presence of new peaks in IR spectrum shown in Fig. 5c. The other characteristic bands at 1732 cm-1 attributed to ester groups of t-BuA, at 1659 cm-1 associated to amide carbonyl groups and ۱۵۳۳ cm-1 assigned to the N-H bond of MBAm bending vibration , 1593 cm-1 and ۱۵۵۷ cm-1 corresponding to the pyridine-stretching vibrations [117, 118] 1149 cm-1, and 1248 cm-1 associated to CO-C and C-N bonds, respectively [118, 119]. Upon the hydrolysis of t-BuA, appearance of a new peak at 1692 cm-1 clearly the presence of carboxyl moieties. Notably, the intensity of C-O-C at ۱۱۴۹ cm-1 was also reduced and can be clearly observed.
FT-IR spectrum (Fig. 6) of prepared Cu(I) NPs catalyst revealed the interaction of TiO2/poly (2-VP-MBAm-t-BuA) with Cu(I) NPs by observation of changes and shifts for the positions of several bands.
The Cu content of polymer was evaluated upon treatment of TiO2/poly (2-VP-MBAm-AA)-CuI (100 mg) with a mixture of Conc. HCl/HNO3 (1:1, 10 ml) by digestion of the copper species. The mixture was transferred into a volumetric flask (100 ml), diluted and then was analyzed by ICP. The Cu concentration was determined from the atomic emission (324.754 nm) by reference to a linear (R = 0.99) calibration curve of (1–4 ppm) of CuI provided by a procedure similar to the sample preparation. The Cu content was defined being 6.6 % w/w. The same procedure was employed to disclose the extent of leaching from the immobilized catalyst after five consecutive runs.
Initially, a mixture of benzylchloride (1 mmol), sodium azide (1.1 mmol), and phenylacetylene (1 mmol) was chosen as a model reaction in the presence of catalytic amount of TiO2/poly (2-VP-MBAm-AA)-CuI and in different solvents (Table 1).
Although the ‘click’ azide-alkyne cycloaddition reaction has been successfully examined in a wide range of common organic solvents, but as illustrated in Table 1, it can be seen that water acts as the most efficient solvent in comparison to the others thus we used water as the solvent of choice. We focused our attention on the reaction in pure water, since this is the solvent of choice in green chemistry as well as being accessible virtually free of cost. Thus, to test the substrate scope of reaction in water various terminal alkynes and α-halo ketones or benzyl halides were successfully examined, establishing the generality of our methodology (Table 2).
It is worthwhile to mention that for the resin, extensive mechanical degradation after its catalytic activity was not observed as for a real heterogeneous catalysis. The supported catalyst should not leach into the reaction mixture since the reusability of the catalyst is much in concern. To study these properties for our new catalytic system, we selected the reaction of benzyl chloride, phenyl acetylene, and sodium azide as a model reaction. We observed no appreciable loss in the catalytic activity after five consecutive runs (Fig. 7), and no need for reloading the catalyst. As a matter of fact, the difference in the Cu content for the fresh and recycled catalyst was not significant after the five run, confirming a low leaching for our new catalyst system.
In this summary, for the first time, we developed a Cu(I), catalytic system with the heterogeneous catalysts merits, for example rapid and easy separation of the catalytic system by simple filtration as well as efficient recovery and reusing it in a one-pot synthesis of 1,4-disubstituted-1H-1,2,3-triazoles via click reaction of terminal alkynes, α-halo ketones and NaN3 in the presence of a new recyclable catalyst at reflux temperature in water as the greenest and most abundant solvent. The 1,2,3-triazoles were obtained regioselectively in satisfactory yields purities, confirmed by comparison of their physical with those of authentic samples and were found being identical.
Furthermore, using water as solvent, operational simplicity, ease of work-up and clean procedure, make this newly introduced catalyst as an useful and important additional strategy to the already reported protocols for the regioselective synthesis of 1,2,3-triazoles. Our observation showed that this catalyst give satisfactory yields in reasonable reaction times and can be used for five consecutive runs, with very low leaching of the immobilized Cu(I). Therefore, this modified TiO2/poly (2-VP-MBAm-AA)-CuI can be considered as an attractive support in the synthesis of polymer supported catalysts in other organic transformations especially those catalyzed by Cu(I). The produced Cu(I) NPs catalyst was characterized by FT-IR, SEM, EDX, ICP–OES methods.
The authors are thankful to Alzahra Research Council for partial financial support.
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APPEALED FROM THE NINETEENTH JUDICIAL DISTRICT COURT IN AND FOR THE PARISH OF EAST BATON ROUGE, LOUISIANA DOCKET NUMBER 538,536 HONORABLE WILSON FIELDS, JUDGE PRESIDING.
Randy B. Ligh, Baton Rouge, LA and Victor R. Loraso, III, Baton Rouge, LA, Counsel for Plaintiffs/Appellees, Emile and Glenn Aites.
Alice Estill, Baton Rouge, LA, Counsel for Defendants/Appellees, Andre Noel, Sr., and Andre's Upholstery Custom Interiors.
Craig D. Gremillion, Baton Rouge, LA, Counsel for Defendant/Appellant, State Farm Fire Casualty Company.
BEFORE: WHIPPLE, HUGHES AND WELCH, JJ.
State Farm Fire and Casualty Company ("State Farm") appeals the trial court's judgment awarding damages to plaintiffs, Emile and Glenn Aites, for injuries sustained by Mr. Aites when he slipped on a ramp while exiting the shop area of Andre's Upholstery and Custom Interiors (Andre's Upholstery"). For the following reasons, we amend the judgment to assign a percentage of fault to Mr. Aites and, as amended, affirm the judgment.
On the drizzling, rainy morning of January 13, 2005, Mr. Emile Aites visited Andre's Upholstery in Baton Rouge, Louisiana, to obtain an estimate from Andre Noel, Sr., the owner of Andre's Upholstery, for the repair of the vinyl top of Mr. Aites's wife's vehicle. Mr. Aites entered the business premises, which were leased by Mr. Noel from premises owner Joel Sanders, by means of a stairway leading into the office area of the premises. After Mr. Aites and Mr. Noel spoke in the office area, both men proceeded through an interior door into the shop or garage area of the premises to view vinyl swatch samples. In addition to an interior doorway from the office area, the garage or shop area could also be accessed from outside through a garage door opening and adjoining ramp.
While the men were in the shop or garage area, Mr. Noel instructed Mr. Aites to drive the vehicle into the garage or shop area to match vinyl swatches to the vinyl top on the vehicle. When he instructed Mr. Aites to retrieve his vehicle, Mr. Noel motioned toward the vehicle, which was parked outside and visible through the open garage door. Mr. Aites, who was holding an umbrella, then began to descend the ramp leading outside from the garage or shop area, walking at a fast pace, to retrieve the vehicle when he slipped on the ramp and fell, fracturing his ankle. As a result of the accident, Mr. Aites had to undergo surgery to repair the ankle.
Thereafter, Mr. Aites and his wife, Glenn Aites, filed suit against Mr. Noel, d/b/a Andre's Upholstery; Mr. Sanders, as owner of the property; and State Farm, the liability insurer of Mr. Sanders, seeking damages as a result of the fall. Following a bench trial, the trial court found Mr. Sanders and State Farm 100% at fault and further found that Mr. Aites was entitled to general and special damages totaling $40,297.94, subject to a $5,000.00 credit in favor of State Farm for medical payments previously made. The trial court also found that Mrs. Aites was entitled to loss-of-consortium damages in the amount of $7,500.00. By judgment dated March 4, 2009, the trial court rendered judgment in favor of Mr. and Mrs. Aites and against State Farm in the amounts set forth in its reasons for judgment.
Notably, State Farm, as Mr. Sanders's insurer, answered the Aiteses' petition herein, but no answer was filed on behalf of Mr. Sanders. Nonetheless, while no answer was ever filed on his behalf, Mr. Sanders appeared at trial, apparently represented by counsel for State Farm. Despite Mr. Sanders's appearance and the trial court's findings of fault, the judgment herein was rendered against State Farm only, and not against Mr. Sanders. Mr. and Mrs. Aites did not appeal the trial court's failure to render judgment against Mr. Sanders, and, while State Farm mentions in a footnote in its brief, that the "judgment should have included Joel E. Sanders," it likewise did not specifically assign this as error.
From this judgment, State Farm appeals, contending that: (1) the trial court erred as a matter of law in finding Mr. Sanders and State Farm liable for Mr. and Mrs. Aites's injuries without first determining whether the ramp in question contained a defect which created an unreasonable risk of harm; and (2) alternatively, the trial court erred in finding Mr. Aites free from fault where he chose to descend a metal ramp in the rain, at a pace faster than walking, while wearing rubber-soled tennis shoes and holding an umbrella. Mr. and Mrs. Aites answered the appeal, contending that their general damage awards were too low.
In its first assignment of error, State Farm contends that the trial court committed legal error in finding Mr. Sanders and State Farm at fault herein while failing to determine whether the ramp at issue contained a defect which created an unreasonable risk of harm and which caused Mr. Aites's injury. Thus, State Farm contends that this court should review the matter de novo and, upon de novo review, should conclude that the Aiteses failed to prove these elements of their claim.
The owner or person having custody of immovable property has a duty to keep such property in a reasonably safe condition. He must discover any unreasonably dangerous condition on the premises and either correct the condition or warn potential victims of its existence. Dauzat v. Curnest Guillot Logging Inc., 2008-0528 (La. 12/2/08), 995 So. 2d 1184, 1186; Bozeman v. Scott Range Twelve Limited Partnership, 2003-0903 (La. App. 1st Cir. 4/2/04), 878 So. 2d 615, 619, writ not considered, 2004-1945 (La. 11/8/04), 885 So. 2d 1142. This duty is the same under the strict liability theory of LSA-C.C. art. 2317 and the negligence theory of LSA-C.C. art. 2315. Under either theory, the plaintiff has the burden of proving that: (1) the property that caused the damage was in the "custody" of the defendant; (2) the property had a condition that created an unreasonable risk of harm to persons on the premises; (3) the unreasonably dangerous condition was a cause in fact of the resulting injury; and (4) the defendant had actual or constructive knowledge of the risk. Bozeman, 878 So. 2d at 619.
Through this assignment of error, State Farm complains that the trial court committed legal error because it failed to make specific findings as to the second and third elements.
At the conclusion of the bench trial herein, the trial court stated that it found "Mr. Sanders and State Farm at fault for the accident." While the trial court did not further expound on its finding of fault, specifically regarding its implicit underlying findings of a defect creating an unreasonable risk of harm or the cause-in-fact element, we disagree with State Farm's assertion that the failure to articulate the particular basis for the court's ruling constitutes legal error interdicting the ruling or affecting the standard of review. We further find no merit in State Farm's seeming implication that the trial court clearly failed to consider these underlying elements necessary to its ultimate finding of fault.
In nonjury cases to recover damages for injury, death, or loss, whether or not requested to do so by a party, the court shall make specific findings that shall include those matters to which reference is made in Paragraph C of Article 1812 of this Code. These findings need not include reasons for judgment.
Further, Paragraph C of Code of Civil Procedure article 1812 pertains to jury trials and lists the issues, in cases to recover damages for injury, death, or loss, for which a trial court, at the request of any party, must submit to the jury special written interrogatories. These issues include: (1) whether a party from whom damages are claimed was at fault and, if so, whether such fault was a legal cause of the damages and the degree of such fault; (2) if appropriate under the facts, whether another party or non-party was at fault and, if so, whether such fault was a legal cause of the damages and the degree of such fault; (3) if appropriate, whether there was negligence attributable to any party claiming damages; and (4) the total amount of special damages and general damages sustained.
In the instant case, the trial court clearly determined that Mr. Sanders and State Farm were at fault for the accident, thereby complying with LSA-C.C.P. art. 1917(B). Moreover, based on our review of the record, and given that a large portion of the trial testimony centered around the alleged defective condition of the ramp, we likewise conclude that the trial court's finding of fault was clearly based on the necessary underlying factual findings of an unreasonably dangerous condition and cause-in-fact. Accordingly, we find no merit to State Farm's argument that the trial court committed legal error in failing to specifically state that the ramp contained a defect that created an unreasonable risk of harm and that the defect caused Mr. Aites's injury. Accordingly, de novo review is not warranted herein.
We further note that State Farm did not request reasons for judgment from the trial court, as it was entitled to do pursuant to LSA-C.C.P. art. 1917(A).
Additionally, we note that the evidence presented at trial established that the ramp was regularly used by pedestrians to enter and exit the shop or garage area of the premises, and there were no signs on the premises warning pedestrians not to use the ramp to enter the shop or garage area. Moreover, the trial court was presented with the opposing opinions of two expert witnesses with regard to whether the ramp presented an unreasonable risk of harm.
Wilfred Gallardo, the Aiteses' safety expert, testified that the metal ramp at issue had a raised diamond plate. He explained that, normally, the raised diamonds have rough ridges on top of them to provide traction, but that when the ridges wear off, all that is left is a "plain raised diamond plate" that is a "smooth surface." His inspection of the ramp revealed that there were no rough ridges on the raised pattern of this particular ramp. Rather, the ramp had a plain raised diamond plate, which he opined was "the same thing as stepping on a piece of metal," and which would be slippery when wet. Mr. Gallardo further stated that when he placed water on the ramp during his inspection, his foot slipped on the ramp despite the fact that he was wearing non-slip shoes. Moreover, while the ramp was designed as a vehicle ramp, Mr. Gallardo noted that it was being utilized as a pedestrian ramp, and it did not have a handrail for use as a pedestrian ramp. Thus, based on the foregoing, Mr. Gallardo opined that it was defective for that particular use. Additionally, Mr. Gallardo testified that, in his opinion, the rust on the ramp would make it "a little bit more slippery with water," noting that as a pedestrian walked on the rusted surface, some of the rust would come off.
Mr. Gallardo testified that the ramp should have been roped off with a sign warning pedestrians not to use it. He testified that alternatively, the ramp could have been painted with a non-skid paint at a mere cost of approximately $50.00.
On the other hand, Fred Vanderbrook, State Farm's expert mechanical engineer, opined that, while the ramp was intended primarily as a vehicle ramp, the raised design on the ramp, which he called a checker-plate design, provided a very good slip-resistant surface for either vehicles or for pedestrians. Mr. Vanderbrook further testified that, in his opinion, the rust on the surface of the ramp also made it "relatively rough" and that rusted surfaces "are pretty slip resistant." Thus, Mr. Vanderbrook did not believe that this ramp presented an unreasonable risk of harm or that it was defective in the manner in which it was maintained.
Mr. Vanderbrook was accepted by the court as an expert in the field of engineering, but not safety.
Mr. Vanderbrook went on to testify that, "in all likelihood," as Mr. Aites was coming down the ramp at an increased rate of speed, Mr. Aites turned and "the motion he was exerting exceeded the coefficient of friction that was available to him," thereby causing him to slip. However, when questioned by the court as to how he determined that Mr. Aites had turned as he was walking down the ramp, Mr. Vanderbrook responded, "Well, that's when a lot of accidents occur in the rain." Mr. Vanderbrook then acknowledged that he did not know whether Mr. Aites had turned or walked straight down the ramp in this particular case.
A trial court may accept or reject in whole or in part the pinion expressed by an expert. The effect and weight to be given expert testimony is within the broad discretion of the trial court.Rao v. Rao, 2005-0059 (La. App. 1st Cir. 11/4/05), 927 So. 2d 356, 365, writ denied, 2005-2453 (La. 3/24/06), 925 So. 2d 1232. Moreover, where there is a difference in opinion between experts on a factual matter, it is within the trier of fact's discretion to favor one opinion over another. Guidroz v. State, through Department of Transportation and Development, 94-0253 (La. App. 1st Cir. 12/22/94), 648 So. 2d 1361, 1365. In the instant case, the trial court obviously chose to credit the testimony and opinions of Mr. Gallardo over those of Mr. Vanderbrook, and we cannot conclude that this choice was an abuse of discretion. Moreover, considering the record as a whole, we cannot conclude that the trial court manifestly erred in its determination that Mr. Sanders and State Farm were at fault herein.
State Farm has not challenged on appeal that Mr. Sanders was the owner of the property at issue or that he was responsible for the ramp on which Mr. Aites slipped. Moreover, the record before us amply supports the findings that Mr. Sanders had knowledge of the dangerous condition of the ramp prior to the accident in question and that the condition of the ramp caused Mr. Aites's injuries.
In this assignment of error, State Farm contends that the trial court erred in failing to find that Mr. Aites's negligence contributed to the accident and in failing to assign any fault to Mr. Aites. Specifically, State Farm avers that Mr. Aites's actions in choosing to exit the shop area of the premises by using the metal ramp at a fast pace while holding an umbrella and wearing tennis shoes rendered Mr. Aites wholly or significantly at fault for his own injuries.
A plaintiff's comparative fault must be determined objectively according to the standard of care expected of a reasonable man under like circumstances. Buckbee v. Aweco, Inc., 614 So. 2d 1233, 1237 (La. 1993). In the instant case, Mr. Aites, was sixty-eight years old at the time of trial. He testified that on the day of the accident, the weather was rainy, though it was drizzling and not raining hard. He acknowledged that the ground and the ramp were wet at the time, but stated that the ramp did not appear out of the ordinary.
The record further reveals that when Mr. Noel instructed Mr. Aites to pull his vehicle into the shop or garage area, Mr. Noel motioned toward the garage opening, indicating that Mr. Aites should exit the shop area through the garage opening and down the ramp. Moreover, there was no barrier or rope across the garage door opening to prevent him or any other customer from exiting in that manner. Indeed, Mr. Aites exited the shop by that route, which was the quickest route to retrieve his vehicle.
Regarding the manner in which he proceeded down the ramp, Mr. Aites stated that he was not running, but acknowledged that he was walking down the ramp at a fast pace because it was raining. Mr. Aites was wearing tennis shoes at the time he slipped on the ramp. Despite the fact that he was walking at a fast pace, according to Mr. Aites, he was being careful.
Considering the foregoing and the record as a whole, we must conclude that the trial court committed manifest error in failing to find that Mr. Aites was comparatively at fault, albeit to a much lesser degree, in causing his accident. While a person may have an impulse to walk hurriedly in the rain to minimize getting wet, the rainy conditions on the morning of the accident dictated that Mr. Aites should have walked more slowly than normal, rather than more quickly, while descending a wet, metal ramp with no handrails. Accordingly, the trial court erred in failing to find that Mr. Aites was also at fault and in failing to apportion any fault to him.
After an appellate court finds a "clearly wrong" apportionment of fault, it should adjust the award, but only to the extent of lowering or raising it to the highest or lowest point respectively which is reasonably within the trial court's discretion.Clement v. Frey, 95-1119 (La. 1/16/96), 666 So. 2d 607, 611. Considering the facts established herein in light of the factors set forth in Watson v. State Farm Fire and Casualty Insurance Co., 469 So. 2d 967, 974, which guides us in the apportionment of fault, we assess ten percent fault to Mr. Aites and ninety percent fault to Mr. Sanders and State Farm and amend the trial court's judgment accordingly. See Leonard v. Ryan's Family Steak Houses, Inc., 2005-0775 (La. App. 1st Cir. 6/21/06), 939 So. 2d 401, 411.
In their answer to appeal, Mr. and Mrs. Aites complain that the trial court's awards of general damages were too low. The trier of fact has much discretion in the assessment of damages. LSA-C.C. art. 2324.1. A reviewing court should not set aside an award of general damages unless an analysis of the facts and circumstances reveals an abuse of the factfinder's discretion in setting the award. Smith v. Roussel, 2000-1028 (La. App. 1st Cir. 6/22/01), 809 So. 2d 159, 167. The discretion vested in the trier of fact is great, and even vast, so that an appellate court should rarely disturb an award of general damages. It is only when the award is, in either direction, beyond that which a reasonable trier of fact could assess for the effects of the particular injury, to the particular plaintiff, under the particular circumstances, that the appellate court should increase or reduce the award. Youn v. Maritime Overseas Corporation, 623 So. 2d 1257, 1261 (La. 1993),cert. denied, 510 U.S. 114, 114 S. Ct. 1059, 127 L. Ed. 2d 379 (1994).
Considering the specific facts in this case, we cannot say that the trial court abused its vast discretion in the $25,000.00 general damage award in favor of Mr. Aites or in the $7,500.00 loss of consortium award to Mrs. Aites herein. Accordingly, we find no merit to this argument.
For the above and foregoing reasons, the trial court's March 4, 2009 judgment is hereby amended to assess Mr. Aites with ten percent fault in causing the accident and to, correspondingly, reduce the percentage of fault attributable to State Farm to ninety percent. Accordingly, the judgment is further amended to reduce the awards in favor of Emile Aites and Glenn Aites each by ten percent. In all other respects, the judgment is affirmed. Costs of this appeal are assessed ten percent to Mr. and Mrs. Aites and ninety percent to State Farm.
AMENDED AND, AS AMENDED, AFFIRMED.


Plaintiff, Billie Johnson, will, pursuant to her previously filed Notice of Intent to Move for New Trial, and does hereby, move the Court for an order to vacate and set aside the verdict of the jury and judgment entered pursuant thereto in favor of Defendants and against Plaintiff Johnson, and to grant Plaintiff a new trial on each of her claims against Defendant for professional negligence pursuant to California Code of Civil Procedure §657 and §657.6 in particular.
This motion will be based on this Notice; the evidence presented at trial; all pleadings, papers and records in this action; the minutes of the Court; and this memorandum of points and authorities; and such additional argument as the Court may permit Plaintiffs to present.
A new trial is proper upon a showing that due to procedural or legal error, an issue of fact requires re-examination after trial by jury, court or referee. Civ. Proc. Code §656. The error must result in a miscarriage of justice. Cal. Const. Art. VI, §13. Upon proper showing, the jury’s verdict and subsequent judgment may be vacated … and a new and further trial granted on all or part of the issues, on application of the party aggrieved … Civ. Proc. Code §657.
A new trial may only be granted on certain grounds specified in Section 657, and the determination of a motion for new trial rests solely within the discretion of the trial court. Shaw v. Pacific Greyhound Lines, 50 Cal.2d 153, 159.